Morphology of Polystyrene Core–dPoly(ethylene oxide) Shell Arborescent Copolymer Micelles from Small-Angle Neutron Scattering Analysis

Arborescent (dendrigraft) copolymers with a branched polystyrene (PS) core grafted at the chain termini with deuterated poly(ethylene oxide) segments (PS-dPEO) were characterized in benzene and acetone by small-angle neutron scattering measurements using the contrast matching technique. While copolymers incorporating a G1 (twice-grafted) PS core aggregated to some extent, the portion of the scattering curve corresponding to non-aggregated copolymer molecules could still be analyzed to determine the shape and segment radial density profile for core and shell. These were derived from the pair distance distribution function P(r) and the scattering length density contrast profile Δρ(r) = ρ(r) ? ρ(solvent), obtained by the indirect Fourier transformation and deconvolution methods. The profiles obtained for the G1 copolymer are consistent with a well-defined PS core–dPEO shell morphology, only observed previously for upper generation (G4) polymers with deuterated PS (dPS) chains grafted randomly on arborescent PS substrates. Detailed morphological analysis could not be carried out for an analogous G3 arborescent PS copolymer terminally grafted with dPEO segments due to extensive aggregation in both solvents.     

Test of Determination of (p,γ) Astrophysical S-Factors Using the Asymptotic Normalization Coefficients from Neutron Transfer Reactions

The asymptotic normalization coefficients （ANCs） for the virtual decay ^17 O→^16 O＋n are derived from the angular distributions of the 16 O（d, p）^17O reaction leading to the ground and first excited states of ^17O, respectively, using the distorted wave Born approximation and the adiabatic wave approximation. The ANCs of ^17F are then extracted according to charge symmetry of mirror nuclei and used to calculate the astrophysical S-factors of ^16 O（p, γ）^17 F leading to the first two states of ^17 F. The present results are in good agreement with those from the direct measurement. This provides a test of this indirect method to determine direct astrophysical S-factors of （P, γ） reaction. In addition, the S-factors at zero energy for the direct captures to the ground and first excited states of ^17 F are presented, without the uncertainty associated with the extrapolation from higher energies in direct measurement.     

Evidence of Vibrational-Induced Rotational Axis Switching for HD(12)C(16)O: New High-Resolution Analysis of the nu(5) and nu(6) Bands and First Analysis of the nu(4) Band (10-µm Region)

Using new high-resolution Fourier transform spectra recorded in Giessen in the 8-12 μm region, a more extended analysis of the nu(5) and nu(6) bands and the first high-resolution study of the nu(4) band of HDCO were performed. As pointed out previously [M. Allegrini, J. W. C. Johns, and A. R. W. McKellar, Can. J. Phys. 56, 859-864 (1978)], the energy levels of the 5(1) and 6(1) states are strongly coupled by A- and B-type Coriolis interactions. On the other hand, it appeared that weaker resonances involving the energy levels of the 4(1) state with those of the 5(1) and 6(1) states also had to be accounted for. Consequently, the calculation of the energy levels was performed taking into account the Coriolis-type resonances linking the energy levels of the {6(1), 5(1), 4(1)} resonating states. Because of the unusually strong Coriolis interaction between nu(5) and nu(6), a nonclassical behavior of the rotational levels of the 5(1) and 6(1) states was observed and it was necessary to use a new Hamiltonian matrix which possesses, as usual, both A- and B-type Coriolis operators in the 5(1) if 6(1) and 6(1) if 4(1) off diagonal blocks but differs from the classical reduced Hamiltonian which is used commonly for planar C(s)-type molecules. More precisely, it proved necessary to include non-orthorhombic terms in the expansion of the rotational Hamiltonian of the 5(1) and 6(1) states. According to the considerations developed by Watson [J. K. G. Watson, in "Vibrational Spectra and Structure," (J. Durig, Ed.), Chap. 1, Elsevier, Amsterdam, 1977], these non-orthorhombic operators which are not symmetry forbidden are usually removed for semirigid C(s)-type molecules by rotational contact transformations. In the present study, the occurrence of terms in {J(x), J(z)} in the expansions of the rotational Hamiltonians for the 5(1) and 6(1) states indicates that the inertial system of HDCO differs for each of the three {6(1), 5(1), 4(1)} resonating states. Therefore, HDCO becomes a good example of vibrational-induced rotational axis switching (VIRAS) which was already suggested as the mechanism responsible for the enhanced densities of coupled states observed in 2-fluoroethanol [H. Li, S. Erza, and L. A. Philips, J. Chem. Phys. 97, 5956-5963 (1992)]. Copyright 2000 Academic Press.     

