Exploring the local solvation structure of redox molecules in a mixed solvent for increasing the Seebeck coefficient of thermocells.

A thermocell is an emerging alternative to thermoelectric devices and exhibits a high Seebeck coefficient () due to the large change of solvation entropy associated with redox reactions. Here, the of -chloranil radicals/dianions (CA˙) in acetonitrile was drastically increased from -1.3 to -2.

Real-time detection of acetone gas molecules at ppt levels in an air atmosphere using a partially suspended graphene surface acoustic wave skin gas sensor.

To improve the quality of modern life in the current society, low-power, highly sensitive, and reliable healthcare technology is necessary to monitor human health in real-time. In this study, we fabricated partially suspended monolayer graphene surface acoustic wave gas sensors (G-SAWs) with a love-mode wave to effectively detect ppt-level acetone gas molecules at room temperature. The sputtered SiO thin film on the surface of a black 36°YX-LiTaO (B-LT) substrate acted as a guiding layer, effectively reducing the noise and insertion loss.

Fluoroalkylated hypervalent sulfur fluorides: radical addition of arylchlorotetrafluoro-λ-sulfanes to tetrafluoroethylene.

Fluorinated groups are essential hydrophobic groups in drug design. Combining a carbon-free tetrafluoro-λ-sulfanyl (SF) group with a polyfluoroalkyl group (R) provides SFR groups, exhibiting high hydrophobicity with a short carbon chain. In this study, various aryltetrafluoro(polyfluoroalkyl)-λ-sulfanes (ArSFR) were synthesized through the radical addition of arylchlorotetrafluoro-λ-sulfanes (ArSFCl) to tetrafluoroethylene.

Using phenolic polymers to control the size and morphology of calcium carbonate microparticles.

Calcium carbonate (CaCO) is a naturally occurring mineral that occurs in biology and is used industrially. Due to its benign nature, CaCO microparticles have found use in the food and medical fields, where the specific size of the microparticles determine their functionality and potential applications. We demonstrate that phenolic polymers with different numbers of hydroxy groups can be used to control the diameter of CaCO microparticles in a range of 2-9 μm, and obtained particles were relatively uniform.

Molecular hybrids of trivacant lacunary polyoxomolybdate and multidentate organic ligands.

Functional molecular inorganic-organic hybrids of lacunary polyoxometalates and organic ligands attract much attention for advanced material applications. However, the inherent instability of lacunary polyoxomolybdates hinders the synthesis of hybrids and their utilization. Herein, we present a viable approach for the synthesis of molecular hybrids of trivacant lacunary Keggin-type polyoxomolybdates and multidentate organic ligands including carboxylates and phosphonates, which is based on the use of a lacunary structure stabilized by removable pyridyl ligands as a starting material.

Field demonstration of UV-LED disinfection at small and decentralized water facilities.

Ultraviolet light-emitting diodes (UV-LED) can be a good option for disinfecting water in small and decentralized facilities. A flow-through UV-LED disinfection module was evaluated at three remote locations in Japan. The disinfection efficiency of the module was monitored for over one year, targeting indigenous Escherichia coli, total coliforms, standard plate count, and heterotrophic plate count (HPC) bacteria.

Organocatalyzed ring-opening reactions of γ-carbonyl-substituted ε-caprolactones.

Side-chain-functionalized aliphatic polyesters are promising as functional biodegradable polymers. We have investigated ring-opening reactions of γ-carbonyl-substituted ε-caprolactones (gCCLs) to obtain poly(ε-caprolactone) (PCL) analogues. Organic catalysts and Sn(Oct) often used for the ring-opening polymerization (ROP) of ε-caprolactone (CL) have been explored to find the conditions for the formation of polymeric products of gCCLs.

Structurally Heterogeneous Amphiphilic Conetworks of Poly(vinyl imidazole) Derivatives with Potent Antimicrobial Properties and Cytocompatibility.

