Synthesis, structure and photophysical properties of a flavin-based platinum(II) complex

We synthesized a thiosemicarbazone-functionalized flavin (Fl-(H)TSC: 2-[2-(3,4-dihydro-7,8-dimethyl-2,4-dioxobenzo[g]pteridin-10(2H)-yl)ethylidene]-hydrazinecarbothioamide) and its Pt(II) complex [Pt(Fl-TSC)(2)], and characterized it using X-ray diffraction, UV-visible absorption and luminescence spectroscopy. X-ray structural analysis for [Pt(Fl-TSC)(2)] revealed that the structure of the isoalloxazine part was almost the same as that in lumiflavin (7,8,10-trimethylisoalloxazine), and the thiosemicarbazone moiety acted as a bidentate ligand to form a PtS(2)N(2) planar conformation. UV-visible absorption and luminescence spectra of these compounds were very similar to those of riboflavin, but the emission intensity and the lifetime decreased considerably. Theoretical calculations suggested that the charge-separated state (Fl˙(-)-TSC˙(+)) contributed to the faster quenching from the (1)π-π* emission state.     

Microwave-assisted functionalization of carbon nanohorns via [2+1] nitrenes cycloaddition

The microwave-assisted functionalization of carbon nanohorns (CNHs) via [2+1] nitrenes cycloaddition, providing well dispersible hybrid materials possessing aziridino-rings covalently grafted onto the graphitic network of CNHs, was accomplished, while condensation of hydroxy-functionalized CNHs with thioctic acid, furnishing an endocyclic disulfide bond extended from the aziridino-rings, allowed the stabilization of Au nanoparticles.     

Search for polytipic structures of gadolinium

Abstract

The trivalent rare-earth element gadolinium has been studied up to 8 GPa and 700°C by energy-dispersive synchrotron x-ray diffraction. Except for the known crystal structures of hcp, Sm-type, and dhcp, no long-period polytypes have been observed. It is found that the hcp structure transforms directly to the dhcp structure with increasing pressure at high temperatures.     

Differences between protein dynamics of hemoglobin upon dissociation of oxygen and carbon monoxide

Protein dynamics of human adult hemoglobin (HbA) upon ligand photolysis of oxygen (O(2)) and carbon monoxide (CO) was investigated using time-resolved resonance Raman (TR(3)) spectroscopy. The TR(3) spectra of the both photoproducts at 1-ns delay differed from that of the equilibrium deligated form (deoxy form) in the frequencies of the iron-histidine stretching [ν(Fe-His)] and methine wagging (γ(7)) modes, and the band intensity of pyrrole stretching and substituent bending (ν(8)) modes. Spectral changes of the O(2) photoproduct in the submicrosecond region were faster than those of the CO photoproduct, indicating that the structural dynamics following the photodissociation is ligand dependent for HbA. In contrast, no ligand dependence of the dynamics was observed for myoglobin, which has a structure similar to that of the subunit of HbA. The structural dynamics and relevance to the functionality of HbA also are discussed.     

Soft Crystals: Flexible Response Systems with High Structural Order

A new material concept of soft crystals is proposed. Soft crystals respond to gentle stimuli such as vapor exposure and rubbing but maintain their structural order and exhibit remarkable visual changes in their shape, color, and luminescence. Various interesting examples of soft crystals are introduced in the article. By exploring the interesting formation and phase-transition phenomena of soft crystals through interdisciplinary collaboration, new materials having both the characteristics of ordered hard crystals and those of flexible soft matter are expected.     

Iridium-catalyzed α-selective deuteration of alcohols

The development of chemoselective C(sp³)-H deuteration is of particular interest in synthetic chemistry. We herein report the α-selective, iridium(iii)-bipyridonate-catalyzed hydrogen(H)/deuterium(D) isotope exchange of alcohols using deuterium oxide (D₂O) as the primary deuterium source. This method enables the direct, chemoselective deuteration of primary and secondary alcohols under basic or neutral conditions without being affected by coordinative functional groups such as imidazole and tetrazole. Successful substrates for deuterium labelling include the pharmaceuticals losartan potassium, rapidosept, guaifenesin, and diprophylline. The deuterated losartan potassium shows higher stability towards the metabolism by CYP2C9 than the protiated analogue. Kinetic and DFT studies indicate that the direct deuteration proceeds through dehydrogenation of alcohol to the carbonyl intermediate, conversion of [Ir^III–H] to [Ir^III−D] with D₂O, and deuteration of the carbonyl intermediate to give the α-deuterated product.

An α-selective, iridium(iii)-bipyridonate-catalyzed hydrogen isotope exchange of alcohols using D₂O has been developed for the direct, chemoselective deuteration of primary and secondary alcohols, thereby providing deuterated bioactive molecules.     

Novel intermolecular carbon radical addition to a nitrone: asymmetric synthesis of alpha-amino acids

A nitrone was used as a synthetically useful radical acceptor in carbon-carbon bond-forming radical reactions; the intermolecular addition of alkyl radicals to chiral glyoxylic nitrone was studied; a high degree of stereocontrol in radical addition to glyoxylic nitrone was achieved to provide a new method for asymmetric synthesis of alpha-amino acids.