Multiscale simulation from atomistic to continuum – coupling molecular dynamics (MD) with the material point method (MPM)

A new multiscale simulation approach is introduced that couples atomistic-scale simulations using molecular dynamics (MD) with continuum-scale simulations using the recently developed material point method (MPM). In MPM, material continuum is represented by a finite collection of material points carrying all relevant physical characteristics, such as mass, acceleration, velocity, strain and stress. The use of material points at the continuum level provides a natural connection with the atoms in the lattice at the atomistic scale. A hierarchical mesh refinement technique in MPM is presented to scale down the continuum level to the atomistic level, so that material points at the fine level in MPM are allowed to directly couple with the atoms in MD. A one-to-one correspondence of MD atoms and MPM points is used in the transition region and non-local elastic theory is used to assure compatibility between MD and MPM regions, so that seamless coupling between MD and MPM can be accomplished. A silicon single crystal under uniaxial tension is used in demonstrating the viability of the technique. A Tersoff-type, three-body potential was used in the MD simulations. The coupled MD/MPM simulations show that silicon under nanometric tension experiences, with increasing elongation in elasticity, dislocation generation and plasticity by slip, void formation and propagation, formation of amorphous structure, necking, and final rupture. Results are presented in terms of stress–strain relationships at several strain rates, as well as the rate dependence of uniaxial material properties. This new multiscale computational method has potential for use in cases where a detailed atomistic-level analysis is necessary in localized spatially separated regions whereas continuum mechanics is adequate in the rest of the material.     

Some results of the growth of semiconductor crystals in microgravity conditions (to the 50th anniversary of Yuri Gagarin’s flight into space)

The history of the growth of semiconductor crystals aboard space vehicles and their subsequent investigation has been described shortly. It has been shown using Ge(Ga), GaSb(Si), and GaSb(Te) crystals as an example that the formation of segregation growth striations can be avoided during their recrystallization by the vertical Bridgman method in conditions of physical simulation of microgravity on the Earth, mainly due to the essential weakening of the thermal gravitation convection. By their structure and impurity distribution, they approach the crystals grown in space. The investigation of recrystallization of Te has made it possible to determine the role of the detachment effect characteristic of the microgravity conditions and the features of the microstructure of the samples that crystallize with a free surface. The analysis of the results obtained from experiments in space allows us to better understand the processes occurring during the crystallization of the melts and to improve the crystal growth in terrestrial conditions.     

Chemical Analysis of Historic Art and Painting Conservation Materials (19th and 20th Centuries) from the National Museum in Krakow by Gas Chromatography–Mass Spectrometry and Fourier Transform Infrared Spectroscopy

Chemical composition of varnishes Vernis a Tableaux Vibert by Lefranc & Cie, Schutzfirnis für Oelgemalde Schmincke's Retuschier-Firnis by Schmincke & Co. Düsseldorf, Tempera-Firnis by Schmincke & Co. Düsseldorf, Bernstein-Gemaldefirniss für Ludwig'sche Petroleumfarben by Dr. Schoenfeld Düsseldorf, and Vernis Martin Pour Laquer by Lefranc & Cie Paris; oil medium Copal en pâte by Duroziez; essential oils Oleum Cupressi by Polak & Schwarz and Oleum Calami by Polak & Schwarz; fixative for charcoal, crayons, and pastels Nr 840/4 by Iskra & Karmański; and restoring medium for paintings Prof. Dr. Büttner's Phobus by Schmincke Düsseldorf were analyzed with gas chromatography–mass spectrometry. The analyses were conducted to obtain information about the exact composition of these products, which are stored at the National Museum in Krakow and were used by conservators. The results of research facilitate understanding of processes used in paintings and planning methods for their conservation.     

