The pH dependence of electron-donating ability of triethanolamine in visible-light driven H2 production system of water-soluble zinc porphyrin, methylviologen and colloidal platinum nanoparticle dispersed with polyvinylpyrrolidone (Pt-PVP) was investigated using a redox potential/pH diagram.

Artificial ligands that recognize membrane receptors with high affinity and specificity provide a means for the precise control of receptor activity and the resulting biological functions. In the present work, we focused on a previously reported DNA aptamer that is a functional mimic of fibroblast growth factor (FGF) and evaluated its receptor specificity. It was revealed that the aptamer works as

Homo- and heterometallic trinuclear complexes with an acyclic N2O6-type ligand, [Ni3(L)2(CH3COO)2]·H2O·MeOH (1) and [NiCu2(L)2(CH3COO)2]·3H2O (2) (H2L = N,N'-(hexane-1,6-diyl)bis(2-hydroxy-3-methoxybenzamide), were prepared, respectively, which characterized crystal structures as well as magnetic properties. The axial Cu-O bond lengths in complex 2 are 2.338-2.413 Å, unlike Ni-O, due to the axial bond

Ring-hydrogenation of 4-propylphenol (4-PP) to 4-propylcyclohexanone, cis- and trans-4-propylcyclohexanols proceeded over graphite-supported palladium catalysts (Pd/G) in aqueous ethanol solution at 573 K without using external hydrogen gas. Compared to Pd/G, graphite-supported platinum (Pt/G) catalysts were active only for hydrogen production and not for the ring-hydrogenation under the same reaction

Using the both quantum chemical and molecular dynamics calculations free energy profiles during membrane permeable processes of Ala-containing cyclic dipeptides were evaluated with moderate computational costs. Since the balance between hydrophobicity and hydrophilicity is a key factor in the membrane permeation processes, Ala-Ala and Ala-Pro might be permeable, but Ala-Asn is not owing to the high

CO2 reduction catalysts are an important aspect of global warming prevention. Herein, electrocatalytic CO2 reduction using Agn(NO3)n+1 clusters is reported. In contrast to various other Ag catalysts that reduce CO2 to CO, these Agn(NO3)n+1 clusters catalyze the electrochemical CO2 reduction reaction to produce HCOOH, with a Faraday efficiency of 33%. A size effect, the Ag valence stability and inorganic

We herein report a direct addition reaction of simple alkylarenes to imines, which is driven by irradiation of the reactants with visible light in the presence of an iridium photoredox complex and a bromide anion. Phenethylamines including densely-substituted derivatives are synthesized in an atom-economical fashion.

Structure transformation of dual reactive coordination polymers in solid state is unique but rarely reported. In this work, dual reactive Znbpe was successfully prepared, whose solid-state structure transformation was realized by UV light and ozone on the same crystal with different order. The products of structure transformation from Znbpe, Znbpe-OL and Znbpe-LO, exhibit similar rod-like morphology

Graphitic carbon nitride (CN) is considered to be an attractive material for application in photoelectrochemical (PEC) water splitting cells and photoelectronic devices. However, it is still a challenge to fabricate high-quality CN films. Herein, high-quality CN films have been synthesized via close-spaced thermal copolymerization of dicyandiamide and cyanuric acid for the first time. This method cannot

Today, people are exposed to a wide variety of different airborne pollutants such as PM2.5 and pollen. It is expected to develop novel materials to avoid their adhesion. The roughness at the interface is very important for the adhesion between such pollutants and a substrate. In this study, we have focused on self-assembling fibers formed from an amphiphilic peptide, Palmitoyl-glycine-histidine (Pal-GH)

Hierarchical structure was successfully created in YNU-5 zeolite by a direct base-treatment. Although the unmodified YNU-5 catalyst was significantly deactivated by heavy coking in hexane cracking, the dealuminated catalyst was much less deactivated. Furthermore, the mesopore/micropore hierarchical structure in the YNU-5 zeolite catalyst suppressed deactivation more than the non-hierarchical, dealuminated

