Chalcogenide derivatives of imidotin cage complexes

Reaction of the secocubane [Sn3(mu2-NHtBu)2(mu2-NtBu)(mu3-NtBu)] (1) with dibutylmagnesium produces the heterobimetallic cubane [Sn3Mg(mu3-NtBu)4] (4) which forms the monochalcogenide complexes of general formula [ESn3Mg(mu3-NtBu)4] (5a, E = Se; 5b, E = Te) upon reaction with elemental chalcogens in THF. By contrast, the reaction of the anionic lithiated cubane [Sn3Li(mu3-NtBu)4]- with the appropriate quantity of selenium or tellurium leads to the sequential chalcogenation of each of the three Sn(II) centres. Pure samples of the mono- or dichalcogenides are, however, best obtained by stoichiometric redistribution reactions of [Sn3Li(mu3-NtBu)4]- and the trichalcogenides [E3Sn3Li(mu3-NtBu)4]- (E = Se, Te). These reactions are conveniently monitored by using 119Sn NMR spectroscopy. The anion [Sn3Li(mu3-NtBu)4]- also acts as an effective chalcogen-transfer reagent in reactions of selenium with the neutral cubane [{Snmu3-N(dipp)}4] (8) (dipp = 2,6-diisopropylphenyl) to give the dimer [(thf)Sn{mu-N(dipp)}2Sn(mu-Se)2Sn{mu-N(dipp)}2Sn(thf)] (9), a transformation that results in cleavage of the Sn4N4 cubane into four-membered Sn2N2 rings. The X-ray structures of 4, 5a, 5b, [Sn3Li(thf)(mu3-NtBu)4(mu3-Se)(mu2-Li)(thf)]2 (6a), [TeSn3Li(mu3-NtBu)4][Li(thf)4] (6b), [Te2Sn3Li(mu3-NtBu)4][Li([12]crown-4)2] (7b') and 9 are presented. The fluxional behaviour of cubic imidotin chalcogenides and the correlation between NMR coupling constants and tin-chalcogen bond lengths are also discussed.     

Enantioselective oxidation of sulfides with hydrogen peroxide catalyzed by vanadium complex of sterically hindered chiral Schiff bases

Sterically hindered chiral Schiff base ligands 4a-d were prepared from an aldehyde derived from BINOL. The vanadium complexes of the ligands catalyze an efficient, enantioselective H₂O₂-promoted sulfoxidation of alkyl aryl sulfides, and enantioselectivities as high as 98-99% ee are observed in the sulfoxidation of benzyl aryl sulfides.     

Dynamic synovial fibroblasts are modulated by NBCn1 as a potential target in rheumatoid arthritis

Rheumatoid arthritis (RA) is an autoimmune disease characterized by aggressive fibroblast-like synoviocytes (FLSs) and pannus formation. Various therapeutic strategies have been developed against inflammatory cytokines in RA in recent decades. Based on the migratory features of FLSs, we examined whether modulation of the migratory module attenuates RA severity. In this study, inflamed synovial fluid-stimulated FLSs exhibited enhanced migration and migratory apparatus expression, and sodium bicarbonate cotransporter n1 (NBCn1) was identified in primary cultured RA-FLSs for the first time. The NBC inhibitor S0859 attenuated the migration of FLSs induced with synovial fluid from patients with RA or with TNF-α stimulation. Inhibition of NBCs with S0859 in a collagen-induced arthritis (CIA) mouse model reduced joint swelling and destruction without blood, hepatic, or renal toxicity. Primary FLSs isolated from the CIA-induced mouse model also showed reduced migration in the presence of S0859. Our results suggest that inflammatory mediators in synovial fluid, including TNF-α, recruit NBCn1 to the plasma membrane of FLSs to provide dynamic properties and that modulation of NBCn1 could be developed into a therapeutic strategy for RA.Subject terms: Chemotaxis, Bone, Ion channel signalling, Rheumatoid arthritis, Drug development     

27Al Magic Angle Spinning Nuclear Magnetic Resonance Study of Al1−x Cr x K(SO4)2·12H2O (x = 0, 0.07, and 0.2)

The physical properties of Al_1?x Cr _x K(SO₄)₂·12H₂O (x = 0, 0.07, and 0.2) were studied as a function of temperature using magic angle spinning nuclear magnetic resonance for ²⁷Al. On the basis of the physical properties of pure AlK(SO₄)₂·12H₂O, the effects of partially replacing Al³⁺ with Cr³⁺ ions were examined. Molecular motion changed with the concentration of Cr³⁺ ions. The relaxation process near 320 K was found to undergo molecular motion as described by the Bloembergen–Purcell–Pound theory. The activation energies, phase transition temperatures, and spin–lattice relaxation times in the rotating frame T _1ρ changed with the concentration of paramagnetic ions.     

