2D hexagonal assembly of a dipolar rotor with a close interval of 0.8 nm using a triptycene-based supramolecular scaffold.

Controlling the rotation of carbon-carbon bonds, which is ubiquitous in organic molecules, to create functionality has been a subject of interest for a long time. In this context, it would be interesting to explore whether cooperative and collective rotation could occur if dipolar molecular rotors were aligned close together while leaving adequate space for rotation. However, it is difficult to realize such structures as bulk molecular assemblies, since molecules generally tend to assemble into the closest packing structure to maximize intermolecular forces.

Manipulating the functionality and structures of π-conjugated polymers utilizing intramolecular noncovalent interactions towards efficient organic photovoltaics.

Careful control of electronic properties, structural order, and solubility of π-conjugated polymers is central to the improvement of organic photovoltaic (OPV) performance. In this work, we designed and synthesized a series of naphthobisthiadiazole-quaterthiophene copolymers by systematically replacing the alkyl groups with ester groups and changing the position of the fluorine groups in the quaterthiophene moiety. These alterations lowered the HOMO and LUMO energy levels and systematically varied the combination of intramolecular noncovalent interactions such as O⋯S and F⋯S interactions in the backbone.

New insights into the oxidation process from neutron and X-ray crystal structures of an O-sensitive [NiFe]-hydrogenase.

[NiFe]-hydrogenase from Miyazaki F is an O-sensitive enzyme that is inactivated in the presence of O but the oxidized enzyme can recover its catalytic activity by reacting with H under anaerobic conditions. Here, we report the first neutron structure of [NiFe]-hydrogenase in its oxidized state, determined at a resolution of 2.20 Å.

Rational design for the fabrication of bulk NiSn alloy catalysts for the synthesis of 1,4-pentanediol from biomass-derived furfural without acidic co-catalysts.

This study describes the rational design for the fabrication of bulk NiSn alloy catalysts for the de/hydration-hydrogenation of biomass-derived furfural (FFald) to 1,4-pentanediol (1,4-PeD) without the acidic co-catalyst. The presence of both hydration active sites (Brønsted acid sites (Ni-SnO)) and hydrogenation active sites (Ni or Ni-Sn alloy) in NiSn alloy could be controlled by changing the pH of Ni-Sn solution during the preparation. Both active sites acted synergistically to catalyse the de/hydration-hydrogenation reactions of FFald to produce a high yield of 1,4-PeD in a batch reaction system at 433 K, 3.

Fine-tuning of the size of supramolecular nanotoroids suppresses the subsequent catenation of nano-[2]catenane.

A judicious combination of ring-closing supramolecular polymerization and secondary nucleation can hierarchically organize a diphenylnaphthalene barbiturate monomer bearing a 3,4,5-tri(dodecyloxy)benzyloxy unit into self-assembled nano-polycatenanes composed of nanotoroids. In our previous study, nano-polycatenanes of variable length have been formed uncontrollably from the monomer that provides nanotoroids with sufficiently wide inner void space wherein secondary nucleation is driven by non-specific solvophobic interaction. In this study, we found that the elongation of the alkyl chain length of the barbiturate monomer decreases the inner void space of nanotoroids while increasing the frequency of secondary nucleation.

Impact of localized surface plasmon resonance on efficiency of zinc oxide nanowire-based organic-inorganic perovskite solar cells fabricated under ambient conditions.

Organometal halide perovskites as hybrid light absorbers have been investigated and used in the fabrication of perovskite solar cells (PSCs) due to their low-cost, easy processability and potential for high efficiency. Further enhancing the performance of solution processed PSCs without making the device architecture more complex is essential for commercialization. In this article, the overall improvement in the performance of ZnO nanowires (NWs)-based PSCs fabricated under ambient conditions, incorporating Ag nanoparticles (NPs) delivering a device efficiency of up to 9.

Slippage- and load-induced changes in the crystalline orientation of oligo(3-methoxythiophene) powder to develop a gold-tone luster.

The achievement of molecular orientation control by rubbing and pressing poly(3-alkylthiophene)s is a powerful technique to improve the performance of organic electronic devices. We report here that the rubbing and pressing of blackish-brown 3-methoxythiophene oligomer powders yield layer and tablet samples with gold tones, respectively. Specular reflectivity, colorimetric, and X-ray diffraction measurements reveal that this gold tone is caused by an increase in the ratio of edge-on lamellar crystallites to face-on ones, which is promoted by rubbing/pressing.

Intermolecular Dynamics of Positively and Negatively Charged Aromatics and Their Isoelectronic Neutral Analogs in Aqueous Solutions.

In this study, we investigated the temperature dependence of intermolecular vibrations and orientational dynamics in the aqueous solutions of imidazole hydrochloride, imidazole, sodium triazolide, and triazole using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES) and steady-state Raman spectroscopy. The difference low-frequency Raman spectra under 250 cm of the aqueous solutions relative to the neat water showed that the spectral shoulder in the high-frequency region at 60-100 cm, assigned to the libration of an aromatic ring, was higher in frequency for the imidazolium cation but lower for the triazolide anion than those of the respective neutral aromatics. The results of the ab initio quantum chemistry calculations of the clusters of the aromatics and water molecule(s) were consistent with the experimental spectra of the aqueous solutions.

