X‐ray absorption spectroscopy at the Ni?K edge in Stackhousia tryonii Bailey hyperaccumulator

Young plants of Stackhousia tryonii Bailey were exposed to 34 mM Ni kg^?1 in the form of NiSO₄· 6H₂O solution and grown under controlled glasshouse conditions for a period of 20 days. Fresh leaf, stem and root samples were analysed in vivo by micro x‐ray absorption spectroscopy (XAS) at the Ni? K edge. Both x‐ray absorption near edge structure and extended x‐ray absorption fine structure spectra were analysed, and the resulting spectra were compared with spectra obtained from nine biologically important Ni‐containing model compounds. The results revealed that the majority of leaf, stem and root Ni in the hyperaccumulator was chelated by citrate. Our results also suggest that in leaves Ni is complexed by phosphate and histidine, and in stems and roots, phytate and histidine. The XAS results provide an important physiological insight into transport, detoxification and storage of Ni in S. tryonii plants. Copyright © 2008 John Wiley & Sons, Ltd.     

Relics in medieval altarpieces? Combining X‐ray tomographic,laminographic and phase‐contrast imaging to visualize thin organic objects in paintings

X‐ray radiography is a common tool in the study of old master paintings. Transmission imaging can visualize hidden paint layers as well as the structure of the panel or canvas. In some medieval altarpieces, relics seem to have been imbedded in the wooden carrier of paintings. These are most probably thin organic fibrous materials such as paper or textile, which in traditional radiography are shadowed by the more absorbing surrounding material. This paper studies the application potential of synchrotron‐based tomographic and laminographic imaging complemented with phase‐contrast imaging for detection of such relics. The techniques are applied to a dummy painting. The results demonstrate that by using these imaging methods it is possible to three‐dimensionally visualize hidden cavities in panels and detect thin fibrous low‐Z materials sandwiched between a high‐Z paint layer and a thick wooden panel.     

Infrared absorption cross sections for acetone (propanone) in the 3 μm region

Infrared absorption cross sections for acetone (propanone), CH₃C(O)CH₃, have been determined in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR) and a multipass cell with a maximum optical path length of 19.3 m. The spectra of mixtures of acetone with dry synthetic air were recorded at 0.015 cm⁻¹ resolution (calculated as 0.9/MOPD using the Bruker definition of resolution) at a number of temperatures and pressures (50-760 Torr and 195-296 K) appropriate for atmospheric conditions. Intensities were calibrated using three acetone spectra (recorded at 278, 293 and 323 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database.     

Self‐trapped N?H vibrational states in the polymorphs of glycine,L‐ and DL‐alanine

The polarized Raman spectra of the oriented single crystals of L ‐ and DL ‐alanine, α‐, β‐ and γ‐polymorphs of glycine have been studied at 3–300 K. Regularly spaced band packets have been observed in the spectral range of 2500–3000 cm⁻¹, with intensity decreasing noticeably on heating. These band packets were interpreted as the manifestations of the existence of N H self‐trapped states in these systems at low temperatures. The analysis of the polarized spectra has shown that the self‐trapping is observed exclusively for the NH stretching vibration of the amino groups, which is related to the NH···O hydrogen bonds along the head‐to‐tail chains of zwitterions in the crystal structures. The wavenumber of this NH stretching vibration, however, was proposed to depend not solely on the length of this NH···O hydrogen bond, but also on the lengths of all the other NH···O hydrogen bonds formed by the NH₃⁺ and the COO⁻ groups in the structure linking the head‐to‐tail chains with each other. The arguments in favor of the hypothesis that the self‐trapping in these systems can be mediated by zero‐point quantum motions, and not by lattice phonons, are considered. The unusually low wavenumber (2500 cm⁻¹) observed for the NH stretching vibration and indicating at the formation of a very strong NH···O bond is interpreted based on considering the effect of the crystalline environment on the formation and properties of the NH···O bonds in the head‐to‐tail chains of amino acid zwitterions. The results are interesting for understanding the factors determining the dynamics and structural instability of crystalline amino acids and also for biophysical chemistry, as the hydrogen bonded chains formed by amino acid zwitterions in the crystals can mimic the peptide chains. Copyright © 2009 John Wiley & Sons, Ltd.     

