A molecular salt with a bulky cation and anion, (H₂bipip)(H)₂[Fe(CN)₆] (1) (H₂bipip²⁺: 4,4′-bipiperidine-1,1′-diium), has been prepared. The salt comprises protons (H⁺) as counter cations. Single-crystal X-ray structure analysis revealed that the proton is trapped between two cyanido ligands of [Fe(CN)₆]⁴⁻ anions, forming a very short N•••H⁺•••N hydrogen bond.

The intrinsic activities of six important transition metals for HI decomposition were identified by kinetic study. Ru showed high activity and a low apparent activation barrier, indicating a good activity at low temperature. Ru/AC (Ru clusters supported on activated carbon) was designed and proved to be a highly active, cost-effective, and long-term durable catalyst for HI decomposition. The present work could contribute to catalyst development for the industrialization of the sulfur-iodine thermochemical cycle for hydrogen production.

We developed a new microspectroscopic system based on the ultrabroadband multiplex coherent anti-Stokes Raman scattering (CARS) process using a CCD camera with an InGaAs image intensifier. Owing to the gated amplification of the CARS signal by the InGaAs Image intensifier, the CARS signal was detected with less than 10 laser shots. As a proof-of-principle study, we applied our system to visualizing the heterogeneous structure of a blended polymer consisting of cellulose acetate and cellulose tris(phenylcarbamate). The clear vibrational contrast was observed under weak excitation conditions.

The heavier phenyl anion analogues, 2-tert-butylgermabenzenyllithium Li⁺·1⁻ and sodium Na⁺·1⁻, were synthesized via aryl elimination from the corresponding 1-Tbt-2-tert-butylgermabenenze 3 (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl). The properties of Li⁺·1⁻ and Na⁺·1⁻ have been elucidated spectroscopically, and structural determination of Na⁺·1⁻ was performed using X-ray diffraction analysis.

Metal-organic frameworks (MOF) of MIL-125 and NH₂-MIL-125 have been successfully coupled with TiO₂ nanotube array through a solvothermal method. MIL-125 and NH₂-MIL-125 demonstrated notably high surface area. MOF/TiO₂ heterojunctions can promote the separation of photo-generated e⁻/h⁺ pairs during the photocatalytic process. Thus both MIL-125 and NH₂-MIL-125 modified TiO₂ nanotube array showed enhanced photocatalytic activity under UV light. Under visible and solar light, NH₂-MIL-125/TiO₂ nanotube array demonstrated the highest photocatalytic response. The reason should be the red shift of optical absorption edge for the narrowed band gap of NH₂-MIL-125.

Pt/CeO₂-ZrO₂-Bi₂O₃/SBA-16 catalysts were prepared to realize complete oxidation of formaldehyde at room temperature. Due to the high oxygen release and storage abilities of the CeO₂-ZrO₂-Bi₂O₃ promoter, formaldehyde was effectively decomposed even with a low amount of the Pt activator. For the Pt(0.7 wt%)/Ce_0.68Zr_0.17Bi_0.15O_2−δ(16 wt%)/SBA-16 catalyst, complete decomposition of formaldehyde was achieved at temperatures as low as 20 °C, and this catalytic activity is higher than the Pt(0.7 wt%)/Ce_0.80Zr_0.20O₂(16 wt%)/SBA-16 case (98% of formaldehyde conversion at 80 °C).

Chalcogenation reactions of stable cyclic digermenes with elemental sulfur and selenium have been examined, resulting in the formation of [Ge₂Ch_2/3C_x] heterocycles, which should be a convenient procedure for the preparation of the cyclic tetrel chalcogenides. Thus, the [Ge₂Ch₃] heterocyclic compounds 5 were isolated for the first time, and the experimental data and theoretical calculations suggested the considerable delocalization of the lone pair on the chalcogen atoms.

Photocatalytic activity has been demonstrated for ZrSnO₄ by controlling the bandgap and the bottom of the conduction band of ZrO₂ and SnO₂. A single-phase with the metastable ZrSnO₄ solid was successfully obtained, and ZrSnO₄ exhibited photocatalytic activity for hydrogen and oxygen production from water under UV irradiation.

Vesicles were prepared from poly(sarcosine)-b-(l-Leu-Aib)₈ (SL16), and the membrane leakage of the encapsulated K⁺ was evaluated to be ca. 4% for 15 min at 30 °C. The osmotically induced leakage of the encapsulated 5(6)-carboxy fluorescein was negligible below 50 °C. The robustness of SL16 vesicle was considered to be due to the interdigitated structure of Leu side chains in the monolayer.

An operationally simple and high-yielding synthetic method for 1E,3E-dienylphosphonates has been developed through the Horner-Wadsworth-Emmons olefination of α,β-unsaturated aldehydes with tetraethyl methylenebisphosphonate, in heterogeneous medium, in the presence of solid potassium carbonate, in refluxing DMF.

A novel hydrophobic ionic liquid including N,N,N′,N′-tetrakis(2-pyridylmethyl)-1,3-diaminopropane-2-amido structures ((IL-TPTNA)⁺NTf₂⁻) was successfully synthesized. Its extraction performance of Eu³⁺ from nitric acid solution was investigated by dissolving in a low viscosity ionic liquid (C₆mim)⁺NTf₂⁻. As a result, it was found that the extraction percentage of Eu³⁺ varied with the pH value. The stripping of extracted metals from (C₆mim)⁺NTf₂⁻ into a receiving phase was successfully achieved under 1.0 M nitric acid conditions. Slope analysis confirmed that (IL-TPTNA)⁺NTf₂⁻ formed a 1:3 complex with Eu³⁺ in the (C₆mim)⁺NTf₂⁻ system. Furthermore, (IL-TPTNA)⁺NTf₂⁻ showed greater preference to heavier lanthanides than lighter ones.

