Search

We present a spatially resolved X-ray magnetic linear dichroism study of high quality micron-sized mixed nickel-cobalt oxide (NCO) crystals. NixCo1-xO was prepared in-situ by high-temperature oxygen-assisted molecular beam epitaxy on a Ru(0001) single crystal substrate. To check the effect of incorporating Ni into the cobalt oxide films, three different compositions were prepared. The element-specific XMLD measurements reveal strong antiferromagnetic contrast at room temperature and magnetic domains up to one micron in size, reflecting the high structural quality of the NCO islands. By means of vectorial magnetometry, the antiferromagnetic spin axis orientation of the domains was determined with nanometer spatial resolution, and found to depend on the stoichiometry of the prepared crystals.

Helicenes are of general interest due to the significant chiral signals in both absorption- and emission-based spectroscopy. Herein, the spectroscopic properties of four recently synthesized azaoxahelicenes are studied using density functional theory methods. The azaoxahelicenes have 7, 9, 10, and 13 units and one to two complete turns of the structure. UV-vis absorption and electronic circular dichroism spectra are determined both in vacuum and in solution using explicit solvation through a combined molecular dynamics/polarizable embedding framework. Additionally, emission and circularly polarized luminescence spectra are determined based on vibronic calculations. The resulting spectra are in good agreement with the experimentally available data, highlighting that both absorption- and emission-based spectra of the systems can be modeled computationally such that reliable predictions can be made for systems that are yet to be synthesized., QC 20230524

In the novel stoichiometric iron-based material RbEuFe4As4, superconductivity coexists with a peculiar long-range magnetic order of Eu 4f states. Using angle-resolved photoemission spectroscopy, we reveal a complex three-dimensional electronic structure and compare it with density functional theory calculations. Multiple super-conducting gaps were measured on various sheets of the Fermi surface. High-resolution resonant photoemission spectroscopy reveals magnetic order of the Eu 4f states deep into the superconducting phase. Both the absolute values and the anisotropy of the superconducting gaps are remarkably similar to the sibling compound without Eu, indicating that Eu magnetism does not affect the pairing of electrons. A complete decoupling between Fe-and Eu-derived states was established from their evolution with temperature, thus unambiguously demonstrating that superconducting and a long-range magnetic orders exist independently from each other. The established electronic structure of RbEuFe4As4 opens opportunities for the future studies of the highly unorthodox electron pairing and phase competition in this family of iron-based superconductors with doping.

In the novel stoichiometric iron-based material RbEuFe4As4, superconductivity coexists with a peculiar long-range magnetic order of Eu 4f states. Using angle-resolved photoemission spectroscopy, we reveal a complex three-dimensional electronic structure and compare it with density functional theory calculations. Multiple super-conducting gaps were measured on various sheets of the Fermi surface. High-resolution resonant photoemission spectroscopy reveals magnetic order of the Eu 4f states deep into the superconducting phase. Both the absolute values and the anisotropy of the superconducting gaps are remarkably similar to the sibling compound without Eu, indicating that Eu magnetism does not affect the pairing of electrons. A complete decoupling between Fe-and Eu-derived states was established from their evolution with temperature, thus unambiguously demonstrating that superconducting and a long-range magnetic orders exist independently from each other. The established electronic structure of RbEuFe4As4 opens opportunities for the future studies of the highly unorthodox electron pairing and phase competition in this family of iron-based superconductors with doping.

We have investigated the spin and oxidation states of Co in Co3BO5 using x-ray magnetic circular dichroism (XMCD) and dc magnetic susceptibility measurements. At low temperatures, XMCD experiments have been performed at the Co K-edge in Co3BO5 and Co2FeBO5 single crystals in the fully ferrimagnetically ordered phase. The Co (K-edge) XMCD signal is found to be related to the Co2+ magnetic sublattices in both compounds, providing strong experimental support for the low-spin (LS) Co3+ scenario. The paramagnetic susceptibility is highly anisotropic. An estimation of the effective magnetic moment in the temperature range 100-250 K correlates well with two Co2+ ions in the high-spin (HS) state and some orbital contribution, while Co3+ remains in the LS state. The crystal structure of the Co3BO5 single crystal has been solved in detail at the T range 296-703 K. The unit cell parameters and volume show anomalies at 500 and 700 K. The octahedral environment of the Co4 site strongly changes with heating. The generalized gradient approximation with Hubbard U correction calculations have revealed that, at low-temperatures, the system is insulating with a band gap of 1.4 eV, and the Co2+ ions are in the HS state, while Co3+ are in the LS state. At high temperatures (T > 700 K), the charge ordering disappears, and the system becomes metallic with all Co ions in 3d7 electronic configuration and HS state. © 2021 American Physical Society.

In the novel stoichiometric iron-based material RbEuFe4As4, superconductivity coexists with a peculiar long-range magnetic order of Eu 4f states. Using angle-resolved photoemission spectroscopy, we reveal a complex three-dimensional electronic structure and compare it with density functional theory calculations. Multiple super-conducting gaps were measured on various sheets of the Fermi surface. High-resolution resonant photoemission spectroscopy reveals magnetic order of the Eu 4f states deep into the superconducting phase. Both the absolute values and the anisotropy of the superconducting gaps are remarkably similar to the sibling compound without Eu, indicating that Eu magnetism does not affect the pairing of electrons. A complete decoupling between Fe-and Eu-derived states was established from their evolution with temperature, thus unambiguously demonstrating that superconducting and a long-range magnetic orders exist independently from each other. The established electronic structure of RbEuFe4As4 opens opportunities for the future studies of the highly unorthodox electron pairing and phase competition in this family of iron-based superconductors with doping.