What are the differences between Hantzsch ester and H2 as two‐hydrogen‐atom donors in acetonitrile on the thermodynamics of elementary steps?

Thermodynamic driving forces of eight possible elementary steps for Hantzsch ester and six possible elementary steps for H₂ to release two hydrogen atoms (2H^?) or ions (H^? and H⁺) in acetonitrile were examined using experimental method or the available related thermodynamic data for the first time, which can facilitate chemists to choose a suitable reducing agent between Hantzsch ester and H₂ to reduce a given organic unsaturated compound in acetonitrile and make a rational diagnosis on the detailed reaction mechanisms. The focus of this paper is to compare the differences between Hantzsch ester and H₂ to release two hydrogen atoms (or ions) on the thermodynamics of elementary steps in acetonitrile. Copyright © 2016 John Wiley & Sons, Ltd.     

Energy dependence of the cross sections for the e<Superscript>+</Superscript>e<Superscript>–</Superscript> → hadrons process near the production threshold for the <Emphasis Type="Italic">N</Emphasis><Emphasis Type="Italic">N̄</Emphasis> pair

The energy dependence of the cross sections for the processes e⁺e^? → π⁺π^?π⁰, K⁺K^?, ηπ⁺π^?, ωπ₀, and K⁺K^?π⁺π^? is studied near the production threshold for a nucleon–antinucleon pair. It is shown that, within the measurement errors, the cross sections in question behave smoothly in this energy region.     

Infrared absorption cross sections for propane (C3H8) in the 3 μm region

Infrared absorption cross sections for propane have been measured in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR). The spectra of mixtures of propane with dry synthetic air were recorded at 0.015 cm⁻¹ resolution (calculated as 0.9/MOPD using the Bruker definition of resolution), at a number of temperatures and pressures appropriate for atmospheric conditions. Intensities were calibrated using two propane spectra (recorded at 278 and 293 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database.     

Infrared absorption cross sections for ethane (C2H6) in the 3 μm region

Infrared absorption cross sections for ethane have been measured in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125/HR). Results are presented for pure ethane gas from spectra recorded at 0.004 cm⁻¹ resolution and for mixtures with dry synthetic air from spectra obtained at 0.015 cm⁻¹ resolution (calculated as 0.9/MOPD using the Bruker definition of resolution), at a number of temperatures and pressures appropriate for atmospheric conditions. Intensities were calibrated using three ethane spectra (recorded at 278, 293, and 323 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database.     

What are the instrumentation requirements for measuring the isotopic composition of net ecosystem exchange of CO2 using eddy covariance methods?

Better quantification of isotope ratios of atmosphere-ecosystem exchange of CO2 could substantially improve our ability to probe underlying physiological and ecological mechanisms controlling ecosystem carbon exchange, but the ability to make long-term continuous measurements of isotope ratios of exchange fluxes has been limited by measurement difficulties. In particular, direct eddy covariance methods have not yet been used for measuring the isotopic composition of ecosystem fluxes. In this article, we explore the feasibility of such measurements by (a) proposing a general criterion for judging whether a sensor's performance is sufficient for making such measurements (the criterion is met when the contribution of sensor error to the flux measurement error is comparable to or less than the contribution of meteorological noise inherently associated with turbulence flux measurements); (b) using data-based numerical simulations to quantify the level of sensor precision and stability required to meet this criterion for making direct eddy covariance measurements of the 13C/12C ratio of CO2 fluxes above a specific ecosystem (a mid-latitude temperate forest in central Massachusetts, USA); (c) testing whether the performance of a new sensor-a prototype pulsed quantum cascade laser (QCL) based isotope-ratio absorption spectrometer (and plausible improvements thereon)-is sufficient for meeting the criterion in this ecosystem. We found that the error contribution from a prototype sensor (approximately 0.2 per thousand, 1 SD of 10 s integrations) to total isoflux measurement error was comparable to (1.5 to 2x) the irreducible 'meteorological' noise inherently associated with turbulent flux measurements above this ecosystem (daytime measurement error SD of approximately 60% of flux versus meteorological noise of 30-40% for instantaneous half-hour fluxes). Our analysis also shows that plausible instrument improvements (increase of sensor precision to approximately 0.1 per thousand, 1 SD of 10 s integrations, and increased sensor stability during the half-hour needed to integrate eddy covariance measurements) should decrease the contribution of sensor error to the point where it is less than the contribution from meteorological noise. This suggests that new sensors using QCL-based isotope ratio absorption spectroscopy should make continuous long-term observations of the isotopic composition of CO2 fluxes via eddy covariance methods feasible.     

