Experimental study of bremsstrahlung and characteristic radiation spectra from laser targets irradiated with ultrashort laser pulses with intensities of up to ∼1019 W/cm2

Results from experimental studies of bremsstrahlung and characteristic radiation spectra from laser targets irradiated with ultrashort laser pulses with intensities of up to ～10¹⁹ W/cm² are presented. The continuous spectra of hard X-ray emission from Ta and Al targets and the line spectrum of copper were measured. The temperature of fast electrons was obtained from the measured hard X-ray spectra, and the K_α radiation yield from Ta was measured. The energy conversion efficiency of laser radiation into the copper characteristic radiation was obtained from the measured yield of K_α radiation.     

Diagnostics of plasma produced by femtosecond laser pulse impact upon a target with an internal nanostructure

X-ray diagnostics of the interaction of femtosecond laser pulses with intensities of 10¹⁶–10¹⁸ W/cm² with CO₂ clusters and frozen nanosize water particles is carried out. The stage of cluster expansion and the formation of a plasma channel, which governs the parameters of the formed X-ray radiation source and accelerated ion flows, is studied. The measurements are based on recording spatially resolved X-ray spectra of H- and He-like oxygen ions. Utilization of Rydberg transitions for spectra diagnostics makes it possible to determine plasma parameters on a time scale of t ∼ 10 ps after the beginning of a femtosecond pulse. The role of the rear edge of the laser pulse in sustaining the plasma temperature at a level of ∼100 eV in the stage of a nonadiabatic cluster expansion is shown. The analysis of the profiles and relative intensities of spectral lines allows one to determine the temperature and density of plasma electrons and distinguish the populations of “thermal” ions and ions that are accelerated up to energies of a few tens of kiloelectronvolts. It is shown that the use of solid clusters made of frozen nanoscale water droplets as targets leads to a substantial increase in the number of fast He-like ions. In this case, however, the efficiency of acceleration of H-like ions does not increase, because the time of their ionization in plasma exceeds the time of cluster expansion.     

Experimental and theoretical studies of the physical processes occurring in thin plane targets irradiated by intense X-ray pulses

Results are presented from experimental and theoretical studies of the interaction of intense X-ray pulses with different types of plane targets, including low-density (～10 mg/cm³) ones, in the Angara-5-1 facility. It is found experimentally that a dense low-temperature plasma forms on the target surface before the arrival of the main heating X-ray pulse. It is demonstrated that the contrast of the X-ray pulse can be increased by placing a thin organic film between the target and the discharge gap. The expansion velocity of the plasma created on the target surface irradiated by Z-pinch-produced X rays was found to be (3–4) × 10⁶ cm/s. A comparison between the simulation and experimental results confirms the validity of the physical-mathematical model used.     

Biomedical applications of photon-induced X-ray fluorescence

An X-ray fluorescence method for in vitro analysis of trace elements is presented. The method is characterized by the use of an X-ray tube with secondary targets as a quasimonoenergetic radiation source, and by “infinitely thin” specimens. Different aspects have been examined in order to optimize the sensitivity of the method. It is extremely important to use secondary targets as pure as possible and collimators internally covered by the same element as the secondary target. It is also important to reduce the contribution at the XRF spectrum of photons scattered by the sample, by the sample support, and by the air. Preconcentration techniques can conveniently also be used to this purpose. In this work, biological samples are preconcentrated by reducing them to ash. Typical sensitivities obtained are in the order of 1–5 ng/cm² in a counting time of 10³ s for elements with atomic number ranging from 24 (chromium) to 40 (zirconium).     

Investigation of the angular distribution and energy spectrum of fast ions produced during irradiation of targets by short laser pulses in the SOKOL-P facility

Results are presented from experimental investigations of the angular distributions and energy spectra of fast ions produced in deuterium polyethylene targets under irradiation by picosecond laser pulses with intensities of up to 2 × 10¹⁸ W/cm² in the SOKOL-P facility. The parameters of ion fluxes were measured by time-of-flight spectrometers based on semiconductor detectors.     

