Modification of magnetic anisotropy in metallic glasses using high-energy ion beam irradiation

Heavy ion irradiation in the electronic stopping power region induces macroscopic dimensional change in metallic glasses and introduces magnetic anisotropy in some magnetic materials. The present work is on the irradiation study of ferromagnetic metallic glasses, where both dimensional change and modification of magnetic anisotropy are expected. Magnetic anisotropy was measured using Mössbauer spectroscopy of virgin and irradiated Fe₄₀Ni₄₀B₂₀ and Fe₄₀Ni₃₈Mo₄B₁₈ metallic glass ribbons. 90 MeV ¹²⁷I beam was used for the irradiations. Irradiation doses were 5×10¹³ and 7.5×10¹³ ions/cm². The relative intensity ratios D ₂₃ of the second and third lines of the Mössbauer spectra were measured to determine the magnetic anisotropy. The virgin samples of both the materials display in-plane magnetic anisotropy, i.e., the spins are oriented parallel to the ribbon plane. Irradiation is found to cause reduction in magnetic anisotropy. Near-complete randomization of magnetic moments is observed at high irradiation doses. Correlation is found between the residual stresses introduced by ion irradiation and the change in magnetic anisotropy.     

Below-bandgap refractive index of AlAs/GaAs multiple quantum wells

Precision reflection measurements were performed on GaAs/AlAs superlattices of the same composition but different layer spacings. Nonlinear-least-squares fits to the data were performed to a single layer. Measurements were extracted for the superlattice thickness, thickness of a disturbed interface layer between the superlattice and substrate, the uniformity in composition and/or spacing and the composition. It was demonstrated that these nondestructive measurements in the infrared region (3000 to 12 000 cm^–1) in conjunction with a simple single layer model are capable of accurately yielding the above quantities with high precision.     

PHOTOCHEMISTRY OF ALL-TRANS- AND 13-CIS-14,15-DIDEUTERIORETINAL

Abstract— All- trans - and 13- cis -14,15-dideuterioretinal were synthesized and their solution photochemistry examined. Quantum yields of trans → cis or cis → trans photoisomerization and the number and ratio of primary photoproducts, determined by high pressure liquid chromatographic analysis, are essentially identical to that of their corresponding retinal isomer. The C-14, C-15 carbon-hydrogen modes play no particularly important role in the deactivation of electronically excited linear polyenes related to retinal.     

Transient absorption spectral evidence for phenyl nitrene as the chain propagator in the photo-initiated autocatalytic chain decomposition of phenyl azide and phenyl isocyanate

Transient absorption spectra were recorded 15 ns to 6 μs following a 266 nm laser pulse for phenyl azide and for phenyl isocyanate in aerated acetonitrile and 3-methylpentane solutions. Transient spectra which are independent of concentration and of delay time, are essentially identical for phenyl azide and for phenyl isocyanate, except at higher energies where phenyl azide absorbs, and are assigned as that of triplet phenyl nitrene. Since there is no spectral evidence for a second species, phenyl nitrene is thought the chain propagator in the autocatalytic chain decomposition that occurs for phenyl azide and for phenyl isocyanate.     

Collagen stability: insights from NMR spectroscopic and hybrid density functional computational investigations of the effect of electronegative substituents on prolyl ring conformations