Measurement of cross sections for inelastic cold-neutron scattering in metals and polymers by the method of (<Emphasis Type="Italic">n, γ</Emphasis>) analysis

The results obtained by measuring the cross sections for the inelastic scattering of very cold neutrons for a number of metals and polymers by the method of a neutron-irradiation analysis are presented. The method is based on simultaneously measuring events of inelastic scattering and neutron capture in the sample under investigation via recording gamma radiation with a semiconductor germanium detector. Neutron capture by a nucleus of the sample is accompanied by the prompt radiation of gamma rays having a known spectrum. Upon inelastic scattering, a neutron acquires thermal energy. Upon leaving the sample, this neutron is absorbed in a special converter that contains the isotope ¹⁰B. The capture of the neutron by a ¹⁰B nucleus is followed by the emission of a 477-keV gamma ray. The probabilities of capture and inelastic scattering are proportional to the respective neutron-interaction cross sections, and the ratio of the recorded detector counts corresponding to events of the two types does not depend on the spectrum of the incident flux of very cold neutrons or on the trajectory of neutron motion in the sample. The sought inelastic-scattering cross section at a fixed sample temperature is calculated by using this ratio and the known cross section for neutron capture by the sample isotope having a known gamma-radiation spectrum.     

Energy scan of cross sections for <Emphasis Type="Italic">e</Emphasis><Superscript>+</Superscript><Emphasis Type="Italic">e</Emphasis><Superscript>–</Superscript> annihilation into quarkonia and light hadrons in the Belle experiment

The cross sections of the reactions e⁺e^– → ?(nS)π⁺π^? (n = 1, 2,3) and e⁺e^– → h _b (nP)π⁺π^? (n = 1, 2) are measured as a function of the cms collision energy from their thresholds up to 11.02 GeV using the data of the Belle experiment operating at the KEKB e⁺e^– collider. The peaks of the ?(10 860) and ?(11020) resonances are observed in the cross sections with an insignificant contribution of the continuum. The decay ?(11020) → h _b (nP)π⁺π^? is found to fully proceed through intermediate isovector states Z _b (10610) and Z _b (10650).     

Measurement of cross sections for processes involving <Emphasis Type="Italic">e</Emphasis><Superscript>+</Superscript><Emphasis Type="Italic">e</Emphasis><Superscript>−</Superscript> annihilation to hadrons at the VEPP-2M collider

Results obtained by measuring, in experiments at the VEPP-2M e ⁺ e ^? collider with the CMD-2 and SND detectors at the Novosibirsk Institute of Nuclear Physics, cross sections for e ⁺ e ^? → hadrons annihilation processes at energies in the range 360 ≤ √s ≤ 1380 MeV are surveyed. The measured cross sections and the vector-meson parameters deduced from an analysis of these cross sections are presented. The cross section for the process e ⁺ e ^? → π ⁺ π ^? is compared with the spectral function for the decay τ ^? → π ^? π ⁰ ν _τ.     

Description of cross sections for photonucleon reactions on tin isotopes at photon energies in the range 2 ≤ <Emphasis Type="Italic">E</Emphasis><Subscript><Emphasis Type="Italic">γ</Emphasis></Subscript> ≤ 140 MeV

A modified model of preequilibrium decay is considered. This model makes it possible to calculate cross sections for multiparticle photonucleon reactions with allowance for the impact of collective isospin effects. Features of the photodisintegration of 101 ≤ A ≤ 135 tin isotopes in the energy range 2 ≤ E _γ ≤ 140 MeV are studied on the basis of this model.     