Towards miniaturization of a structural genomics pipeline using micro-expression and microcoil NMR

In structural genomics centers, nuclear magnetic resonance (NMR) screening is in increasing use as a tool to identify folded proteins that are promising targets for three-dimensional structure determination by X-ray crystallography or NMR spectroscopy. The use of 1D ¹H NMR spectra or 2D [¹H,¹⁵N]-correlation spectroscopy (COSY) typically requires milligram quantities of unlabeled or isotope-labeled protein, respectively. Here, we outline ways towards miniaturization of a structural genomics pipeline with NMR screening for folded globular proteins, using a high-density micro-fermentation device and a microcoil NMR probe. The proteins are micro-expressed in unlabeled or isotope-labeled media, purified, and then subjected to 1D ¹H NMR and/or 2D [¹H,¹⁵N]-COSY screening. To demonstrate that the miniaturization is functioning effectively, we processed nine mouse homologue protein targets and compared the results with those from the “macro-scale” Joint Center of Structural Genomics (JCSG) high-throughput pipeline. The results from the two pipelines were comparable, illustrating that the data were not compromised in the miniaturized approach.     

High resolution solid-state NMR spectroscopy of the <Emphasis Type="Italic">Yersinia pestis</Emphasis> outer membrane protein Ail in lipid membranes

The outer membrane protein Ail (Adhesion invasion locus) is one of the most abundant proteins on the cell surface of Yersinia pestis during human infection. Its functions are expressed through interactions with a variety of human host proteins, and are essential for microbial virulence. Structures of Ail have been determined by X-ray diffraction and solution NMR spectroscopy, but those samples contained detergents that interfere with functionality, thus, precluding analysis of the structural basis for Ail’s biological activity. Here, we demonstrate that high-resolution solid-state NMR spectra can be obtained from samples of Ail in detergent-free phospholipid liposomes, prepared with a lipid to protein molar ratio of 100. The spectra, obtained with ¹³C or ¹H detection, have very narrow line widths (0.40–0.60 ppm for ¹³C, 0.11–0.15 ppm for ¹H, and 0.46–0.64 ppm for ¹⁵N) that are consistent with a high level of sample homogeneity. The spectra enable resonance assignments to be obtained for N, CO, CA and CB atomic sites from 75 out of 156 residues in the sequence of Ail, including 80% of the transmembrane region. The ¹H-detected solid-state NMR ¹H/¹⁵N correlation spectra obtained for Ail in liposomes compare very favorably with the solution NMR ¹H/¹⁵N TROSY spectra obtained for Ail in nanodiscs prepared with a similar lipid to protein molar ratio. These results set the stage for studies of the molecular basis of the functional interactions of Ail with its protein partners from human host cells, as well as the development of drugs targeting Ail.     

Mixed ligation to vanadium(III): Synthesis,spectra and structures of bis(acetylacetonato)(o-phenanthroline)vanadium(III) fluoroborate and bis(acetylacetonato)(o-phenanthroline)vanadium(III) perchlorate

Two mixed ligand vanadium(III) complexes bis(acetylacetonato)(phenanthroline)vanadium(III) fluoroborate (1) and bis(acetylacetonato)(phenanthroline)vanadium(III) perchorate (2) have been prepared and characterized by UV–Vis, IR, ¹H NMR spectroscopic techniques and single crystal X-ray diffraction. The electronic spectra are as expected for V(III) in an octahedral environment. The ¹H NMR spectra are typical of paramagnetic V(III) species. The complexes have crystallized with dichloromethane solvate and are isomorphous. The coordination sphere is composed of vanadium in a distorted octahedral environment, ligated to two bidentate chelating acetylacetonate ligands through the oxygen atoms and two phenanthroline nitrogens.     

STUDIES OF A CHEMICALLY MODIFIED OLIGODEOXYNUCLEOTIDE CONTAINING A 5-ATOM AMIDE BACKBONE WHICH EXHIBITS IMPROVED BINDING TO RNA

Chimeric oligodeoxyribonucleotides where the phosphodiester linkage -C3′-O-PO_2^? -O-CH₂-C4′- of DNA is substituted by the amide linkage -C3′-CH₂-CH^*(CH₃)-CO-NH-CH₂-C4′ (^*either R or S stereochemistry) have been prepared and their binding to RNA targets have been investigated. Incorporation of a single amide unit increases the T_m by approximately 1.4–1.9°C. Circular dichroic spectra of these modified duplexes are similar to the wildtype DNA/RNA.     