Hexagonal manganites, such as h-LuMnO3, are ferroelectric with its polar axis along the hexagonal axis and have a narrow electronic bandgap (≈ 1.5 eV). Using Pt electrodes, h LuMnO3 single crystals display a strong rectification, characteristic of a Schottky diode, and a large photoresponse. It is found that the short circuit photocurrent Jsc along the polar axis is modulated (up to 25 %) by the direction of the ferroelectric polarization P, leading to a short circuit photocurrent loop that mimics the ferroelectric polarization, and by polarization back switching. However, a non-switchable Jsc persists. Diffusion photocurrent is shown to dominate current-in-plane measurements and contributes to the non-switchable Jsc. This observation illustrates the dramatic role of the large optical absorption in hexagonal manganites. The accompanying optical dichroism shall challenge disentangling a genuine bulk photovoltaic response in h-LuMnO3 single crystal contributing to the non-switchable Jsc. Epitaxial thin films may offer a suitable alternative.

Metallic nanoparticles are small particles, with dimensions of less than 100 nm, which have unique characteristics. For example, the color of a nanoparticle solution is given by the surface plasmon resonance, in contrast to only absorbance of a molecule. Metallic nanoparticles have been used in the antiquity for the production of colored glass. Many of the medieval cathedral red windows are in fact, stained with gold nanoparticles. However, presenting just a red solution to a class and explaining that the solution contains gold nanoparticles can be disappointing as the red color can be obtained in many different ways without the need of nanoparticles. Something peculiar, like dichroism, can, on the other hand, shine the interest of an observer to the "nano-world". Dichroic nanoparticles show different colors when illuminated from the front (scattering) or from the back (transmission). This effect is unique for nanoparticles and nanostructures in general and can generate the "WOW"effect in class or during public demonstrations. In this article we present a simple synthesis of dichroic silver and gold nanoparticles. Solutions of such nanoparticles are a stunning visual media for demonstrations, outreach and engaging audience in the "nano"world.

Surface roughness plays an important role in regulating protein adsorption to biomaterial surfaces and modulating the subsequent inflammatory response. In this study, we examined the role of surface nanotopography on albumin adsorption, unfolding and subsequent immune responses. To achieve the objectives of the study, we create model surfaces of hill-like nanoprotrusions by covalently immobilizing gold nanoparticles (AuNPs) of predetermined sizes (16, 38, and 68 nm) on a functional plasma polymer layer. The amount of adsorbed albumin increased with the increase in surface area caused by greater surface nanotopography scales. Circular dichroism spectroscopy was used to evaluate albumin conformational changes and pointed to loss of ?-helical structure on all model surfaces with the greatest conformational changes found on the smooth surface and the surface with largest nanotopography features. Studies with differentiated THP-1 cells (dTHP-1) demonstrated that immune cells interacted with surface adsorbed albumin via their scavenger receptors, which could bind to exposed peptide sequences caused by surface induced unfolding of the albumin. Pre-adsorption of albumin resulted in an overall decrease in the level of expression of pro-inflammatory cytokines from dTHP-1 cells. On the other hand, pre-adsorption of albumin led in an increase in the production of anti-inflammatory markers, which suggests a switch to the M2 pro-healing phenotype. The knowledge obtained from this study could instruct the design of healthcare materials where the generation of targeted surface nanotopography and pre-adsorption of albumin may enhance the biomaterial biocompatibility and lead to faster wound healing. © 2021 The Authors

The Lycurgus cup is an ancient glass artefact that shows dichroism as it looks green when a white light is reflected on it and a red colouring appears when a white light is transmitted through it. This peculiar dichroic effect is due to silver and gold nanoparticles present in the glass. In this research we show the synthesis of dichroic silver nanoparticles and their embedding in a 3D printable nanocomposite. The addition of gold nanoparticles to the silver nanoparticle composite, gave a 3D printable nanocomposite with the same dichroism effect of the Lycurgus cup.

An open-source program named VeloxChem has been developed for the calculation of electronic real and complex linear response functions at the levels of Hartree–Fock and Kohn–Sham density functional theories. With an object-oriented program structure written in a Python/C++ layered fashion, VeloxChem enables time-efficient prototyping of novel scientific approaches without sacrificing computational efficiency, so that molecular systems involving up to and beyond 500 second-row atoms (or some 10,000 contracted and in part diffuse Gaussian basis functions) can be routinely addressed. In addition, VeloxChem is equipped with a polarizable embedding scheme for the treatment of the classical electrostatic interactions with an environment that in turn is modeled by atomic site charges and polarizabilities. The underlying hybrid message passing interface (MPI)/open multiprocessing (OpenMP) parallelization scheme makes VeloxChem suitable for execution in high-performance computing cluster environments, showing even slightly beyond linear scaling for the Fock matrix construction with use of up to 16,384 central processing unit (CPU) cores. An efficient—with respect to convergence rate and overall computational cost—multifrequency/gradient complex linear response equation solver enables calculations not only of conventional spectra, such as visible/ultraviolet/X-ray electronic absorption and circular dichroism spectra, but also time-resolved linear response signals as due to ultra-short weak laser pulses. VeloxChem distributed under the GNU Lesser General Public License version 2.1 (LGPLv2.1) license and made available for download from the homepage https://veloxchem.org. This article is categorized under: Software > Quantum Chemistry Electronic Structure Theory > Density Functional Theory Theoretical and Physical Chemistry > Spectroscopy., QC 20200429