We demonstrate that a dipole-dipole interaction of the benzo[c][1,2,5]thiadiazole moieties, directional H-bond formation of carboxy groups, and a rigid molecular skeleton enable to yield a structurally-predictable two-dimensional hydrogen-bonded organic framework BTIA-1 from tetratopic carboxylic acid. Activated form BTIA-1a was revealed to have BET surface area of 237 m2g−1 and show selective adsorption

Since the development of imidazo[1,5-a]pyridinylidenes (imidazo[1,5-a]pyridine carbenes: IPCs) by Lassaletta, Alcarazo, and Glorius, these have been applied as ligands in catalysts, albeit that only few productive examples have been reported so far. Nevertheless, some productive IPC catalytic systems have recently been developed by several research groups, including ours. In the present account, our

Ag nanoparticle (NP)-incorporated AgI have been formed in the pores of TiO2 nanocrystalline film ([email protected]/mp-TiO2) by a successive ionic layer adsorption and reaction-photoreduction method. [email protected]/mp-TiO2 stably shows visible-light activity for the degradaion of 2-naphthol used as a model hydrosphere pollutant. Photoelectrochemical measurements indicated that the photocatalytic

Hydrogenation reactions using a non-fossil-based hydrogen sources upgrade ubiquitous molecules to useful chemicals with low environmental load and can be promoted on nanoscale inorganic catalysts (nanocatalysts). This review discusses determining factors that enhance the catalytic activity and selectivity of thermal and electrochemical hydrogenation reactions using nanocatalysts, of which the reactivity

Amphiphilic diarylethene with tri(ethylene glycol) chains as a hydrophilic moiety and octylcarbamoyl chain as a hydrophobic moiety formed a supramolecular assembly by hydrophobic interactions in water. The closed-ring isomer formed bunched vesicles made of strongly curled bilayers. When methylcellulose was added to the suspension, sheets with a width of several hundred micrometers were mainly obtained

Antibody mimetics are proteins smaller than antibodies that have antigen-binding properties. Here, we used a combination of informatic selection and experimental verification to identify from a public database several candidate scaffold proteins. From those candidates, we selected a protein with high thermal stability, bacterial expression, and mutation tolerance and used molecular engineering and

We investigated the synthesis of poly(carbon sulfide) by electroreductive polymerization of CS2. For example, a polymer was obtained in 10% yield as a black solid consisting of both crystal and amorphous states by constant potential electrolytic reduction in acetonitrile solution of Bu4NBF4. Its electrical conductivity after doping by iodine was 1.7 x 10−2 S/m. By contrast, electrical conductivity

This paper describes the syntheses of four types of nitrile N-oxides (NOs) and the studies on the thermal isomerization of NOs to isocyanates (Isocs). It is found that a bulky electron-withdrawing substituent at the ortho position of NO tends to suppress the thermal degradation of NO. The reaction rates for the thermal reactions appear to be dependent on the initial concentration. The reaction orders

Helicenes are one of attracted non-planar polycyclic aromatic hydrocarbons with their unique optical and electronic properties. In recent years, the chemistry of “multiple helicenes” with plural helicities in a single molecule has also grown rapidly as one of the research areas due to intriguing properties such as highly distorted structures, multidimensional intermolecular interactions, and the enhanced

A novel hypercrosslinked polymer (HCPs) was prepared via Friedel-Crafts alkylation reaction of Schiff base with benzene and formaldehyde dimethyl acetal (FDA) promoted by FeCl3. The HCPs was then through a metalation with Pd(II) to form heterogeneous catalyst. The protocol featured with low cost, mild conditions, available materials, easy separation and high yield. Physicochemical methods, including

Real-time observation of an electrochemical reaction at a solid–liquid interface was performed using fluorescence-yield wavelength-dispersive soft X-ray absorption spectroscopy (XAS). A dedicated electrochemical cell was prepared for this study. As a model experiment, an electrochemical oxygen evolution reaction (OER) was observed in alkaline solution (0.1 M NaOH) on the surface of a Pt thin film working

A set of electronic-structure informatics (ESI) descriptors was applied to classify modes of toxic action (MoA) of 245 phenol derivatives to the growth of Tetrahymena pyriformis. The extreme gradient boosting classification (XGBC) method was performed for classification where the synthetic minority oversampling technique (SMOTE) was employed to overcome the imbalance in the MoA classification data

We demonstrate here that DNA-binding small molecules stabilize hairpin structures formed in short tandem repeat sequences, leading to efficient contractions of repeats during in vitro DNA synthesis. Repeat contraction by synthetic small molecules shows a repeat-number and sequence selective manner.

