Gravitational energy-momentum density in teleparallel gravity

In the context of a gauge theory for the translation group, a conserved energy-momentum gauge current for the gravitational field is obtained. It is a true spacetime and gauge tensor, and transforms covariantly under global Lorentz transformations. By rewriting the gauge gravitational field equation in a purely spacetime form, it becomes the teleparallel equivalent of Einstein's equation, and the gauge current reduces to the Moller's canonical energy-momentum density of the gravitational field.     

Simplest Monodentate Imidazole Stabilization of the oxy‐Tyrosinase Cu2O2 Core: Phenolate Hydroxylation through a CuIII Intermediate

Tyrosinases are ubiquitous binuclear copper enzymes that oxygenate to Cu^II₂O₂ cores bonded by three histidine Nτ‐imidazoles per Cu center. Synthetic monodentate imidazole‐bonded Cu^II₂O₂ species self‐assemble in a near quantitative manner at ?125 °C, but Nπ‐ligation has been required. Herein, we disclose the syntheses and reactivity of three Nτ‐imidazole bonded Cu^II₂O₂ species at solution temperatures of ?145 °C, which was achieved using a eutectic mixture of THF and 2‐MeTHF. The addition of anionic phenolates affords a Cu^III₂O₂ species, where the bonded phenolates hydroxylate to catecholates in high yields. Similar Cu^III₂O₂ intermediates are not observed using Nπ‐bonded Cu^II₂O₂ species, hinting that Nτ‐imidazole ligation, conserved in all characterized Ty, has functional advantage beyond active‐site flexibility. Substrate accessibility to the oxygenated Cu₂O₂ core and stabilization of a high oxidation state of the copper centers are suggested from these minimalistic models.     

Nonlinear compression of optical solitons

In this paper, we consider nonlinear Schrödinger (NLS) equations, both in the anomalous and normal dispersive regimes, which govern the propagation of a single field in a fiber medium with phase modulation and fibre gain (or loss). The integrability conditions are arrived from linear eigen value problem. The variable transformations which connect the integrable form of modified NLS equations are presented. We succeed in Hirota bilinearzing the equations and on solving, exact bright and dark soliton solutions are obtained. From the results, we show that the soliton is alive, i.e. pulse area can be conserved by the inclusion of gain (or loss) and phase modulation effects.     

Spectroscopic studies of the interaction of ferrous bleomycin with DNA

Bleomycin is an antibiotic used in cancer chemotherapy for its ability to achieve both single- and double-strand cleavage of DNA through abstraction of the deoxyribose C4'-H. Magnetic circular dichroism (MCD) and X-ray absorption (XAS) spectroscopies have been used to study the interaction of the biologically relevant FeIIBLM complex with DNA. Calf thymus DNA was used as the substrate as well as short oligonucleotides, including one with a preferred 5'-G-pyrimidine-3' cleavage site [d(GGAAGCTTCC)2] and one without [d(GGAAATTTCC)2]. DNA binding to FeIIBLM significantly perturbs the FeII active site, resulting in a change in intensity ratio of the d d transitions and a decrease in excited-state orbital splitting (5Eg). Although this effect is somewhat dependent on length and composition of the oligonucleotide, it is not correlated to the presence of a 5'-G-pyrimidine-3' cleavage site. No effect is observed on the charge-transfer transitions, indicating that the H-bonding recognition between the pyrimidine and guanine base does not perturb Fe-pyrimidine backbonding. Azide binding studies indicate that FeIIBLM bound to either oligomer has the same affinity for N3-. Parallel studies of BLM structural derivatives indicate that FeIIiso-PEPLM, in which the carbamoyl group is shifted on the mannose sugar, forms the same DNA-bound species as FeIIBLM. In contrast, FeIIDP-PEPLM, in which the -aminoalanine group is absent, forms a new species upon DNA binding. These data are consistent with a model in which the primary amine from the -aminoalanine is an FeII ligand and the mannose carbamoyl provides either a ligand to the FeII or significant second-sphere effects on the FeII site; intercalation of the bithiazole tail into the double helix likely brings the metal-bound complex close enough to the DNA to create steric interactions that remove the sugar groups from interaction with the FeII. The fact that the FeII active site is perturbed regardless of DNA sequence is consistent with the fact that cleavage is observed for both 5'-GC-3' and nonspecific oligomers and indicates that different reaction coordinates may be active, depending on orientation of the deoxyribose C4'-H.     

Microwave absorption studies of MgB2 superconductor

Microwave absorption studies have been carried out on MgB₂ superconductor using a standard X-band EPR spectrometer. The modulated low-field microwave absorption signals recorded for polycrystalline (grain size ∼ 10 μm) samples suggested the absence of weak-link character. The field dependent direct microwave absorption has been found to obey a ✓H dependence with two different slopes, which indicated a transition from strongly pinned lattice to flux flow regime.     

Effect of substrate temperature on electrical and magnetic properties of epitaxial La1−x Pb x MnO3 films

Epitaxial La_1−x Pb _x MnO₃ (LPMO) thin films, grown on (100) SrTiO₃ substrates by laser ablation technique at different temperatures between 600 and 850°C, have been characterized for electrical and magnetic properties. The temperature dependence of resistivity showed that the metal-insulator transition temperature (T _MI) decreases with increasing substrate temperature, which has been attributed to decrease in Pb content in the filsm. The YBa₂Cu₃O _x /La_1−x MnO₃ heterostructures, exhibiting both superconductivity and ferromagnetism, have been fabricated.     

Defining the electronic and geometric structure of one-electron oxidized copper-bis-phenoxide complexes

The geometric and electronic structure of an oxidized Cu complex ([CuSal](+); Sal = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV-vis-NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal](+) (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal](+), affording exclusively a Cu(III) species in the solid state (4-300 K). Variable-temperature solution studies suggest that [CuSal](+) exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal(*)](+) (S = 1) and the high-valent metal form [Cu(III)Sal](+) (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine-bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSal(red)](+) (Sal(red) = N,N'-bis(3,5-di- tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)-ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu-bis-phenoxide complexes.