Molecular dynamics simulation study on graphene-nanoribbon-resonators tuned by adjusting axial strain

A tunable graphene-nanoribbon (GNR)-resonator was investigated via classical molecular dynamics simulations. Resonance frequencies increased with increasing externally applied gate-force and axial-strain, and could be tuned above several hundred GHz. Tunable resonance frequencies achieved from the gate force were higher than those achieved from the axial-strain. The operating frequencies of GNR-resonators without axial-strain or with small axial-strains were most widely tuned by the gate, and almost linearly increased with increasing mean deflection. As the axial strain increased, the tunable ranges of the GNR-resonators were exponentially decreased, although the operating frequencies increased. GNR-resonators without axial-strain could be applied to wide-range-tuners, whereas GNR-resonators with high axial-strain could be applied to high-frequency-fine-tuners.     

Practical and efficient applications of novel dioxaborolanes and dioxaborinanes in the synthesis of corresponding boronates and their use in the palladium-catalyzed cross coupling reactions

The syntheses of boronates derived from the reaction of dioxaborolanes and dioxaborinanes with either organolithium or organomagnesium reagents are investigated along with their subsequent use in the palladium cross coupling reaction. The intrinsic stability of these cyclic esters contributes to their facile reaction with both lithium and magnesium nucleophiles at mild and safe conditions. We have found that many of the reactions proceed at room temperature which is a significant improvement over the traditional routes which require cryogenic temperatures. The scope of these reactions and their practical application to large scale process synthesis is described.     

Micromorphology of epicuticular wax structures of the garden strawberry leaves by electron microscopy: Syntopism and polymorphism

Ultrastructural aspects of leaf epicuticular wax structures were investigated in the garden strawberry Fragaria × ananassa by scanning and transmission electron microscopy. Both the adaxial and abaxial surfaces of two cultivars (Maehyang and Red Pearl) were collected and subjected to surface observations and ultrathin sections. The most prominent leaf epicuticular wax structures included membraneous platelets and angular rodlets. Most wax platelets were membraneous, and appeared to protrude from the surface at an acute angle. Angular rodlets were usually bent and had rather distinct facets in the abaxial surface of the two cultivars. Membraneous platelets were predominant on the adaxial surface of Maehyang, whereas the adaxial surface of Red Pearl was characterized by angular rodlets. However, both cultivars possessed angular rodlets on the abaxial surface, simultaneously. The combination of air-drying without vacuum and in-lens imaging of secondary electron signals with a field emission gun could impart the superb resolution at low electron dose with minimal specimen shrinkage. In vertical profiles of the leaf epidermis, epicuticular waxes were observed above the cuticle layer, and measured approximately as 50 nm in thickness. The natural epicuticular waxes were seemingly mixtures of electron-dense microfibrils, and heterogeneous in shape on ultrathin sections. Distinct crystal-like strata could be hardly discernable in the wax structures. These results suggest that the garden strawberry has the nature of syntopism within one plant and polymorphism within the same species in the formation and occurrence of leaf epicuticular waxes.     

Abnormal Li diffusion in β-LiGa by the formation of defect complex

The diffusion coefficients of Li in the NaTl-type Li intermetallic compound of β-LiGa have been measured by using a short-lived radioactive diffusion tracer. As the tracer, the α-emitting radioisotope of ⁸Li delivered as the energetic and pulsed beam from Tokai Radioactive Ion Accelerator Complex (TRIAC) was implanted into the β-LiGa compounds with the composition in the range of about 43 to 54 at.% Li. By analyzing the time-dependent yields of the α-particles measured according to the repetition cycle of the beam, the tracer diffusion coefficients were extracted over the wide range of Li composition. Abnormal composition-dependence of Li diffusion coefficients in β-LiGa was observed; the stoichiometric β-LiGa showed the highest diffusivity of Li. By referring to the composition-dependent diffusivity of Li in the iso-structural β-LiAl and β-LiIn, we could identify the abnormal diffusion of Li in very Li-poor composition of β-LiGa. The anomaly has been discussed qualitatively in terms of the formation of defect complex and the interaction between the constitutional defects.     

MR microscopy of micron scale structures

Magnetic resonance (MR) microscopy of up to 1–5-μm resolutions have been reported previously. The tested phantom structures, however, had widths one order of magnitude bigger than the reported resolutions, e.g., spherical beads or capillary tubes of tens-of-micron diameters or wall thicknesses have been imaged. In this study, we fabricated structures having a few micron widths on a silicon wafer and imaged them using our 1-μm-resolution MR microscopy at 14.1 T. Micron scale width structures were, for the first time, resolved by MR microscopy.