Phase diagram and oxygen annealing effect of FeTe1−xSex iron-based superconductor

Phase diagrams of as-grown and O₂-annealed FeTe_1?xSe_x determined from magnetic susceptibility measurement were obtained. For as-grown samples, the antiferromagnetic order was fully suppressed in the range region x≥0.15, and weak superconductivity appeared when x≥0.1. Beginning at x=0.5, weak superconductivity was found to evolve into bulk superconductivity. Interestingly, for O₂-annealed samples, complete suppression of magnetic order and the occurrence of bulk superconductivity were observed when x≥0.1. We found that O₂-annealing induces bulk superconductivity for FeTe_1?xSe_x. Oxygen probably plays a key role in the suppression of the magnetic order and the appearance of bulk superconductivity.     

Experimental study on the reaction pathway of α‐haloacetophenones with nucleophiles: direct substitution or carbonyl addition?

The reaction of PhCOCH₂Cl with OH^– gave the expected α‐substituted alcohol (PhCOCH₂OH) in addition to three dimer products. To clarify whether the substitution product is formed by direct S_N2 or via carbonyl addition, the reaction of PhCOCH₂Cl and OMe^– was examined. The reaction gave two products, PhCOCH₂OH as the major product after acid hydrolysis and PhCOCH₂OMe as the minor product. An electron‐withdrawing substituent on the phenyl ring enhanced the overall reactivity and gave more alcohol than ether. It was concluded that the alcohol was formed via carbonyl addition‐epoxidation route, whereas the ether was formed by the direct substitution route. Copyright © 2012 John Wiley & Sons, Ltd.     

Large-scale quantum mechanical simulations of carbon nanowires

The stability of quasi-one-dimensional structures of carbon is investigated using a generalized tight-binding molecular-dynamics scheme. Large-scale simulations are made possible by the parallel implementation of the diagonalization routines. Our results show that these structures can be stable provided that their geometries consist of a core of four-fold coordinated atoms, surrounded by a three-fold coordinated outer surface accommodating one of the most stable reconstructions of bulk diamond structure.     

Freely Falling 2-Surfaces and the Effective Gravitational Mass

We derive an expression for the effectivegravitational mass for any closed spacelike 2-surface.This effective gravitational energy is defined directlythrough the geometrical quantity of the freely falling 2-surface and thus is well adapted to intuitiveexpectation that the gravitational mass should bedetermined by the motion of a test body moving freely inthe gravitational field. We find that this effective gravitational mass has a reasonable positivevalue for a small sphere in the non-vacuum space-timesand can be negative for the vacuum case. Further, thiseffective gravitational energy is compared with the quasi-local energy based on the (2 + 2)formalism of General Relativity. Although some gaugefreedoms exist, analytic expressions of the quasi-localenergy for vacuum cases are the same as the effective gravitational mass. Especially, we see that thecontribution from the cosmological constant is the samein general cases.     

A Compound I Mimic Reveals the Transient Active Species of a Cytochrome P450 Enzyme: Insight into the Stereoselectivity of P450-Catalysed Oxidations

Catching the structure of cytochrome P450 enzymes in flagrante is crucial for the development of P450 biocatalysts, as most structures collected are found trapped in a precatalytic conformation. At the heart of P450 catalysis lies Cpd I, a short-lived, highly reactive intermediate, whose recalcitrant nature has thwarted most attempts at capturing catalytically relevant poses of P450s. We report the crystal structure of P450BM3 mimicking the state in the precise moment preceding epoxidation, which is in perfect agreement with the experimentally observed stereoselectivity. This structure was attained by incorporation of the stable Cpd I mimic oxomolybdenum mesoporphyrin IX into P450BM3 in the presence of styrene. The orientation of styrene to the Mo-oxo species in the crystal structures sheds light onto the dynamics involved in the rotation of styrene to present its vinyl group to Cpd I. This method serves as a powerful tool for predicting and modelling the stereoselectivity of P450 reactions.     

Double Naphthalene‐Tagged Cyclodextrin‐Peptide Capable of Exhibiting Guest‐Induced Naphthalene Excimer Fluorescence

A cyclodextrin‐peptide hybrid (17NNβ) bearing two naphthalene units in the peptide side chain has been designed and synthesized as a novel chemosensor molecule. Circular dichroism study of the compound revealed that the peptide has α‐helix structure with a helix content of 41%. The peptide revealed both monomer and excimer emission and the intensity of the excimer emission increased while that of the monomer emission decreased upon addition of the guest compound. This behavior was observed for various guest molecules, suggesting that the system can be used for detecting molecules in aqueous solution.     

Charge–discharge performances of Li–S battery using NaI–NaBH4–LiI solid electrolyte

Journal of Solid State Electrochemistry - In this study, Li–S batteries were fabricated using 9(15NaI∙NaBH4)∙LiI as the solid electrolyte, and their charge–discharge...     

Improvement of Antibody Activity by Controlling Its Dynamics Using the Glycan–Lectin Interaction

Antibody dynamics on membranes, such as endocytosis and clustering, are vital in determining antibody functions. In this study, we demonstrated that glycan conjugation can modulate antibody dynamics through the glycan–lectin interaction to regulate its potency. The anti-HER2 antibody, an anti-breast-cancer antibody, was conjugated with galactose-containing N-glycan, and its internalization was suppressed by interaction with galectin-3, leading to enhanced complement-dependent cytotoxic (CDC) activity. This glycan–antibody conjugate is proposed as a new approach to modulate antibody activity and may provide an alternative strategy for redeveloping antibody drugs that do not exhibit sufficient activity.     

Synthesis of Quaternary and Tertiary Carbon-Substituted Arenes by Lewis Base Promoted Site-Selective Coupling with Allylic Nucleophiles

A practical method for the preparation of quaternary and tertiary allyl-substituted heteroarenes by site-selective couplings of heteroaryl nitriles and allylic nucleophiles is disclosed. Transformations utilize readily accessible stable reagents, proceed in the presence of a Lewis base activator, and undergo aryl-C(sp³) quaternary and tertiary carbon formation with high γ-selectivity (up to >98 : 2 γ : α).