Abilities of Antioxidants to Eliminate the Peroxyl Radical Derived from 2,2′-Azobis(2-Amidinopropane) Dihydrochloride (AAPH)

Electron spin resonance (ESR) of 5-(2,2-dimethyl-1,3-propoxy cyclophosphoryl)-5-methyl-1-pyrroline N-oxide (CYPMPO) spin adducts of free radicals derived from the UV irradiation of 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH) under rapid scanning condition was examined. The ESR signal obtained was the superposition of two spectra, the spin adduct of the alkoxyl radical [CYPMPO-ORa, Ra = C(CH₃)₂-C(⁺NH₂Cl^?)NH₂] and the peroxyl radical (CYPMPO-OORa). The decay rate of CYPMPO-OORa was 8,400 times that of CYPMPO-ORa. The order of the k _SB/k _ST values (the slope of the Stern–Volmer’s plot) for the peroxyl radical (RaOO·) was l-ascorbic acid > caffeic acid > rutin ~ Trolox ~ (+)-catechin ~ glutathione (reduced), which was almost the same order as that for the alkoxyl radical (RaO·). Though the k _SB/k _ST value of each antioxidant for the peroxyl radical was about half of that for the alkoxyl radical, the ratios of the values of antioxidants to that of trolox (the relative ORAC values) were almost the same between the peroxyl and alkoxyl radicals. The relative oxygen radical absorbance capacity (ORAC) values of polyphenols estimated by the ORAC-ESR assay using both peroxyl and alkoxyl radicals were smaller than those by the ORAC-FL assay.     

Transformation from δ-FeOOH to hematite in the presence of trace Fe(II)

δ-FeOOH, a poorly crystalline iron oxyhydroxide, can transform to the more stable iron oxyhydroxide or oxide. In the present work, the transformation from δ-FeOOH to goethite and hematite in the presence of trace Fe(II) has been investigated. The results show that Fe(II) can catalyze this transformation of δ-FeOOH. Based on experimental results and literature data, it is confirmed that two transformation mechanisms exist in the current system. One is the catalytic dissolution of δ-FeOOH, which leads to the formation of both hematite and goethite. The other is the catalytic solid-state transformation from δ-FeOOH to hematite. Which mechanism predominates depends on the temperature, pH, heating rate, etc. The results reveal that high temperatures (in the range from room temperature (RT) to 100 °C) favor the solid-state transformation as well as the formation of hematite. Given the structural relationships observed between δ-FeOOH and hematite, it is possible that the solid-state transformation from δ-FeOOH to hematite can exist.     

Measurement of the total cross section difference ΔσT(pp) in the energy range from 0.43 to 2.4 GeV

The SATURNE II polarized proton beam and the Saclay frozen spin polarized proton target were used to measure the total cross section difference Δσ_T = −2σ_{1 tot} at 26 energies between 0.43 and 2.4 GeV. Here Δσ_T is the total cross section difference for transverse beam and target spins parallel and antiparallel, respectively, and σ_1tot is one of spin-dependent terms in the total cross section σ_tot. The energy dependence of Δσ_T below 1 GeV shows similar structures as for Δσ_L. An additional minimum appears at about 1.3 GeV, which involves a structure in singlet spin partial waves.     