Testing the vibrational exciton and the local mode models on the instructive cases of dicarvone,dipinocarvone, and dimenthol vibrational circular dichroism spectra

The vibrational circular dichroism (VCD) spectra of dicarvone ( 1 ), dipinocarvone ( 2 ), and dimenthol ( 3 ) have been recorded in the range 900–3200 cm⁻¹, encompassing the mid-infrared (mid-IR), the CO stretching, and the CH-stretching regions. For compound 3 also, the fundamental and the first overtone OH stretching regions have been investigated by IR/NIR absorption and VCD. Density functional theory (DFT) calculations allow one to interpret the IR and VCD spectra and to confirm the configuration/conformational studies previously conducted by X-ray diffraction. The most intense VCD signals are associated with the vibrational normal modes involving symmetry-related groups close to the CC bond connecting covalently the two molecular units. The vibrational exciton (VCDEC) model is fruitfully tested on the VCD data of compounds 1 and 2 for the spectroscopic regions at ~1700 cm⁻¹, and the local mode model is tested on compound 3 at ~3500 and ~6500 cm⁻¹. For compounds 1 and 2 also, ECD spectra are reported, and the exciton mechanism is tested also there, and connections to the VCDEC model are examined.     

Inhibition of Catalase by Tea Catechins in Free and Cellular State: A Biophysical Approach

Tea flavonoids bind to variety of enzymes and inhibit their activities. In the present study, binding and inhibition of catalase activity by catechins with respect to their structure-affinity relationship has been elucidated. Fluorimetrically determined binding constants for (−)-epigallocatechin gallate (EGCG) and (−)-epicatechin gallate (ECG) with catalase were observed to be 2.27×10⁶ M⁻¹ and 1.66×10⁶ M⁻¹, respectively. Thermodynamic parameters evidence exothermic and spontaneous interaction between catechins and catalase. Major forces of interaction are suggested to be through hydrogen bonding along with electrostatic contributions and conformational changes. Distinct loss of α-helical structure of catalase by interaction with EGCG was captured in circular dichroism (CD) spectra. Gallated catechins demonstrated higher binding constants and inhibition efficacy than non-gallated catechins. EGCG exhibited maximum inhibition of pure catalase. It also inhibited cellular catalase in K562 cancer cells with significant increase in cellular ROS and suppression of cell viability (IC₅₀ 54.5 µM). These results decipher the molecular mechanism by which tea catechins interact with catalase and highlight the potential of gallated catechin like EGCG as an anticancer drug. EGCG may have other non-specific targets in the cell, but its anticancer property is mainly defined by ROS accumulation due to catalase inhibition.     

Ultrahigh charging of dust grains by the beam−plasma method for creating a compact neutron source

Generation of high-voltage high-current electron beams in a low-pressure (P = 0.1–1 Torr) gas discharge is studied experimentally as a function of the discharge voltage and the sort and pressure of the plasma-forming gas. The density of the plasma formed by a high-current electron beam is measured. Experiments on ultrahigh charging of targets exposed to a pulsed electron beam with an energy of up to 25 keV, an electron current density of higher than 1 A/cm², a pulse duration of up to 1 μs, and a repetition rate of up to 1 kHz are described. A numerical model of ultrahigh charging of dust grains exposed to a high-energy electron beam is developed. The formation of high-energy positive ions in the field of negatively charged plane and spherical targets is calculated. The calculations performed for a pulse-periodic mode demonstrate the possibility of achieving neutron yields of higher than 10⁶ s^–1 cm^–2 in the case of a plane target and about 10⁹ s^–1 in the case of 10³ spherical targets, each with a radius of 250 μm.     