Monolayer VSe2, featuring both charge density wave and magnetism phenomena, represents a unique van der Waals magnet in the family of metallic 2D transition-metal dichalcogenides (2D-TMDs). Herein, by means of in situ microscopy and spectroscopic techniques, including scanning tunneling microscopy/spectroscopy, synchrotron X-ray and angle-resolved photoemission, and X-ray absorption, direct spectroscopic signatures are established, that identify the metallic 1T-phase and vanadium 3d1 electronic configuration in monolayer VSe2 grown on graphite by molecular-beam epitaxy. Element-specific X-ray magnetic circular dichroism, complemented with magnetic susceptibility measurements, further reveals monolayer VSe2 as a frustrated magnet, with its spins exhibiting subtle correlations, albeit in the absence of a long-range magnetic order down to 2 K and up to a 7 T magnetic field. This observation is attributed to the relative stability of the ferromagnetic and antiferromagnetic ground states, arising from its atomic-scale structural features, such as rotational disorders and edges. The results of this study extend the current understanding of metallic 2D-TMDs in the search for exotic low-dimensional quantum phenomena, and stimulate further theoretical and experimental studies on van der Waals monolayer magnets. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Background: Nanotechnology, even if unknowingly, has been used for millennia. The occurrence of shiny colors in pottery and glass made hundreds and thousand of years ago is due to the presence of nanoparticles in the fabrication of such ornaments. In the last decade, 3D printing has revolutionized fabrication and manufacturing processes, making it easier to produce, in a simple and fast way, 3D objects. Results: In this paper we show how to fabricate a 3D-printable nanocomposite composed of dichroic gold nanoparticles and a 3D-printable polymer. The minute amount of gold nanoparticles used for obtaining the dichroic effect does not influence the mechanical properties of the polymer nor its printability. Thus, the nanocomposite can be easily 3D-printed using a standard 3D printer and shows a purple color in transmission and a brownish color in reflection. Conclusion: This methodology can be used not only by artists, but also for studying the optical properties of nanoparticles or, for example, for the 3D fabrication of optical filters.

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., Export Date: 9 May 2018; Article; CODEN: RSINA; Correspondence Address: Müller, L.; Deutsches Elektronen-Synchrotron DESY, FS-CXSGermany; email: Leonard.Mueller@desy.de; Funding details: SFB 925, DFG, California Department of Fish and Game; Funding details: A3, DFG, California Department of Fish and Game; Funding details: B3, DFG, California Department of Fish and Game; Funding details: B2, DFG, California Department of Fish and Game; Funding details: Knut och Alice Wallenbergs Stiftelse; Funding text: Financial support by DFG within SFB 925, projects B3, A3, and B2 is gratefully acknowledged. M.H.B. acknowledges support from the Knut and Alice Wallenberg foundation. QC 20180529

A terpyridine- and guanine-functionalized peptide was developed that could form different morphologies by self-assembly or coordination with Fe2+ in dimethyl sulfoxide. The self-assembly of the peptide is attributed to the G-quartet formation of a guanine moiety and intermolecular terpyridine π-π stacking. Upon the addition of Fe2+, a Fe2+-(terpyridine)2 complex is formed that turns the square-planar self-assembly to a three-dimensional self-assembly. As a consequence, a variety of interesting morphologies and chemical properties were observed. The self-assembled polymers were studied by nuclear magnetic resonance spectroscopy, ultraviolet-visible and fluorescence spectroscopy, viscosity measurement, circular dichroism, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, dynamic light scattering, and atomic force microscopy. This external stimuli driven self-assembly of a peptide may be further applied to drug delivery applications., Export Date: 13 February 2018; Article; Correspondence Address: Wu, J.; Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and TechnologyChina; email: jcwu@ecust.edu.cn; Funding details: CSC, China Scholarship Council; Funding details: 21778017; Funding details: 91529101; Funding details: 21572057. QC 20180227

The magnetic anisotropy and exchange coupling between spins localized at the positions of 3d transition metal atoms forming two-dimensional metal-organic coordination networks (MOCNs) grown on a Au(111) metal surface are studied. In particular, we consider MOCNs made of Ni or Mn metal centers linked by 7,7,8,8-tetracyanoquinodimethane (TCNQ) organic ligands, which form rectangular networks with 1: 1 stoichiometry. Based on the analysis of X-ray magnetic circular dichroism (XMCD) data taken at T = 2.5 K, we find that Ni atoms in the Ni-TCNQ MOCNs are coupled ferromagnetically and do not show any significant magnetic anisotropy, while Mn atoms in the Mn-TCNQ MOCNs are coupled antiferromagnetically and do show a weak magnetic anisotropy with in-plane magnetization. We explain these observations using both a model Hamiltonian based on mean-field Weiss theory and density functional theory calculations that include spin-orbit coupling. Our main conclusion is that the antiferromagnetic coupling between Mn spins and the in-plane magnetization of the Mn spins can be explained by neglecting effects due to the presence of the Au(111) surface, while for Ni-TCNQ the metal surface plays a role in determining the absence of magnetic anisotropy in the system.

A study of the initial stages of crystallization in RF magnetron-sputtered ferrite garnet films is reported, in which a series of ultrathin Bi2Dy1Fe4Ga1O12 layers is fabricated and characterized. The spectral and temperature dependencies of magnetic circular dichroism (MCD) of these films are studied in the temperature range from 300 K down to 8 K. Measured magneto-optical properties are reported in the spectral range between 300 and 600 nm. In ultrathin garnets at temperatures below 160 K, we found that between 360 and 520 nm, the spectral MCD dependencies were typical of bismuth-substituted garnets with high levels of gallium dilution in the tetrahedral sublattice. The MCD signal strength measured at its 440 nm peak grows linearly with reducing temperature between 160 K and 8 K. This observed temperature dependency of MCD differed dramatically from these measured in thicker (3.7 nm) nanocrystalline garnet films. The peak MCD signal at 440 nm in these 3.7 nm-thick samples grows linearly from 215 K down to 100 K, resembling the same dependency seen in 1.7 nm films. In thinnest layers of thickness 0.6 nm, no MCD signals were observed at any temperature in the range between 8 and 300 K.

This thesis is about the multicolored gradients seen when using certain dichroic color lters with artificial light. As of now, this phenomenon lacks a unambiguous descriptor, and “Goniochromatic Gradient” is proposed. With help of optical physics, the science of color vision and information about dichroic products, principles for the relationship between goniochromatic gradients and dichroic filters are formulated for anyone interested in exploring this visual phenomenon.