Two-photon excitable boron complex based on tridentate imidazo[1,5-]pyridine ligand for heavy-atom-free mitochondria-targeted photodynamic therapy.

We have synthesized a cyan fluorescent boron complex based on a tridentate imidazo[1,5-]pyridine ligand. The boron complex was found to have potential applications as not only a chiroptical material but also a heavy-atom-free mitochondria-targeted photosensitizer for cancer treatment.

Unravelling the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol catalysed by supported RANEY® Ni-Sn alloy catalysts.

Bimetallic Ni-Sn alloys have been recognised as promising catalysts for the transformation of furanic compounds and their derivatives into valuable chemicals. Herein, we report the utilisation of a supported bimetallic RANEY® nickel-tin alloy supported on aluminium hydroxide (RNi-Sn()/AlOH; is Ni/Sn molar ratio) catalysts for the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol (1,4-PeD). The as prepared RNi-Sn(1.

Photo-modulation of supramolecular polymorphism in the self-assembly of a scissor-shaped azobenzene dyad into nanotoroids and fibers.

Recent advances in the research field of supramolecularly engineered dye aggregates have enabled the design of simple one-dimensional stacks such as fibers and of closed structures such as nanotoroids (nanorings). More complex and advanced supramolecular systems could potentially be designed using a molecule that is able to provide either of these distinct nanostructures under different conditions. In this study, we introduced bulky but strongly aggregating cholesterol units to a scissor-shaped azobenzene dyad framework, which affords either nanotoroids, nanotubes, or 1D fibers, depending on the substituents.

Fluorescent supramolecular polymers of barbiturate dyes with thiophene-cored twisted π-systems.

Because supramolecular polymerization of emissive π-conjugated molecules depends strongly on π-π stacking interaction, the formation of well-defined one-dimensional nanostructures often results in a decrease or only a small increase of emission efficiency. This is also true for our barbiturate-based supramolecular polymers wherein hydrogen-bonded rosettes of barbiturates stack quasi-one-dimensionally through π-π stacking interaction. Herein we report supramolecular polymerization-induced emission of two regioisomeric 2,3-diphenylthiophene derivatives functionalized with barbituric acid and tri(dodecyloxy)benzyl wedge units.

Nitroxyl Catalysts for Six-Membered Ring Bromolactonization and Intermolecular Bromoesterification of Alkenes with Carboxylic Acids.

We developed a nitroxyl-catalyzed bromoesterification of alkenes with bromo reagents, which includes a six-membered ring bromolactonization of alkenyl carboxylic acids catalyzed by AZADO as the nitroxyl radical catalyst, and an intermolecular bromoesterification of alkenes with carboxylic acids using NMO as the -oxide catalyst. We also accomplished a remote diastereoselective bromohydroxylation via an AZADO-catalyzed six-membered ring bromolactonization and a subsequent ring cleavage reaction with alkylamines to furnish ε-bromo-δ-hydroxy amides with high diastereoselectivity.

Formation of pressurizable hydrogel-based vascular tissue models by selective gelation in composite PDMS channels.

Vascular tissue models created are of great utility in the biomedical research field, but versatile, facile strategies are still under development. In this study, we proposed a new approach to prepare vascular tissue models in PDMS-based composite channel structures embedded with barium salt powders. When a cell-containing hydrogel precursor solution was continuously pumped in the channel, the precursor solution in the vicinity of the channel wall was selectively gelled because of the barium ions as the gelation agent supplied to the flow.

Valosin-containing Protein is a Target of 5'-l Fuligocandin B and Enhances TRAIL Resistance in Cancer Cells.

Fuligocandin B () is a novel natural product that can overcome TRAIL resistance. We synthesized enatiomerically pure fuligocandin B () and its derivative 5'-I fuligocandin B (), and found that the latter had an improved biological activity against the human gastric cancer cell line, AGS. We attached a biotin linker and photoactivatable aryl diazirine group to 5'-I fuligocandin B (), and employed a pull-down assay to identify valosin-containing protein (VCP/p97), an AAA ATPase, as a 5'-I fuligocandin B () target protein.

Effects of light wavelength on MEG ERD/ERS during a working memory task.

We investigated the effects of light wavelengths on cortical oscillatory activity associated with working memory processes. Cortical activity responses were measured using magnetoencephalography (MEG) while participants performed an auditory Sternberg memory task during exposure to light of different wavelength. Each trial of the memory task consisted of four words presented as a memory set and one word presented as a probe.

Plasma physics. Stochastic electron acceleration during spontaneous turbulent reconnection in a strong shock wave.

Explosive phenomena such as supernova remnant shocks and solar flares have demonstrated evidence for the production of relativistic particles. Interest has therefore been renewed in collisionless shock waves and magnetic reconnection as a means to achieve such energies. Although ions can be energized during such phenomena, the relativistic energy of the electrons remains a puzzle for theory.

Native zona pellucida structure is required for completion of sperm acrosome reaction in porcine fertilization.

In fertilization in vitro, the penetration rate of zona-intact porcine oocytes by cryopreserved epididymal spermatozoa was about 100% while that of zona-free oocytes was only 30%. Spermatozoa treated with calcium ionophore A23187 penetrated both zona-intact and zona-free oocytes at the rate of more than 90%. Treatment of spermatozoa with solubilized procine zonae pellucidae hardly induced acrosome reaction and did not increase the penetration rate.