A validation of SpekPy: A software toolkit for modelling X-ray tube spectra

PurposeTo validate the SpekPy software toolkit that has been developed to estimate the spectra emitted from tungsten anode X-ray tubes. The model underlying the toolkit introduces improvements upon a well-known semi-empirical model of X-ray emission.Materials and methodsUsing the same theoretical framework as the widely-used SpekCalc software, new electron penetration data was simulated using the Monte Carlo (MC) method, alternative bremsstrahlung cross-sections were applied, L-line characteristic emissions were included, and improvements to numerical methods implemented. The SpekPy toolkit was developed with the Python programming language. The toolkit was validated against other popular X-ray spectrum models (50 to 120 kVp), X-ray spectra estimated with MC (30 to 150 kVp) as well as reference half value layers (HVL) associated with numerous radiation qualities from standard laboratories (20 to 300 kVp).ResultsThe toolkit can be used to estimate X-ray spectra that agree with other popular X-ray spectrum models for typical configurations in diagnostic radiology as well as with MC spectra over a wider range of conditions. The improvements over SpekCalc are most evident at lower incident electron energies for lightly and moderately filtered radiation qualities. Using the toolkit, estimations of the HVL over a large range of standard radiation qualities closely match reference values.ConclusionsA toolkit to estimate X-ray spectra has been developed and extensively validated for central-axis spectra. This toolkit can provide those working in Medical Physics and beyond with a powerful and user-friendly way of estimating spectra from X-ray tubes.     

Solid-state NMR sequential assignments of the amyloid core of full-length Sup35p

Sup35p is a yeast prion and is responsible for the [PSI ⁺] trait in Saccharomyces cerevisiae. With 685 amino acids, full-length soluble and fibrillar Sup35p are challenging targets for structural biology as they cannot be investigated by X-ray crystallography or NMR in solution. We present solid-state NMR studies of fibrils formed by the full-length Sup35 protein. We detect an ordered and rigid core of the protein that gives rise to narrow and strong peaks, while large parts of the protein show either static disorder or dynamics on time scales which interfere with dipolar polarization transfer or shorten the coherence lifetime. Thus, only a small subset of resonances is observed in 3D spectra. Here we describe in detail the sequential assignments of the 22 residues for which resonances are observed in 3D spectra: their chemical shifts mostly corresponding to β-sheet secondary structure. We suspect that these residues form the amyloid core of the fibril.     

Acetyl pyridine-based palladium(II) compounds as an artificial metallonucleases

Palladium(II) complexes of type [Pd(Lⁿ)Cl₂] and [Pd(bdt)(Lⁿ)] have been synthesized using 2-acetyl pyridine derivatives(Lⁿ) and benzene-12-dithiol(bdt). The synthesized complexes have been characterized by various analytical techniques like thermo gravimetric analysis, elemental analysis, conductance measurement, and spectroscopic techniques like elemental analysis, mass spectra, absorption spectra, IR, ¹H NMR, energy-dispersive X-ray spectroscopy. The interaction of the complexes with calf-thymus DNA (CT-DNA) has been explored by absorption titration, viscosity measurement methods. Based on the observations, an intercalative binding mode of DNA has been proposed. In order to provide additional evidence for the intercalation mode of binding between the complex and CT-DNA, fluorescence titration experiment was performed. In addition, molecular modeling study has been carried out with the aim of establishing the complex’s binding mode. Antibacterial activity study of the complexes have been screened against pathogenic bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Serratia marcescens, and Pseudomonas aeruginosa. Gel electrophoresis assay demonstrates that all the complexes can cleave the pUC19 plasmid DNA.     

Diagnostics of fast processes in laser plasmas after the irradiation of low-density media in the mishen facility

New experimental data on the laser irradiation of low-density porous materials in the Mishen facility are presented and discussed. A wide set of optical and X-ray diagnostics was used to analyze the physical processes in porous media with different microstructures and specific densities of 1–30 mg/cm³ exposed to laser pulses with λ=1.054 µm, τ=3 ns, and I=10¹³–10¹⁴ W/cm². The features of laser absorption and scattering and the processes of energy transfer in porous media were investigated for different average densities, thicknesses, and microstructures of the targets and different incidence angles of the laser beam. It was found that the material microstructure (chaotic or quasi-ordered) significantly affected the formation and dynamics of a plasma produced inside the irradiated samples that model the components of the advanced targets used in inertial confinement fusion research.     