The magnetic anisotropy and exchange coupling between spins localized at the positions of 3d transition metal atoms forming two-dimensional metal-organic coordination networks (MOCNs) grown on a Au(111) metal surface are studied. In particular, we consider MOCNs made of Ni or Mn metal centers linked by 7,7,8,8-tetracyanoquinodimethane (TCNQ) organic ligands, which form rectangular networks with 1: 1 stoichiometry. Based on the analysis of X-ray magnetic circular dichroism (XMCD) data taken at T = 2.5 K, we find that Ni atoms in the Ni-TCNQ MOCNs are coupled ferromagnetically and do not show any significant magnetic anisotropy, while Mn atoms in the Mn-TCNQ MOCNs are coupled antiferromagnetically and do show a weak magnetic anisotropy with in-plane magnetization. We explain these observations using both a model Hamiltonian based on mean-field Weiss theory and density functional theory calculations that include spin-orbit coupling. Our main conclusion is that the antiferromagnetic coupling between Mn spins and the in-plane magnetization of the Mn spins can be explained by neglecting effects due to the presence of the Au(111) surface, while for Ni-TCNQ the metal surface plays a role in determining the absence of magnetic anisotropy in the system.

This thesis is about the multicolored gradients seen when using certain dichroic color lters with artificial light. As of now, this phenomenon lacks a unambiguous descriptor, and “Goniochromatic Gradient” is proposed. With help of optical physics, the science of color vision and information about dichroic products, principles for the relationship between goniochromatic gradients and dichroic filters are formulated for anyone interested in exploring this visual phenomenon.

Microgels are interesting as potential delivery systems for antimicrobial peptides. In order to elucidate membrane interactions of such systems, we here investigate effects of microgel charge density on antimicrobial peptide loading and release, as well as consequences of this for membrane interactions and antimicrobial effects, using ellipsometry, circular dichroism spectroscopy, nanoparticle tracking analysis, dynamic light scattering and z-potential measurements. Anionic poly(ethyl acrylate-co-methacrylic acid) microgels were found to incorporate considerable amounts of the cationic antimicrobial peptides LL-37 (LLGDFFRKSKEKIGKEFKRIVQRIKDFLRNLVPRTES) and DPK-060 (GKHKNKGKKNGKHNGWKWWW) and to protect incorporated peptides from degradation by infection-related proteases at high microgel charge density. As a result of their net negative z-potential also at high peptide loading, neither empty nor peptide-loaded microgels adsorb at supported bacteria-mimicking membranes. Instead, membrane disruption is mediated almost exclusively by peptide release. Mirroring this, antimicrobial effects against several clinically relevant bacteria (methicillin-resistant Staphylococcus aureus (MRSA), Escherichia coli, and Pseudomonas aeruginosa) were found to be promoted by factors facilitating peptide release, such as decreasing peptide length and decreasing microgel charge density. Microgels were further demonstrated to display low toxicity towards erythrocytes. Taken together, the results demonstrate some interesting opportunities for the use of microgels as delivery systems for antimicrobial peptides, but also highlight several key factors which need to be controlled for their successful use., QC 20180327

A study of the initial stages of crystallization in RF magnetron-sputtered ferrite garnet films is reported, in which a series of ultrathin Bi2Dy1Fe4Ga1O12 layers is fabricated and characterized. The spectral and temperature dependencies of magnetic circular dichroism (MCD) of these films are studied in the temperature range from 300 K down to 8 K. Measured magneto-optical properties are reported in the spectral range between 300 and 600 nm. In ultrathin garnets at temperatures below 160 K, we found that between 360 and 520 nm, the spectral MCD dependencies were typical of bismuth-substituted garnets with high levels of gallium dilution in the tetrahedral sublattice. The MCD signal strength measured at its 440 nm peak grows linearly with reducing temperature between 160 K and 8 K. This observed temperature dependency of MCD differed dramatically from these measured in thicker (3.7 nm) nanocrystalline garnet films. The peak MCD signal at 440 nm in these 3.7 nm-thick samples grows linearly from 215 K down to 100 K, resembling the same dependency seen in 1.7 nm films. In thinnest layers of thickness 0.6 nm, no MCD signals were observed at any temperature in the range between 8 and 300 K.

The magnetic anisotropy and exchange coupling between spins localized at the positions of 3d transition metal atoms forming two-dimensional metal-organic coordination networks (MOCNs) grown on a Au(111) metal surface are studied. In particular, we consider MOCNs made of Ni or Mn metal centers linked by 7,7,8,8-tetracyanoquinodimethane (TCNQ) organic ligands, which form rectangular networks with 1: 1 stoichiometry. Based on the analysis of X-ray magnetic circular dichroism (XMCD) data taken at T = 2.5 K, we find that Ni atoms in the Ni-TCNQ MOCNs are coupled ferromagnetically and do not show any significant magnetic anisotropy, while Mn atoms in the Mn-TCNQ MOCNs are coupled antiferromagnetically and do show a weak magnetic anisotropy with in-plane magnetization. We explain these observations using both a model Hamiltonian based on mean-field Weiss theory and density functional theory calculations that include spin-orbit coupling. Our main conclusion is that the antiferromagnetic coupling between Mn spins and the in-plane magnetization of the Mn spins can be explained by neglecting effects due to the presence of the Au(111) surface, while for Ni-TCNQ the metal surface plays a role in determining the absence of magnetic anisotropy in the system.

Tetragonally strained interstitial Fe-Co-B alloys were synthesized as epitaxial films grown on a 20 nm thick Au0.55Cu0.45 buffer layer. Different ratios of the perpendicular to in-plane lattice constant c/a = 1.013, 1.034 and 1.02 were stabilized by adding interstitial boron with different concentrations 0, 4, and 10 at.%, respectively. Using ferromagnetic resonance (FMR) and x-ray magnetic circular dichroism (XMCD) we found that the total orbital magnetic moment significantly increases with increasing c/a ratio, indicating that reduced crystal symmetry and interstitial B leads to a noticeable enhancement of the effect of spin-orbit coupling (SOC) in the Fe-Co-B alloys. First-principles calculations reveal that the increase in orbital magnetic moment mainly originates from B impurities in octahedral position and the reduced symmetry around B atoms. These findings offer the possibility to enhance SOC phenomena - namely the magnetocrystalline anisotropy and the orbital moment - by stabilizing anisotropic strain by doping 4 at.% B. Results on the influence of B doping on the Fe-Co film microstructure, their coercive field and magnetic relaxation are also presented.