Collagen-like peptides of the type (Pro-Pro-Gly)(10) fold into stable triple helices. An electron-withdrawing substituent at the H(gamma)(3) ring position of the second proline residue stabilizes these triple helices. The aim of this study was to reveal the structural and energetic origins of this effect. The approach was to obtain experimental NMR data on model systems and to use these results to validate computational chemical analyses of these systems. The most striking effects of an electron-withdrawing substituent are on the ring pucker of the substituted proline (Pro(i)) and on the trans/cis ratio of the Xaa(i-1)-Pro(i) peptide bond. NMR experiments demonstrated that N-acetylproline methyl ester (AcProOMe) exists in both the C(gamma)-endo and C(gamma)-exo conformations (with the endo conformation slightly preferred), N-acetyl-4(R)-fluoroproline methyl ester (Ac-4R-FlpOMe) exists almost exclusively in the C(gamma)-exo conformation, and N-acetyl-4(S)-fluoroproline methyl ester (Ac-4S-FlpOMe) exists almost exclusively in the C(gamma)-endo conformation. In dioxane, the K(trans/cis) values for AcProOMe, Ac-4R-FlpOMe, and Ac-4S-FlpOMe are 3.0, 4.0, and 1.2, respectively. Density functional theory (DFT) calculations with the (hybrid) B3LYP method were in good agreement with the experimental data. Computational analysis with the natural bond orbital (NBO) paradigm shows that the pucker preference of the substituted prolyl ring is due to the gauche effect. The backbone torsional angles, phi and psi, were shown to correlate with ring pucker, which in turn correlates with the known phi and psi angles in collagen-like peptides. The difference in K(trans/cis) between AcProOMe and Ac-4R-FlpOMe is due to an n-->pi interaction associated with the Bürg-Dunitz trajectory. The decrease in K(trans/cis) for Ac-4S-FlpOMe can be explained by destabilization of the trans isomer because of unfavorable electronic and steric interactions. Analysis of the results herein along with the structures of collagen-like peptides has led to a theory that links collagen stability to the interplay between the pyrrolidine ring pucker, phi and psi torsional angles, and peptide bond trans/cis ratio of substituted proline residues.     

Long‐Lived Spin States for Low‐Field Hyperpolarized Gas MRI

Parahydrogen induced polarization was employed to prepare a relatively long‐lived correlated nuclear spin state between methylene and methyl protons in propane gas. Conventionally, such states are converted into a strong NMR signal enhancement by transferring the reaction product to a high magnetic field in an adiabatic longitudinal transport after dissociation engenders net alignment (ALTADENA) experiment. However, the relaxation time T₁ of ～0.6 s of the resulting hyperpolarized propane is too short for potential biomedical applications. The presented alternative approach employs low‐field MRI to preserve the initial correlated state with a much longer decay time T_LLSS=(4.7±0.5) s. While the direct detection at low‐magnetic fields (e.g. 0.0475 T) is challenging, we demonstrate here that spin‐lock induced crossing (SLIC) at this low magnetic field transforms the long‐lived correlated state into an observable nuclear magnetization suitable for MRI with sub‐millimeter and sub‐second spatial and temporal resolution, respectively. Propane is a non‐toxic gas, and therefore, these results potentially enable low‐cost high‐resolution high‐speed MRI of gases for functional imaging of lungs and other applications.     

Heterogeneous Solution NMR Signal Amplification by Reversible Exchange

A novel variant of an iridium‐based organometallic catalyst was synthesized and used to enhance the NMR signals of pyridine in a heterogeneous phase by immobilization on polymer microbead solid supports. Upon administration of parahydrogen (pH₂) gas to a methanol mixture containing the HET‐SABRE catalyst particles and the pyridine, up to fivefold enhancements were observed in the ¹H NMR spectra after sample transfer to high field (9.4 T). Importantly, enhancements were not due to any residual catalyst molecules in solution, thus supporting the true heterogeneity of the SABRE process. Further significant improvements may be expected by systematic optimization of experimental parameters. Moreover, the heterogeneous catalyst is easy to separate and recycle, thus opening a door to future potential applications varying from spectroscopic studies of catalysis, to imaging metabolites in the body without concern of contamination from expensive and potentially toxic metal catalysts or accompanying organic molecules.     

The influence of a transverse magnetic field on a subnormal glow discharge in air

In subnormal glow discharge under d.c. excitation at different pressure in a varying transverse magnetic field (0 to 30 G) some measurements have been carried out for various initial average tube currents. The voltage across the discharge increases and average tube current and residual current decreases in the magnetic field. With the help of Beckman’s expression [4] for the axial field and the electron density distribution in a transverse magnetic field the observed variation of current and voltage can be satisfactorily explained. The variation of axial electric field with transverse magnetic field can be represented to a fair degree of accuracy by the derived equation. The behaviour of residual current with magnetic field has been observed in these oscillations.