Applicability of chemical derivatization – X-ray photoelectron spectroscopy (CD–XPS) to the characterization of complex matrices: case of electrosynthesized polypyrroles

Problems arising in the application of XPS coupled with derivatization reactions (CD-XPS) to the characterization of complex matrices are stressed by considering the case of polypyrroles electrosynthesized from aqueous solution. In these materials oxygen– and nitrogen–carbon functionalities are contemporaneously present, as well as acidic, basic, charged and reducible groups. The derivatizing agents titanium di-isopropoxide-bis(2,4-pentanedionate) (TAA), trifluoroethanol (TFE) and pentafluorophenylhydrazine (PFPH) were used to label the C–OH, COOH and CO groups, respectively, in the pristine (PPY) and in the overoxidized (PPYox) polymer. The case shows that, when real samples are analysed, only the correlation among the information present in all the available spectra can supply the key to the interpretation of CD-XPS data, such as the actual stoichiometry and secondary effects. In particular, it is showed that PFPH cannot be used as a reliable derivatizing agent for CO groups in PPYox, due to the competition of a side reaction (already reported for hydrazines) occurring on this particular substrate. This effect may be disregarded if a thorough control of the stoichiometry is not performed.     

Total (complete) and ionization cross-sections of argon and krypton by positron impact from 15 to 2000 eV – Theoretical investigations

Considering interactions and scattering of positrons with argon (Ar) and krypton (Kr) atoms, we have calculated total cross-sections (Q _T?=?Q _el?+?Q _inel ) using complex spherical potentials for these systems. In positron?Catom scattering it is difficult to bifurcate the ionization and cumulative excitation contained in the total inelastic cross-section. An approximate method called CSP-ic (complex scattering potential-ionization contribution) similar to electron?Catom scattering has been applied to bifurcate ionization and cumulative excitation cross-sections at energies from the threshold to 2000?eV. Adequate comparisons of the present results are made, with available data.     

Level density and radiative strength functions from (n th,2γ) reactions and basic properties of the 96Mo nucleus

Published data on the intensities of two-step cascades to 12 final-state levels of the ⁹⁶Mo nucleus are approximated by using a set of possible random dependences of the level density and radiative strength functions for primary E1 and M1 transitions. The average values of these parameters of gamma decay for any excitation energies and for gamma transitions agree well with basic dependences revealed to date from similar experiments for 42 nuclei in the mass-number range 40 ≤ A ≤ 200, but they are inconsistent with the generally accepted ideas of the parameters of the cascade gamma decay of compound states of nuclei having high level densities.     

Neutron Background from the (α, n) Reaction on 13C in the EDELWEISS-II experiment on direct search for weakly interacting particles of nonbaryonic cold dark matter

The purpose of the work is to evaluate the neutron background from an additional neutron source, the (α, n) reaction on ¹³C, in the polyethylene neutron shielding of the EDELWEISS-II experiment on the search for weakly interacting cold matter particles. The characteristic length of radon diffusion into polyethylene is obtained, the neutron energy spectrum is constructed, and the neutron flux from the (α, n) reaction is evaluated.     

The mechanism of the 7Li(d, 2α)n reaction from Ed = 3 to 15 MeV

The ⁷Li(d, 2α)n reaction proceeds almost entirely through excitation and sequential decay of the 16.63 and 16.92 MeV levels in ⁸Be, for incident energies 1 to 13 MeV above their threshold. The energy dependence for forming these levels with the neutron emitted at 0° is approximately that predicted assuming the neutron is a spectator from the incident deuteron. None of the individual spectra, the angular dependence of the cross section at fixed E_d, or the bombarding-energy-dependence of the cross section for forming the levels is consistent with the involvement of a spectator neutron from the ⁷Li target.     

NMR relaxation study of disorder in the mixed system BP x GPI(1–x) and the low temperature transition from classical to quantum rotation

¹H NMR spin-lattice relaxation time (T ₁) studies have been carried out in the temperature range 100 K to 4 K, at two Larmor frequencies 11.4 and 23.3 MHz, in the mixed system of betaine phosphate and glycine phosphite (BP_xGPI_(1–x)), to study the effects of disorder on the proton group dynamics. Analysis of T ₁ data indicates the presence of a number of inequivalent methyl groups and a gradual transition from classical reorientations to quantum tunneling rotations. At lower temperatures, microstructural disorder in the local environments of the methyl groups, result in a distribution in the activation energy (E_a ) and the torsional energy gap (E ₀₁). For certain values of x, the magnetisation recovery shows biexponential behaviour at lower temperatures.