The epitaxial growth of cubic BiFeO3 ultrathin films on SrTiO3 (001) substrates by off-axis RF sputtering is demonstrated, suitable to X-ray spectroscopies interface investigation. X-ray photoelectron diffraction is used as a tool to probe the long-range crystal order and to track the transition from amorphous to epitaxial growth as a function of deposition parameters. Further spectroscopic measurements, in particular, X-ray linear dichroism on the Fe L 3, 2 edge, confirm the heteroepitaxial growth of BiFeO3 and clearly indicate a 3+ valence state for the iron cation. Finally, XPS is used to reconstruct the band alignment diagram, which results in a staggered configuration with a remarkable energy shift of the SrTiO3 band edges which can ultimately favor the n-type doping of SrTiO3.

The chiral nonanuclear Tb(III) clusters [Tb-9(sal-(R)-Bt)(16)(mu-OH)(10)]+[NO3]-(Tb-(R)-Bt: sal-(R)-Bt=(R)-2-butyl salicylate) and [Tb9 (sal-(S)-Bt)(16)(mu-OH)(10)](+)[NO3](-)(Tb-(S)-Bt: sal-(S)-Bt=(S)-2-butyl salicylate) were found to exhibit a unique magneto-optical property: the Faraday effect. The clusters were composed of 9 Tb(III) ions bridged by 10 mu-OHs and 16 chiral salicylic acid esters. The Faraday rotation angle of Tb-(R)-Bt was greater than that of Tb-(S)-Bt, indicating that the Faraday effect was affected by the chirality of the Tb(III) clusters. The chiroptical properties of the Tb(III) clusters were estimated using circular dichroism and circularly polarized luminescence. In this study, a new finding concerning chiral magneto-optical properties was investigated.

The chiral nonanuclear Tb(III) clusters [Tb-9(sal-(R)-Bt)(16)(mu-OH)(10)]+[NO3]-(Tb-(R)-Bt: sal-(R)-Bt=(R)-2-butyl salicylate) and [Tb9 (sal-(S)-Bt)(16)(mu-OH)(10)](+)[NO3](-)(Tb-(S)-Bt: sal-(S)-Bt=(S)-2-butyl salicylate) were found to exhibit a unique magneto-optical property: the Faraday effect. The clusters were composed of 9 Tb(III) ions bridged by 10 mu-OHs and 16 chiral salicylic acid esters. The Faraday rotation angle of Tb-(R)-Bt was greater than that of Tb-(S)-Bt, indicating that the Faraday effect was affected by the chirality of the Tb(III) clusters. The chiroptical properties of the Tb(III) clusters were estimated using circular dichroism and circularly polarized luminescence. In this study, a new finding concerning chiral magneto-optical properties was investigated.

A successful elucidation of the near-ultraviolet electronic circular dichroism spectrum of a short double-stranded DNA is reported. Time-dependent density functional theory methods are shown to accurately predict spectra and assign bands on the microscopic base-pair scale, a finding that opens the field for using circular dichroism spectroscopy as a sensitive nanoscale probe of DNA to reveal its complex interactions with the environment. (Chemical Equation Presented)., QC 20240110

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. © 2015 American Chemical Society., References: Mason, W.R., (2007) A Practical Guide to Magnetic Circular Dichroism Spectroscopy, , Wiley: New York; Voelter, W., Records, R., Bunnenberg, E., Djerassi, C., Magnetic Circular Dichroism Studies. VI. Investigation of Some Purines, Pyrimidines, and Nucleosides (1968) J. Am. Chem. Soc., 90, p. 6163; Djerassi, C., Bunnenberg, E., Elder, D.L., Organic Chemical Applications of Magnetic Circular Dichroism (1971) Pure Appl. Chem., 25, pp. 57-90; Coriani, S., Jørgensen, P., Ruud, K., Rizzo, A., Olsen, J., Ab Initio Determinations of Magnetic Circular Dichroism (1999) Chem. Phys. Lett., 300, pp. 61-68; Coriani, S., Hättig, C., Jørgensen, P., Helgaker, T., Gauge-Origin Independent Magneto-Optical Activity within Coupled Cluster Response Theory (2000) J. Chem. Phys., 113, pp. 3561-3572; Kjærgaard, T., Jansik, B., Jørgensen, P., Coriani, S., Michl, J., Gauge-Origin-Independent Coupled Cluster Singles and Doubles Calculation of Magnetic Circular Dichroism of Azabenzenes and Phosphabenzene using London Orbitals (2007) J. Phys. Chem. A, 111, pp. 11278-11286; Seth, M., Ziegler, T., Banerjee, A., Autschbach, J., Van Gisbergen, S.J.A., Baerends, E.J., Calculation of the A Term of Magnetic Circular Dichroism Based on Time Dependent-Density Functional Theory I. Formulation and Implementation (2004) J. Chem. Phys., 120, pp. 10942-10954; Seth, M., Ziegler, T., Autschbach, J., Ab Initio Calculation of the C/D Ratio of Magnetic Circular Dichroism (2005) J. Chem. Phys., 122, p. 094112; Seth, M., Ziegler, T., Calculation of the B term of Magnetic Circular Dichroism. A Time-Dependent Density Functional Approach (2007) J. Chem. Theory Comput., 3, pp. 434-447; Seth, M., Ziegler, T., Calculation of Magnetic Circular Dichroism Spectra with Time-Dependent Density Functional Theory (2010) Adv. Inorg. Chem., 62, pp. 41-109; Solheim, H., Frediani, L., Ruud, K., Coriani, S., An IEF-PCM Study of Solvent Effects on the Faraday B Term of MCD (2008) Theor. Chem. Acc., 119, pp. 231-244; Solhe