In this study, phenolphthaleins have been introduced into hybrid tetraarylethylene bridged six-membered benzene rings and five-membered thiophene rings to construct new multifunctional molecules responding to UV/Vis light, acid/base and water. Results showed that the titled molecules exhibited distinctive photochromism and acid-base discoloration in solution, PMMA and solid state, and displayed typical

A Cu-mediated ortho-selective C–H cyanation of phenols with ethyl cyanoformate as the cyano source has been developed. The key to success is the introduction of 4,4’-di-tert-butyl-2,2’-bipyridine (dtbpy) bidentate auxiliary on the phenol oxygen, which is easily attachable, detachable, and recyclable. The newly developed protocol is tolerated to several carbonyl functional groups, which are incompatible

Local charge carrier dynamics in diketopyrrolopyrrole (DPP)-tetrabenzoporphyrin (BP)-based bulk heterojunction (BHJ) films are investigated by optical pump-terahertz probe spectroscopy. Here we focus on the effect of the alkyl chain lengths of DPP on the carrier dynamics. In contrast to the large difference in the power conversion efficiency, similar dynamics are observed between C10-DPP-BP and C4-DPP-BP

The Huynh electronic parameter (HEP) is a modern alternative method to determine ligand donor strengths by 13C NMR spectroscopy of metal NHC complexes containing the ligand of interest. Using the HEP, the electronic properties of numerous classical Werner-type and organometallic ligands have been evaluated thus far. Moreover, it has been extended to the HEP2, which provides a means to measure bidentate

A garnet-type electrolyte sheet for all-solid-state batteries was fabricated by modified cold sintering method. The pores in the electrolyte sheet were closed during the cold sintering process, and the grain-boundary resistance was reduced. The impurity phase formed after cold sintering was removed by annealing treatment at higher temperatures.

Pt nanoparticles confined in hollow mesoporous nanoreactors ([email protected]) are prepared by using Pt ions containing polymer micelles as templates. The unique hollow mesoporous nanostructures result in the greatly improved catalytic performance for deep hydrogenations of phenolic compounds to the corresponding cyclohexanol derivatives under mild reaction conditions.

A spectrally narrow band edge emission is generated in the green region from cadmium-free quantum dots comprised of silver indium gallium sulfide coated by gallium sulfide shells. The thickness of the gallium sulfide shell is increased by using gallium tris(diethyldithiocarbamate) as a supplementary precursor showing a strong adhesion with the quantum dot cores. Photoluminescence intensity and spectral

A series of dipolar-type terphenyl derivatives 1–3 featuring an electron donor (p-NMe2C6H4 group) and acceptor (p-NO2C6H4 group) unit was synthesized and their photophysical properties were investigated. By using aromatic heterocycles (thiophene, furan, pyrrole) as the π-linkers between the donor and acceptor units, significant effects on the bathochromic shift and enhancement of the two-photon absorption

Facilely synthesized thioether amphiphile can self-assemble into nanotubes in water. The nanotubes exhibit quick reactive oxygen species (ROS)-responsivity in H2O2 or against the ultraviolet-triggered ROS from the encapsulated corannulene. Oxidation of the thioether amphiphile disassembles the long nanotubes into short ones and eventually into solubilized amphiphile.

Alkaline earth metal salts of chiral bis-sulfonimide were prepared in this study. Asymmetric Diels-Alder reactions catalyzed by these metal salts were examined to evaluate the performance of bis-sulfonimide as a chiral ligand. The Diels-Alder reaction between 2-propenoyl pyrazole and cyclopentadiene catalyzed by the calcium salt afforded the cycloaddition product with moderate stereoselectivity.

