Circular dichroism of polyethylenimine containing optically active thymine derivatives as grafted pendants

Optical properties of linear polyethylenimine containing optically active (+)- or (?)-2-(thymin-1-yl)propionyl group as grafted pendant were investigated by circular dichroism (CD) and compared with those of the related monomer and dimer model compounds. CD spectra of the polymer in neutral aqueous solution were different from those of related model compounds, which suggest that the polymer exists in some ordered conformation (at least locally) to allow exciton coupling of π–π^* (B_2u) transition in the base chromophores along the polymer chain. This ordered conformation tends to be randomized on heating. The effects of complementary base pairing on the CD spectra have also been studied by using a linear polyethylenimine containing (±)-2-(adenin-9-yl) propionyl grafts and its related monomer and dimer models.     

Impact of the macrocyclic structure and dynamic solvent effect on the reactivity of a localised singlet diradicaloid with π-single bonding character

Localised singlet diradicals are key intermediates in bond homolysis processes. Generally, these highly reactive species undergo radical–radical coupling reaction immediately after their generation. Therefore, their short-lived character hampers experimental investigations of their nature. In this study, we implemented the new concept of “stretch effect” to access a kinetically stabilised singlet diradicaloid. To this end, a macrocyclic structure was computationally designed to enable the experimental examination of a singlet diradicaloid with π-single bonding character. The kinetically stabilised diradicaloid exhibited a low carbon–carbon coupling reaction rate of 6.4 × 10³ s⁻¹ (155.9 μs), approximately 11 and 1000 times slower than those of the first generation of macrocyclic system (7.0 × 10⁴ s⁻¹, 14.2 μs) and the parent system lacking the macrocycle (5 × 10⁶ s⁻¹, 200 ns) at 293 K in benzene, respectively. In addition, a significant dynamic solvent effect was observed for the first time in intramolecular radical–radical coupling reactions in viscous solvents such as glycerin triacetate. This theoretical and experimental study demonstrates that the stretch effect and solvent viscosity play important roles in retarding the σ-bond formation process, thus enabling a thorough examination of the nature of the singlet diradicaloid and paving the way toward a deeper understanding of reactive intermediates.

An extremely long-lived localised singlet diradical with π-single bonding character is found in a macrocyclic structure that retards the radical–radical coupling reaction by the “stretch and solvent-dynamic effects”.     

Biotransformation of benzaldehyde-type and acetophenone-type derivatives by Pharbitis nil hairy roots

The glucosylation of some coumarin and flavone derivatives on incubation with the hairy roots of morning glory (Pharbitis nil) was previously reported. We further studied the biotransformation of benzaldehyde- and acetophenone-type derivatives. Vanillin and isovanillin were reduced to alcoholic derivatives and glucosylated at the phenolic and the alcoholic hydroxyl groups. In the case of 3,4-dihydroxybenzaldehyde, the formyl group was reduced and the 3-hydroxyl or 4-hydroxyl groups were glucosylated to give monoglucosides. The 3-hydroxyl group was predominantly glucosylated to the 4-hydroxyl group. 4-beta-D-Glucopyranosyloxy-3-methoxybenzylalcohol was obtained in low yield. In time-course experiments with vanillin, it was found that the high-level reduction of the formyl group and glucosylation of the phenolic hydroxyl group occurred, and finally 4-O-beta-D-glucopyranosylvanillylalcohol was obtained as the main product. In the case of 3,4-dimethoxybenzaldehyde, 3,4,5-trimethoxybenzaldehyde, and salicylaldehyde, the formyl groups were reduced, and then the hydroxyl groups at the benyl position were glucosylated to give alcoholic glucosides in relatively high yields. In 4-hydroxy-3-methoxyacetophenone, the 4-hydroxyl group was glucosylated and two dimerized glucosides, biphenyl and biphenylether types, were obtained in low yields. In acetophenone, 1-beta-D-glucopyranosyloxy-1-phenylethane and 2-beta-D-glucopyranosyloxyacetophenone were obtained. As mentioned above P. nil hairy roots showed various biotransformative activities including glucosylation of phenolic and benzylic hydroxyl groups, reduction of the formyl group near the benzene ring, and phenol oxidation dimerization. The glucosylation reaction was especially interesting for the production of valuable glucosides.     

Field survey of Glycyrrhiza plants in Central Asia (3). Chemical characterization of G. glabra collected in Uzbekistan

The chemical characteristics of Glycyrrhiza glabra L. were investigated at a habitat in Uzbekistan. HPLC analysis of the underground parts indicated that glycyrrhizin contents varied from 3.3 to 6.1% of dry weight, and that glabridin, a species-specific flavonoid for G. glabra, was detected in all underground samples (0.08-0.35% of dry weight). HPLC analysis of the leaves indicated that G. glabra plants collected in the present study could be divided into two types, RT-type and IQ-type, according to their major flavonol glycosides, rutin or isoquercitrin, respectively.     

Data-driven exploration for pressure-induced superconductors using diamond anvil cell with boron-doped diamond electrodes and undoped diamond insulating layer

ABSTRACT

Data-driven exploration for pressure-induced superconductors was performed based on the high-throughput first-principles screening of electronic band structures. In the screening conditions, we focused on the characteristics including a narrow band gap, flat band feature, and possibility of metallization under high pressure. The 27 promising compounds were screened out from the database of Atomwork for the candidates of new pressure-induced superconductors. Among the candidates, we actually synthesized three compounds in a single crystal, and all candidates exhibited the pressure-induced superconductivity. For the in-situ electrical transport measurements, we developed a novel configuration of diamond anvil cell with boron-doped diamond electrodes and an undoped diamond insulating layer. The discovered new pressure-induced superconductors via the data-driven approach and the developed diamond anvil cell were summarized in this paper.     

Aurophilic Interactions in Multi-Radical Species: Electronic-Spin and Redox Properties of Bis- and Tris-[(Nitronyl Nitroxide)-Gold(I)] Complexes with Phosphine-Ligand Scaffolds

Multinuclear Au^I complexes with two or three nitronyl nitroxide-2-ide radical anion and phosphine-ligand scaffolds, (NN-Au)₂-1 o , (NN-Au)₂-1 m , and (NN-Au)₂-1 p , have been synthesized to investigate the influence of Au^I−Au^I (aurophilic) interactions on the properties of multispin molecular systems. The desired complexes were successfully prepared in moderate yields in a one-pot synthesis from the corresponding phosphine ligand, Au^I source, parent NN, and sodium hydroxide. Among the prepared complexes, (NN-Au)₂-1 o , in which an aurophilic interaction was clearly observed by crystal structure analysis, showed characteristic spin−spin interactions, electrochemical properties, and solvatochromic behavior. The results from theoretical calculations also suggested that the differences in properties between complex (NN-Au)₂-1 o and the other complexes are due to intramolecular aurophilic interactions.     

Coexistence of wave propagation and oscillation in the photosensitive Belousov-Zhabotinsky reaction on a circular route

The photosensitive Belousov-Zhabotinsky (BZ) reaction was investigated on a circular ring, which was drawn using computer software and then projected on a film soaked with BZ solution using a liquid-crystal projector. Under the initial conditions, a chemical wave propagated with a constant velocity on the black ring under a bright background. When the background was rapidly changed to dark, coexistence of the oscillation on part of the ring and propagation of the chemical wave on the other part was observed. These experimental results are discussed in relation to the nature of the photosensitive BZ reaction and theoretically reproduced based on a reaction-diffusion system using the modified Oregonator model.