A series of chiral synthetic compounds is reported that shows intricate but specific hierarchical assembly because of varying positions of coordination and hydrogen bonds. The evolution of the aggregates (followed by absorption spectroscopy and temperature-dependent circular dichroism studies in solution) reveal the influence of the proportion of stereogenic centers in the side groups connected to the chromophore ring in their optical activity and the important role of pyridyl groups in the self-assembly of these chiral macrocycles. The optical activity spans 2 orders of magnitude depending on composition and constitution. Two of the aggregates show very high optical activity even though the isolated chromophores barely give a circular dichroism signal. Molecular modeling of the aggregates, starting from the pyridine-zinc(II) porphyrin interaction and working up, and calculation of the circular dichroism signal confirm the origin of this optical activity as the chiral supramolecular organization of the molecules. The aggregates show a broad absorption range, between approximately 390 and 475 nm for the transitions associated with the Soret region alone, that spans wavelengths far more than the isolated chromophore. The supramolecular assemblies of the metalloporphyrins in solution were deposited onto highly oriented pyrolitic graphite in order to study their hierarchy in assembly by atomic force microscopy. Zero and one-dimensional aggregates were observed, and a clear dependence on deposition temperature was shown, indicating that the hierarchical assembly took place largely in solution. Moreover, scanning electron microscopy images of porphyrins and metalloporphyrins precipitated under out-of-equilibrium conditions showed the dependence of the number and position of chiral amide groups in the formation of a fibrillar nanomaterial. The combination of coordination and hydrogen bonding in the complicated assembly of these molecules-where there is a clear hierarchy fo, QC 20161222

We herein report the synthesis and characterization of ABC-type triblock copolymers containing two complementary association motifs and investigate their folding into well-defined polymeric nanoparticles under diluted conditions via intramolecular orthogonal hydrogen bonding. The precursor ABC-type triblock copolymers are prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization bearing primary alkyl bromide on A, protected alkyne on B, and protected hydroxyl pendant groups on the C units. The dithioester groups of the RAFT polymers are quantitatively removed by radical-induced reduction before the side-chain functionalization. The complementary motifs, i.e., Hamilton wedge (HW, A block), benzene-1,3,5-tricarboxamide (BTA, B block), and cyanuric acid (CA, C block), are incorporated into the linear triblock copolymers side chains via postfunctionalization. The self-assembly processes of the HW and CA supramolecular motifs are followed by nuclear magnetic resonance (1H NMR) spectroscopy at ambient and elevated temperature in various solvents. The helical BTA stack formation is monitored by circular dichroism (CD) spectroscopy. In addition, the final aggregates formed by these two orthogonal forces, namely HW-CA pseudo-cross-linking and BTA stacking, are characterized by static and dynamic light scattering (SLS and DLS) as well as atomic force microscopy (AFM). © 2015 American Chemical Society.

As part of a program of preparing metal complexes which exhibit unique affinities towards different DNA structures, we have synthesised the novel Schiff base complex N,N'-bis-4-(hydroxysalicylidine)meso-diphenylethylenediaminenickel(ii) (), via the reaction of meso-1,2-diphenylethylenediamine and 2,4-dihydroxybenzaldehyde. This compound was subsequently reacted with 1-(2-chloroethyl)piperidine or 1-(2-chloropropyl)piperidine, to afford the alkylated complexes N,N'-bis-(4-((1-(2-ethyl)piperidine)oxy)salicylidine)meso-1,2-diphenylethylenediaminenickel(ii) () and N,N'-bis-(4-((1-(3-propyl)piperidine)oxy)-salicylidine)meso-1,2-diphenylethylenediaminenickel(ii) (), respectively. These complexes were characterised by microanalysis and X-ray crystallography in the solid state, and in solution by (1)H and (13)C NMR spectroscopy. Electrospray ionisation mass spectrometry (ESI-MS) was used to confirm the identity of () and (). The affinities of () and () towards a discrete 16 mer duplex DNA molecule, and examples of both tetramolecular and unimolecular DNA quadruplexes, was explored using a variety of techniques. In addition, the affinity of two other complexes () and (), towards the same DNA molecules was examined. Complexes () and () were prepared by methods analogous to those which afforded () and (), however 1,2-phenylenediamine was used instead of meso-1,2-diphenylethylenediamine in the initial step of the synthetic procedure. The results of ESI-MS and DNA melting temperature measurements suggest that () and () exhibit a lower affinity than () and () towards the 16 mer duplex DNA molecule, while circular dichroism (CD) spectroscopy suggested that none of the four complexes had a major effect on the conformation of the nucleic acid. In contrast, ESI-MS and CD spectroscopy suggested that both () and () show significant binding to a tetramolecular DNA quadruplex. The results of ESI-MS and Fluorescence Resonance Energy Transfer (FRET) assays indicated that () and () did not

We have measured the effect of the temperature on the polarization-resolved characteristics of a 1550-nm singletransverse mode vertical-cavity surface-emitting laser (VCSEL). Two double polarization switchings (PS) are observed. For low temperatures a PS from longer to shorter wavelengths (Type II PS) followed by the opposite PS (Type I) is observed. For higher temperatures Type I followed by Type II PS are measured. A simple expression relating the spin flip rateto the dichroism, differential gain, threshold current and PS current is derived. With this expression the dependence of the spin-flip rate on the temperature is obtained.

The X-ray absorption spectra of actinides are discussed with an emphasis on the fundamental effects that influence their spectral shape, including atomic multiplet theory, charge transfer theory and crystal field theory. Many actinide spectra consist of a single peak and it is shown that the use of resonant inelastic X-ray emission spectra (RIXS) has the potential to reveal many new features in the X-ray absorption spectra of actinides. The new range of RIXS beamlines will allow the determination of new structures in the X-ray absorption spectra that have been hitherto invisible. This has the potential to become an important tool in the determination of the electronic structure of actinides.