Density functional theory calculation is applied to predict the stability constants for Eu3+ and Am3+ complexes in aqueous solution for molecular modelling of novel separation agents for minor actinides over lanthanides. Logarithm of experimental stability constants correlates with calculated complex formation enthalpies with high reproducibility (R2 > 0.98). Prediction of stability constants of novel

The crystal structure of a bisporphyrin cleft molecule revealed that the head-to-head dimeric structure is directed by the intermolecular self-complementary hydrogen-bonding interactions of amide groups and π-π stacking interactions. The UV/Vis absorption spectrum of the homodimeric structure in the solid-state resulted in a broad Soret band. Time-dependent density functional theory (TD-DFT) calculation

Cage siloxanes modified with diisopropylsilanol groups were synthesized and crystallized into a layered structure containing 1,3,5-trimethylbenzene molecules in the interlayer voids, which indicates that the organic groups attached to the silanol groups have an important role in the assembling behavior of cage siloxanes.

A metal-free covalent triazine framework was synthesized from 2,4,6-tricyano-1,3,5-triazine (TCT-CTF) through open-system and liquid-phase synthesis using trifluoromethanesulfonic acid as both a catalyst and a solvent. In conventional closed-system methods, metal ions used as catalysts remained even after purification, and large quantities could not be synthesized. The proposed method solved these

We investigate the response speed of thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) brushes by in situ electrical monitoring, which are grafted by surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP) on a gate electrode of a field-effect transistor (FET). A PNIPAAm brush shows the slow-phase-transition behavior for 5–6 h after a

siRNA was complexed with a β-1,3-glucan schizophyllan and intravenously administrated into mouse. The complexed siRNA was escaped from renal excretion and remained in blood. The monocytes in spleen were found to capture the complex and cause the longer residence time of the complexed siRNA as well as increased size of the complex.

A biased acid site distribution in mordenite (MOR), which refers to the enrichment of acid sites within 8-membered ring (MR) channels, was observed with the addition of N-methyl-2-pyrrolidone (NMP) in the initial gel and verified by the enhanced activity in dimethyl ether (DME) carbonylation reaction. This is the first time that lactam has been proved effective in regulating acid site distribution

The volume function was employed to predict crystal structures. Face-centered cubic and hexagonal close-packed structures were identified as minima on the function. The optimization of the function with the actual ethane crystal resulted in largely similar orientations of the molecules. Searching on the function from a random structure resulted in some minima, including a structure similar to the actual

Here we demonstrate that a guanine-to-adenine substitution within guanine repeat sequences in the MSH 5’-UTR weakens G-quadruplex stability, leading to increased protein synthesis. The abnormal protein synthesis was effectively restored to the original level with a guanine-tethered oligonucleotide by the sequence-specific reintroduction of a hetero RNA–DNA G-quadruplex into the SNP site of the 5’ UTR

A luminescent ionic liquid containing a cationic rhenium tricarbonyl complex was synthesized. UV photoirradiation of this liquid in the presence of an organic solvent vapor caused a color change and luminescence quenching via photochemical ligand exchange, thereby enabling the photocontrol of vapochromism.

Here we proposed α-l-arabinofuranosidase from Clostridium thermocellum as an enzyme for signal amplification in bioanalysis whose activity does not exist in human cells. Combination of this enzyme and β-galactosidase enabled simultaneous detection of two different antigens on live cells.

Recently, the methylammonium lead triiodide perovskite (MAPbI3) has shown great development potential in the solar cell field, and its efficiency as a perovskite solar cell (PCE) has reached 25.2%. However, poor stability is still a problem that restricts its wide application. Compared with the polycrystalline film material of MAPbI3 perovskite, the single crystal MAPbI3 material is much more stable

Here, we report the solvent dependence of the photoinduced anion exchange reaction of cesium lead halide perovskite nanocrystals (NCs) in solutions containing halomethane solvents such as CHCl3. The anion exchange speed can be controlled by the proportion of CHCl3 to NCs. The fast anion exchange reaction in CHCl3 induces the formation of defect sites on the NC surface. In contrast, the slow anion exchange

Stable organic radicals with unpaired electrons exhibit vivid physical characteristics such as magnetic and electron-conducting properties, while being assumed as non-emissive chemical species. This highlight review introduces the luminescence properties of radicals and radical-ligated metal complexes as emerging functions of open-shell molecular systems. Their unique photofunctions will expand the