We report the construction of amphiphilic conetwork (APCN)-based surfaces with potent antimicrobial activity and biofilm inhibition ability. The construction strategy is based on the separation of lipophilic alkyl groups (>C6) from the cationic network to obtain good antibacterial properties. The reaction of partially alkylated poly(vinyl imidazole) with the activated halide compounds followed by coating a glass or poly(dimethylsiloxane) (PDMS) sheet leads to the formation of the APCN surface.

Design of a robust and strong-acid MOF platform for selective ammonium recovery and proton conductivity.

Metal-organic frameworks (MOFs) are potential candidates for the platform of the solid acid; however, no MOF has been reported that has both aqueous ammonium stability and a strong acid site. This manuscript reports a highly stable MOF with a cation exchange site synthesized by the reaction between zirconium and mellitic acid under a high concentration of ammonium cations (NH). Single-crystal XRD analysis of the MOF revealed the presence of four free carboxyl groups of the mellitic acid ligand, and the high first association constant (p) of one of the carboxyl groups acts as a monovalent ion-exchanging site.

A dinuclear Rh(-i)/Rh(i) complex bridged by biphilic phosphinine ligands.

Bimetallic complexes have enabled precise control of catalysis by accumulating two discrete metal centres. In these complexes, bridging ligands are essential to combine multiple metals into one molecule. Among some bridging modes, an unsymmetric bridging mode will differentiate the electronic structures of the two metal centres.

Preoperative stoma site marking reduces postoperative stoma-related complications in emergency surgery: A single center retrospective cohort study.

Background And Objective: Stoma site marking is an important factor in reducing stoma-related complications, thereby influencing the long-term quality of life in the elective setting. The impact of preoperative stoma site marking in emergency stoma creation is largely unknown. We aimed to determine whether preoperative stoma site marking in emergency stoma creation reduces stoma-related complications.

Photoluminescence control by atomically precise surface metallization of C-centered hexagold(i) clusters using N-heterocyclic carbenes.

The properties of metal clusters are highly dependent on their molecular surface structure. The aim of this study is to precisely metallize and rationally control the photoluminescence properties of a carbon(C)-centered hexagold(i) cluster (CAu) using N-heterocyclic carbene (NHC) ligands with one pyridyl, or one or two picolyl pendants and a specific number of silver(i) ions at the cluster surface. The results suggest that the photoluminescence of the clusters depends highly on both the rigidity and coverage of the surface structure.

Development of fluorogenic substrates for colorectal tumor-related neuropeptidases for activity-based diagnosis.

The M3 metalloproteases, neurolysin and THOP1, are neuropeptidases that are expressed in various tissues and metabolize neuropeptides, such as neurotensin. The biological roles of these enzymes are not well characterized, partially because the chemical tools to analyse their activities are not well developed. Here, we developed a fluorogenic substrate probe for neurolysin and thimet oligopeptidase 1 (THOP1), which enabled the analysis of enzymatic activity changes in tissue and plasma samples.

Hysteresis behavior in the unfolding/refolding processes of a protein trapped in metallo-cages.

Confinement of molecules in a synthetic host can physically isolate even their unstable temporary structures, which has potential for application to protein transient structure analysis. Here we report the NMR snapshot observation of protein unfolding and refolding processes by confining a target protein in a self-assembled coordination cage. With increasing acetonitrile content in CDCN/HO media (50 to 90 vol%), the folding structure of a protein sharply denatured at 83 vol%, clearly revealing the regions of initial unfolding.

Each side chain of cyclosporin A is not essential for high passive permeability across lipid bilayers.

We compared the passive permeability of cyclosporin A (CsA) derivatives with side chain deletions across lipid bilayers. CsA maintained passive permeability after losing any one of the side chains, which suggests that the propensity of the backbone of CsA is an important component for high passive permeability.

Photocatalytic formation of a gas permeable layer selectively deposited on supported metal nanoparticles for sintering-resistant thermal catalysis.