A spherical tensor expansion is carried out to express the resonant inelastic scattering cross-section as a sum of products of fundamental spectra with tensors involving wavevectors and polarization vectors of incident and scattered photons. The expression presented in this paper differs from that of the influential article by Carra et al. (Phys. Rev. Lett. 74, 3700, 1995) because it does not omit interference terms between electric dipole and quadrupole contributions when coupling each photon to itself. Some specific cases of the spherical tensor expansion are discussed. For example the case of isotropic samples is considered and the cross-section is expressed as a combination of only three fundamental spectra for the situation where electric dipole or electric quadrupole transitions in the absorption process are followed by electric dipole transitions in the emission. This situation includes the case of untextured powder samples, which corresponds to the most frequent situation met experimentally. Finally, it is predicted that some circular dichroism may be observed on isotropic samples provided that the circular polarization of the scattered beam can be detected.

This study was designed to understand the role and implications of MUC16 cytoplasmic tail in breast cancer pathogenesis. We would like to update our findings with respect to it since our last report submission. One important question towards this end was whether MUC16 indeed undergoes cleavage, which was addressed using a dual-epitope tagging (N-ter FLAG and C-ter HA). We demonstrated that cleavage of MUC16 could be taking place in the membrane proximal region (twelve amino acids), however deletion of these twelve amino acids partially abrogated the cleavage. Further, Circular Dichroism (CD spectra) analysis using the bacterially purified protein showed an increased alpha helical nature of the protein at acidic pH (5.8). In addition, we demonstrate that the cellular location for the cleavage is Golgi apparatus and the acidic pH in the Golgi is critical for the cleavage. We therefore believe that structural changes brought about by the acidic pH in the Golgi is probably the major reason for the cleavage of MUC16 C-ter and this could be auto-proteolytic in nature. Besides, we verified our preliminary observation of N-glycosylation using site directed mutagenesis approach and we demonstrate that MUC16 C-ter undergoes N-glycosylation and this is critical for the stability of the protein. Here we have demonstrated that, MUC16 C-ter undergoes pH dependent cleavage in the Golgi apparatus and it takes place in the membrane proximal region of the protein. It undergoes Ubiquitylation and N-glycosylation, which are required for its stability. We are furthering our studies to understand the functional and mechanistic insight into its role in cancer pathogenesis., The original document contains color images.

We report the observation of the dichroism effect in simple wire grid structures made of graphite on a paper substrate, i.e. we investigate the feasibility of drawing polarizers for the THz band using conventional graphite-based lead pencils. The displacement of the maximum frequency of the selective absorption phenomenon by varying the wire pitch hints at a polarizing behavior. Measurements of the maximum and minimum of transmission efficiency, extinction ratio and degree of polarization are carried out with a transmission fiber THz-TDS setup. Experimental results show a 9 dB extinction ratio for an inexpensive (<1$) home-made component. (C) 2014 Optical Society of America

We report the observation of the dichroism effect in simple wire grid structures made of graphite on a paper substrate, i.e. we investigate the feasibility of drawing polarizers for the THz band using conventional graphite-based lead pencils. The displacement of the maximum frequency of the selective absorption phenomenon by varying the wire pitch hints at a polarizing behavior. Measurements of the maximum and minimum of transmission efficiency, extinction ratio and degree of polarization are carried out with a transmission fiber THz-TDS setup. Experimental results show a 9 dB extinction ratio for an inexpensive (<1$) home-made component. (C) 2014 Optical Society of America

Motivated by recent experiments on circular dichroism in the photoelectron momentum distributions from strong-field ionization of chiral molecules [C. Lux, Angew. Chem. Int. Ed. 51, 5001 (2012)1433-785110.1002/anie.201109035; C. S. Lehmann, J. Chem. Phys. 139, 234307 (2013)JCPSA60021-960610.1063/1.4844295], we investigate the origin of this effect theoretically. We show that it is not possible to describe photoelectron circular dichroism with the commonly used strong-field approximation due to its plane-wave nature. We therefore apply the Born approximation to the scattering state and use this as a continuum-state correction in the strong-field approximation. We obtain electron distributions for the molecules camphor and fenchone. In order to gain physical insight into the process, we study the contributions of individual molecular orientations. © 2014 American Physical Society.

The temperature-dependent 1s2p resonant inelastic X-ray scattering (RIXS) spectra of CoO have been measured with 0.3 eV overall resolution, and the RIXS planes have been analyzed with multiplet calculations. The analysis of the high-resolution 1s2p RIXS plane allows a more detailed determination of the ground-state electronic structure, as compared to Is X-ray absorption spectroscopy (XAS). The apparent absence of interference effects suggests that the lifetime broadening of the pre-edge states is (significantly) reduced from the edge lifetime broadening. The temperature-dependent RIXS planes are explained as a combination of the ground state and first excited state due to thermal population of the excited state, which are a result of the symmetry distortion, 3d spin orbit coupling, and magnetic exchange interactions. No features due to charge transfer and nonlocal transitions are observed due to the relatively small cobalt oxygen overlap as compared to higher valent systems. The successful determination of the spin state and crystal field parameters using hard X-ray experiments promises to make 1s2p RIXS a useful technique for in situ transition metal oxide studies.