Modeling the physico‐chemistry of acid sulfate waters through Raman spectroscopy of the system FeSO4?H2SO4?H2O

Mine waters containing extremely high concentrations of sulfuric acid and dissolved iron are found in the Rio Tinto (Spain) area. In this study, Raman spectroscopy has been used to investigate the speciation of the system iron(II)–sulfuric acid–water as an approach to study Rio Tinto's stream water. Several solutions of aqueous sulfuric acid containing iron(II) sulfate in the range 0–1.65 mol/kg were prepared, and qualitative and quantitative analyses of the ions present in the solutions were carried out using Raman spectroscopy. The intrinsic features of Raman spectroscopy allowed the identification of the species present in solution and calculation of the species concentration through band‐fitting of the Raman spectra. The activity coefficient product of the system iron(II) sulfate–sulfuric acid–water as a function of salt concentration is reported. Previous findings on the formation of iron(II) hexahydrate complexes in the mentioned system have been corroborated by means of Raman spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.     

Measurement of the cross sections for <Emphasis Type="Italic">π</Emphasis><Superscript>+</Superscript><Emphasis Type="Italic">π</Emphasis><Superscript>−</Superscript> production in <Emphasis Type="Italic">pp</Emphasis> collisions at energies below 1 GeV

The cross sections for the reaction pp → ppπ ⁺ π ^? are measured at several values of the incident-proton energy. The resulting values are compared with other results, including values obtained previously for a deuteriumtarget, as well as with the predictions of a theoreticalmodel. This comparison reveals that, at energies below 850 MeV, the use of the impulse approximation in extracting the cross sections for double pion production on a free nucleon from data obtained with deuteron targets is illegitimate.     

Silica Nanoparticles as Adhesives for Biological Tissues? Re‐Examining the Effect of Particles Size,Particle Shape,and the Unexpected Role of Base

Development of new, effective, and patient‐friendly adhesives for biological tissues is important for medical and surgical practices such as bleeding control and organ repairing. While some commercially available silica nanoparticles such as LUDOX SM‐30 have shown adhesive properties for biological tissues, the role of inorganic base present in the adhesive properties of the silica nanoparticles has not been examined. Moreover, it remained unclear how the size and the shape of silica nanoparticles affect the adhesion properties. To address these questions, synthesis and characterization of a series of uniform silica nanostructures with different sizes and shapes is carried out. Unexpectedly, none of the synthesized silica nanostructures without additional inorganic base shows adhesion properties against liver tissues. Such surprising phenomena motivate to examine other factors in the commercial silica nanoparticles as tissue adhesives, and reach a conclusion that the inorganic base plays a key role in the adhesion properties. It is believed that this study answers the important question whether silica nanoparticles can act as biological adhesives or not. The conclusion also gives a lesson to other scientists and engineers in design and exploration of new biological adhesives.     

Truncated forms of the second-rank orthorhombic Hamiltonians used in magnetism and electron magnetic resonance (EMR) studies are invalid—Why it went unnoticed for so long?

This paper deals with the truncated forms of the second-rank orthorhombic Hamiltonians employed in magnetism and electron magnetic resonance (EMR) studies. Consideration of the intrinsic features of orthorhombic Hamiltonians reveals that the truncations, which consist in omission of one of three interdependent orthorhombic terms, are fundamentally invalid. Implications of the invalid truncations are: loss of generality of quantized spin models, misinterpretation of physical properties of systems studied (e.g. maximum rhombicity ratio and relative parameter values), and inconsistent notations for Hamiltonian parameters that hamper direct comparison of data from various sources. Truncated Hamiltonian forms identified in our survey are categorized and systematically reviewed. Examples are taken from studies of various magnetic systems, especially those involving transition ions, as well as model magnetic systems. The pertinent studies include magnetic ordering in three- and lower dimensions, e.g. [(CH₃)₄N]MnCl₃ (TMMC), canted ferromagnets, Haldane gap antiferromagnets, single molecule magnets exhibiting macroscopic quantum tunneling, e.g. Mn₁₂ complexes with spin S=10. Our study provides better insight into magnetic and spectroscopic properties of pertinent magnetic systems, which calls for reconsideration of the experimental and theoretical results based on invalid truncated Hamiltonians. The physical nature of Hamiltonians used in magnetism and EMR studies and other types of inappropriate terminology occurring, especially in model magnetism studies, require separate discussion.