Nanoparticle aggregation of supported metal catalysts at high temperatures is a serious problem that causes a drop in catalytic performance. This study investigates the protection of metal nanoparticles from sintering by selectively forming nanoscale SiO shells on Pd supported on TiO by ultraviolet (UV) light irradiation. The proton-coupled reduction reaction increases the local pH around Pd nanoparticles, resulting in hydrolysis of tetraethoxyorthosilicate (TEOS) in only the vicinity of the metal.

Label-free quantification of passive membrane permeability of cyclic peptides across lipid bilayers: penetration speed of cyclosporin A across lipid bilayers.

Cyclic peptides that passively penetrate cell membranes are under active investigation in drug discovery research. PAMPA (Parallel Artificial Membrane Permeability Assay) and Caco-2 assay are mainly used for permeability measurements in these studies. However, permeability rates across the artificial membrane and the cell monolayer used for these assays are intrinsically different from the ones across pure lipid bilayers.

Particle size effect on millimeter-wave absorption, rotation, and ellipticity of gallium-substituted epsilon iron oxide.

Various applications employ millimeter waves. For example, the carrier frequencies of vehicle radar in advanced driver assistance systems are 76-81 GHz millimeter waves. Here, we investigate the particle size effect on millimeter-wave absorption of gallium-substituted epsilon iron oxide ε-Ga Fe O with = 0.

Diamond-rich crystalline nanosheets seeded with a Langmuir monolayer of arachidic acid on water.

The enigmatic self-assembling ability of nanodiamond (ND) particles has been discovered herein. Diamond-rich crystalline nanosheets with thickness of approximately ∼25 nm were grown from a Langmuir monolayer of arachidic acid (AA) at the interface between air and a dilute aqueous ND solution. Their fine rectangular shapes with uniform uniaxial birefringence indicate appreciable crystallinity, thus supporting that they are hydrated colloidal crystals of homogeneous ND particles.

Moderate molecular recognitions on ZnO -plane and their selective capture/release of bio-related phosphoric acids.

Herein, we explore the hidden molecular recognition abilities of ZnO nanowires uniformly grown on the inner surface of an open tubular fused silica capillary liquid chromatography. Chromatographic evaluation revealed that ZnO nanowires showed a stronger intermolecular interaction with phenylphosphoric acid than any other monosubstituted benzene. Furthermore, ZnO nanowires specifically recognized the phosphate groups present in nucleotides even in the aqueous mobile phase, and the intermolecular interaction increased with the number of phosphate groups.

Free energy surface of initial cap formation in carbon nanotube growth.

Initial cap formation is an important process of carbon nanotube (CNT) growth where a hexagonal carbon network is lifted off from the catalyst surface. In this study, free energy surface (FES) of initial cap formation in the CNT growth is investigated by metadynamics simulation. A two-dimensional collective variable (CV) space is newly developed to examine the complicated formation process of the cap structure, which consists of the formation of a hexagonal carbon network and lift-off of the network from the catalyst surface.

Gramicidin A accumulates in mitochondria, reduces ATP levels, induces mitophagy, and inhibits cancer cell growth.

Gramicidin A (1) is a linear 15-mer peptidic natural product. Because of its sequence of alternating d- and l-chirality, 1 folds into a β-helix in a lipid bilayer and forms a head-to-head dimer to function as a transmembrane channel for monovalent cations (H, Na, and K). The potent anticancer activity of 1 was believed to be mainly attributed to the free ion diffusion across the plasma membrane.

Molecular design of near-infrared (NIR) fluorescent probes targeting exopeptidase and application for detection of dipeptidyl peptidase 4 (DPP-4) activity.

Monitoring the activities of proteases is an important requirement in biological and medical research. Near-infrared (NIR) fluorescent probes are particularly useful for fluorescence imaging, due to the high penetration of NIR and the low autofluorescence in tissue for this wavelength region, but most current NIR fluorescent probes for proteases are targeted to endopeptidase. Here, we describe a new molecular design for NIR fluorescent probes that target exopeptidase by utilizing the >110 nm blueshift of unsymmetrical Si-rhodamines upon amidation of the N atom of their xanthene moiety.