Vitetta and colleagues identified and characterized a putative vascular leak peptide (VLP) consensus sequence in recombinant ricin toxin A-chain (RTA) that contributed to dose-limiting human toxicity when RTA was administered intravenously in large quantities during chemotherapy. We disrupted this potentially toxic site within the more stable RTA1-33/44-198 vaccine immunogen and determined the impact of these mutations on protein stability, structure and protective immunogenicity using an experimental intranasal ricin challenge model in BALB/c mice to determine if the mutations were compatible. Single amino acid substitutions at the positions corresponding with RTA D75 (to A, or N) and V76 (to I, or M) had minor effects on the apparent protein melting temperature of RTA1-33/44-198 but all four variants retained greater apparent stability than the parent RTA. Moreover, each VLP( ) variant tested provided protection comparable with that of RTA1-33/44-198 against supralethal intranasal ricin challenge as judged by animal survival and several biomarkers. To understand better how VLP substitutions and mutations near the VLP site impact epitope structure, we introduced a previously described thermal stabilizing disulfide bond (R48C/T77C) along with the D75N or V76I substitutions in RTA1-33/44-198. The D75N mutation was compatible with the adjacent stabilizing R48C/T77C disulfide bond and the Tm was unaffected, whereas the V76I mutation was less compatible with the adjacent disulfide bond involving C77. A crystal structure of the RTA1-33/44-198 R48C/T77C/D75N variant showed that the structural integrity of the immunogen was largely conserved and that a stable immunogen could be produced from E. coli. We conclude that it is feasible to disrupt the VLP site in RTA1-33/44-198 with little or no impact on apparent protein stability or protective efficacy in mice and such variants can be stabilized further by introduction of a disulfide bond., Published in Toxins, v5 p224-248, 29 Jan 2013. The original document contains color images. Sponsored in part by DoD and DTRA. Prepared in collaboration with the United States Army Medical Research Institute of Infectious Diseases, Frederick, MD, Walter Reed Army Institute of Research, Silver Spring, MD, and the Naval Research Laboratory, Washington, D.C. Prepared in cooperation with NOVA Research, Inc., Alexandria, VA.

We present a systematic computational study of circular intensity difference (CID) in electric-field-induced second harmonic generation (EFISHG) of some representative chiral natural amino acids (Alanine, Arginine, Aspartic Acid, Cysteine and Tryptophan), taking into account the electric-dipole, electric-quadrupole and magnetic-dipole interactions. The calculations are performed by applying cubic response theory at both Hartree-Fock and Density Functional theory levels, the latter with the popular Becke-three parameters, Lee, Yang and Parr (B3LYP) functional. Special focus is given to the basis set, electron correlation and origin dependence of the properties. The full set of molecular parameters defined by Lam and Thirunamachandran in their reference theoretical paper published in 1982 [J. Chem. Phys., 1982, 77, 3810] is obtained and discussed. This permits the prediction of the CID observable for different possible experimental setups., QC 20220126

Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of IOP Publishing for personal use, not for redistribution. The definitive version was published in Journal of Optics 15 (2013): 094007, doi:10.1088/2040-8978/15/9/094007., Polarized light microscopy provides unique opportunities for analyzing the molecular order in manmade and natural materials, including biological structures inside living cells, tissues, and whole organisms. 20 years ago, the LC-PolScope was introduced as a modern version of the traditional polarizing microscope enhanced by liquid crystal devices for the control of polarization, and by electronic imaging and digital image processing for fast and comprehensive image acquisition and analysis. The LCPolScope is commonly used for birefringence imaging, analyzing the spatial and temporal variations of the differential phase delay in ordered and transparent materials. Here we describe an alternative use of the LC-PolScope for imaging the polarization dependent transmittance of dichroic materials. We explain the minor changes needed to convert the instrument between the two imaging modes, discuss the relationship between the quantities measured with either instrument, and touch on the physical connection between refractive index, birefringence, transmittance, diattenuation, and dichroism., This work was supported by a fellowship of the Human Frontiers Science Program awarded to SM and a grant from the National Institute of Biomedical Imaging and Bioengineering (grant Nr. R01EB002045) awarded to RO. MS acknowledges support from the National Institute of General Medical Sciences/NIH (grant R01-GM101701)., 2014-09-10

Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of IOP Publishing for personal use, not for redistribution. The definitive version was published in Journal of Optics 15 (2013): 094007, doi:10.1088/2040-8978/15/9/094007., Polarized light microscopy provides unique opportunities for analyzing the molecular order in manmade and natural materials, including biological structures inside living cells, tissues, and whole organisms. 20 years ago, the LC-PolScope was introduced as a modern version of the traditional polarizing microscope enhanced by liquid crystal devices for the control of polarization, and by electronic imaging and digital image processing for fast and comprehensive image acquisition and analysis. The LCPolScope is commonly used for birefringence imaging, analyzing the spatial and temporal variations of the differential phase delay in ordered and transparent materials. Here we describe an alternative use of the LC-PolScope for imaging the polarization dependent transmittance of dichroic materials. We explain the minor changes needed to convert the instrument between the two imaging modes, discuss the relationship between the quantities measured with either instrument, and touch on the physical connection between refractive index, birefringence, transmittance, diattenuation, and dichroism., This work was supported by a fellowship of the Human Frontiers Science Program awarded to SM and a grant from the National Institute of Biomedical Imaging and Bioengineering (grant Nr. R01EB002045) awarded to RO. MS acknowledges support from the National Institute of General Medical Sciences/NIH (grant R01-GM101701)., 2014-09-10

We demonstrate numerically and experimentally a conjugated gammadion chiral metamaterial that uniaxially exhibits huge optical activity and circular dichroism, and gives a negative refractive index. This chiral design provides smaller unit cell size and larger chirality compared with other published planar designs. Experiments are performed at GHz frequencies (around 6 GHz) and are in good agreement with the numerical simulations., The original document contains color images. Prepared in cooperation with Intelligent Fusion Technology, Inc., Germantown, MD.

Fast folding techniques use optical spectroscopic tools to monitor protein folding or unfolding dynamics after a fast triggering such as the laser induced temperature jump. These techniques have greatly improved time resolution of experiments and provide new opportunities for comparison between theory and simulations. However, the direct comparison is still difficult due to two main challenges: a gap between folding relevant timescales (microseconds or above) and length of molecular dynamics simulations (typically tens to hundreds of nanoseconds), and difficulty in directly calculating spectroscopic observables from simulation configurations. This review is focused on recent advances in addressing these two challenges. We describe new methodology that allows simulating folding timescales with an emphasis on Markov State Models. We also review progress on modeling infrared, circular dichroism, and fluorescence spectroscopic signals from protein conformations. At last, we discuss a few studies that directly simulate time-resolved spectroscopy of temperature jump induced unfolding dynamics for a few small proteins. These studies not only provide direct validation of theoretical models, but also greatly improve our understanding of protein folding mechanisms by connecting ensemble averaged spectroscopic observables with atomistic protein conformations.