Metallic perchlorate salts of N-isopropyl-and N-Cyclohexyl-2-pyrrolidinone

A series of metal perclorate complexes of N- isopropyl-2-pyrrolidinone (NIPP) and N-cyclohexyl- 2-pyrrolidinone (NCHP) have been synthesized, showing coordination through the carbonyl oxygen atom. These complexes have compositions with the general formulas [M(NIPP)_{4 or 6}]²⁺(ClO₄)₂ and [M(NCHP)₆]²⁺(ClO₄)₂ [M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)]. They have been characterized by IR spectra, electrical conductivity measurements, magnetic moments, X-ray diffraction patterns and electronic absorption spectra.     

High-energy ion generation by short laser pulses

This paper reviews the many recent advances at the Center for Ultrafast Optical Science (CUOS) at the University of Michigan in multi-MeV ion beam generation from the interaction of short laser pulses focused onto thin foil targets at intensities ranging from 10¹⁷ to 10¹⁹ W/cm². Ion beam characteristics were studied by changing the laser intensity, laser wavelength, target material, and by depositing a well-absorbed coating. We manipulated the proton beam divergence using shaped targets and observed nuclear transformation induced by high-energy protons and deuterons. Qualitative theoretical approaches and fully relativistic two-dimensional particle-in-cell simulations modeled energetic ion generation. Comparison with experiments sheds light on ion energy spectra for multi-species plasma, the dependences of ion-energy on preplasma scale length and solid density plasma thickness, and laser-triggered isotope yield. Theoretical predictions are also made with the aim of studying ion generation for high-power lasers with the energies expected in the near future, and for the relativistic intensity table-top laser, a prototype of which is already in operation at CUOS in the limits of several-cycle pulse duration and a single-wavelength spot size.     

A novel chemiluminescent flow injection analysis of trace amounts of rutin by its inhibition of the luminol–hydrogen peroxide reaction catalyzed by tetrasulfonated colbalt phthalocyanine

Based on the inhibition effect of rutin on the luminol–hydrogen peroxide chemiluminescence (CL) system catalyzed by tetrasulfonated colbalt phthalocyanine (CoTSPc), a sensitive flow‐injection CL method has been developed for the determination of rutin. The CL reaction mechanism was carefully investigated by examining CL emission spectra, UV–visible spectra and variation of reaction conditions. It was found that there existed a linear relationship between CL intensity and the concentration of rutin in the range of 8.0 × 10^?9 to 1.0 × 10^?6 mol L^?1, and the detection limit is 3.8 × 10^?9 mol L^?1. This proposed method is sensitive, convenient and simple, and has been applied to the determination of rutin in commercial rutin tablets with satisfactory results. Copyright © 2009 John Wiley & Sons, Ltd.     

Fluorescent bovine serum albumin interacting with the antitussive quencher dextromethorphan: a spectroscopic insight

The interaction of dextromethorphan hydrobromide (DXM) with bovine serum albumin (BSA) is studied by using fluorescence spectra, UV–vis absorption, synchronous fluorescence spectra (SFS), 3D fluorescence spectra, Fourier transform infrared (FTIR) spectroscopy and circular dichroism under simulated physiological conditions. DXM effectively quenched the intrinsic fluorescence of BSA. Values of the binding constant, K_A, are 7.159 × 10³, 9.398 × 10³ and 16.101 × 10³ L/mol; the number of binding sites, n, and the corresponding thermodynamic parameters ΔG°, ΔH° and ΔS° between DXM and BSA were calculated at different temperatures. The interaction between DXM and BSA occurs through dynamic quenching and the effect of DXM on the conformation of BSA was analyzed using SFS. The average binding distance, r, between the donor (BSA) and acceptor (DXM) was determined based on Förster's theory. The results of fluorescence spectra, UV–vis absorption spectra and SFS show that the secondary structure of the protein has been changed in the presence of DXM. Copyright © 2015 John Wiley & Sons, Ltd.