Positive suppression of photocatalytic activity of TiO2 used for an antireflection film or UV-light protection material is required while maintaining its white color and transmittance of visible light. In this study, TiO2 nanosheets co-doped with trace amounts of transition metals were synthesized. The photocatalytic activity of the TiO2 nanosheets for the decomposition of organic compounds was significantly

A novel sandwich N-fused porphyrin rhodium complex (Rh-1-Br) comprising a brominated N-fused porphyrin (1-Br) and an isomerized cyclooctadiene ligand was synthesized and characterized. X-ray crystallographic analysis revealed a 1,5-cyclooctadiene isomerization into allylic C–H activated κ1,η3-C8H12 unit bound to the Rh center. The rotational dynamics of κ1,η3-C8H12 ring in Rh-1-Br was discussed using

Symmetrically branched glyceryl oligomers possessing thiol at apex were synthesized. After treatment on the surface of silver-plating metal piece, its water contact angle was significantly decreased.

This paper proposed using the linear response function (LRF) of Kohn-Sham orbitals for checking the convergence regarding thickness in periodic slab-and-vacuum model calculations. The effectiveness was demonstrated using the alkaline earth metal oxide (001) surface. The calculated LRF decreases and converges to zero toward the opposite side of a slab. The proposed LRF scheme can be used as a guide

Enantioselective oxidative couplings of 4-hydroxycarbazoles using a chiral dinuclear vanadium(v) complex have been achieved for the first time. Under the mild reaction conditions, the corresponding dimeric 4-hydroxycarbazoles were obtained in up to 90% ee.

Unsupported Ni2P catalysts synthesized by the hydrothermal method were studied for the direct dehydrogenative conversion of methane to hydrocarbons. The unsupported Ni2P catalyst showed smaller crystallite size and porous surface structure due to the absence of calcination and reduction at higher temperatures and performed better catalytic activity at 1173 K. It has been found that the simple hydrothermal

Nitrogen-doped carbon-supported Co/Cu bimetallic catalysts were found to catalyze olefination of aldehydes with ethyl diazoacetate. In the presence of triaryl phosphine with electron-withdrawing groups, various aromatic aldehydes could be converted into unsaturated esters in good to high yields. The system is heterogeneous, allowing for recovery and reuse of the catalyst for several runs without significant

The loss on ignition (LOI) of fatty acids (FAs; including carbon numbers of C8–C24) in vegetal and animal organic reference samples at 200–500°C was examined. The total FAs in the samples preferentially disappeared through LOI operation compared to the other compounds. The average carbon numbers in total FAs did not change substantially from their original values due to LOI, regardless of the temperature

The dimethyl naphthalene composition is used as an indicator to estimate the source organic matter of crude oil. This study examined the effect of maturation on this indicator. Heating experiments were performed on dimethyl naphthalenes and immature coal. The composition of indicator naphthalenes in terrestrial organic matter decreased with maturation. This study concluded that the dimethyl naphthalene

A polyamide-based nanocomposite reverse osmosis membrane was fabricated by introducing tannic acid coated carbon nanotubes (CNTs) into the oil-phase solution of trimesoyl chloride using an interfacial polymerization approach. The obtained membrane exhibits high permeate flux (67.6 L/m2h), salt rejection (99.4%), fouling resistance, antibacterial and anti-adhesion properties. After silver nanoparticles

In the present paper, we report about the mechanism of water and oil repellency (both static and dynamic) of methacrylate-based polymers with fluoroalkyl group side chains. Surface rearrangement has the greatest effect on dynamic water repellency, although surface composition mainly affects static water repellency. However, both static and dynamic oil repellences are influenced significantly by the

Direct utilization of combustible waste as an energy resource is very attractive for improving waste-to-energy conversion efficiency. Herein, we report a high-performance solid oxide fuel cell (SOFC) that can be supplied continuously with plastic waste as a fuel. Iron(III) oxide powder functioned as a pseudofuel in the ion transfer process and as a catalyst for gasification of the plastic. The resultant