Sumanene, a C_3v-symmetric pristine buckybowl, afforded a dearomatization reaction with OsO₄ to give the di-adduct at both the internal and peripheral positions. Density functional theory (DFT) calculation revealed that the distortion of the curved system significantly decreased the energy barrier for the dearomatization.

Classification of chemical elements in the reaction cell of an inductively coupled plasma mass spectrometer (ICP-MS) was first reported based on the affinities with multiple elements, i.e. sulfur, oxygen, and fluorine. The data were summarized in the periodic table based on the affinity with each of the three elements mentioned above. An example of the application of the present results was illustrated by analyzing Y and La in the matrix of Sr and Ba, offering apparently improved background equivalent concentration (BEC) and detection limits (DL).

We have shown that an anion radical of C₆₀ (C₆₀^•−) is readily formed in a nitrobenzene (NB) solution containing tetraphenylborate by solar-light irradiation. Applying this photochemical reaction of C₆₀, we examined a voltammetric behavior of C₆₀^•− by using an electron conductor separating oil-water (ECSOW) system consisting of NB and water (W) phases. Based on the behavior, we can successfully attain spontaneous generation of hydrogen gas in a photovoltaic cell with NB and W phases.

Species concentration profiles produced from pyrolysis of n-heptane and isooctane diluted in argon were measured behind reflected shock waves at temperatures of 1000–1500 K and pressures of 1.2–2.6 atm. Simulation was performed using a chemical kinetic model based on KUCRS. The model reproduced the concentration profiles of n-heptane and isooctane surprisingly well over experimental conditions, while it did not cover some product species. The model was updated including additional species and reactions to reproduce concentration profiles of products.

A copper-containing nitrite reductase (NiR) catalyzes NO₂⁻ reduction in denitrifying bacteria. The reaction mechanism was proposed based on the trimeric crystal structure. In this study, a small angle neutron scattering (SANS) experiment with NiR from Achromobacter cycloclastes (AcNiR) was performed, and the first solution structure was obtained. The obtained radius of gyration, the calculation of the scattering curve from the available pdb structure and ab initio modelling all indicate a trimeric structure of AcNiR in solution.

A synthetic method for 1,2-dihydroisoquinolines via the 6-endo-dig cyclization of 2-alkynylaldimines and nucleophilic addition has been developed. When the 2-alkynylaldimines were reacted with various nucleophiles such as nitromethane, dimethyl malonate, phenylacetylene, hydrosilane, allylstannane, and ketene silyl acetal in the presence of a rhenium catalyst, the corresponding 1,2-dihydroisoquinolines were obtained in moderate to good yields.

A decarbonylative aryl thioether synthesis by nickel catalysis is described. After optimization of the reaction conditions, two air-stable Ni catalytic systems [Ni(OAc)₂/PⁿBu₃ and Ni(OAc)₂/dppb] were identified. Using these catalysts, various aryl thioesters can be converted to the corresponding aryl thioethers in decarbonylative fashion.

2,5-Diphenylthiophene-based macrocycles were synthesized by Ni-mediated coupling of the corresponding building units. X-ray analysis revealed that the cyclic trimer had a saddle-shaped structure due to the steric demands of the biphenyl and thiophene-phenylene units, whereas DFT calculation showed that the cyclic dimer had a rigid and almost coplanar structure regardless of the steric hindrance between the benzene rings of the biphenyl units. Moreover, the packing diagram of the cyclic trimer showed alternating stacked layers of macrocycles and solvent molecules.

Iron-catalyzed cross-coupling reaction of alkyl halides with alkyl Grignard reagents by the combined use of cyclopentadienyl ligand and 1,3-butadiene additive is described. The reaction smoothly proceeds at room temperature using unactivated alkyl bromides and fluorides via non-radical mechanism, which is in sharp contrast with hitherto known Fe-catalyzed cross-coupling reactions of alkyl halides.

This study presents a new evaluation method of static friction using a sinusoidal motion evaluation system in which the friction probe moves regularly under sinusoidal motion on polytetrafluoroethylene surface. The dependence of the static frictional force on the normal force is consistent with the classical power law model. Additionally, the friction energy during the pre-sliding process from the friction profile is estimated.

Here we present a liposome non-covalently coated with immunoglobulin G (IgG) by using a peptide ligand to the constant region of IgG. IgG coated on the liposome still maintained binding ability to a complementary antigen protein but it was not recognized by Fcγ receptors (FcγRs) of monocytes. The stealth feature of the IgG-coated liposome may be useful to avoid clearance by macrophages in vivo to extend the blood half-life of the liposome.

A novel square-planar cyclic tetranuclear nickel(II) complex coordinated by im-H₂bizn⁻ ligand (Him-H₂bizn = 4,5-bis(4,5-dihydro-1H-imidazol-2-yl)imidazole), [Ni^II₄(im-H₂bizn)₄(MeOH)₄(py)₄](ClO₄)₄·2ether (py = pyridine), has been synthesized. The tetranickel(II) complex crystallized in C2/m space group and exhibited antiferromagnetic intramolecular coupling with J = −24 K. The complex arrests ClO₄⁻ ion by moderate O–H•••O and weak multipoint C–H•••O hydrogen bonds.

We performed Raman spectroscopy of Co-doped Li₂O (CDL), a cathode material for lithium-ion batteries. During the charge process of CDL, the spectra showed a new peak at 790 cm⁻¹, assignable to peroxide. The charge range where the peak was observed coincided with the range where oxygen gas was generated from the reaction of the charged CDL with water using platinum as catalyst. The peak was reduced and disappeared during discharge. This indicated the formation/decomposition of peroxide in CDL during charge/discharge.

A highly active Pd/Cu cooperative catalytic system based on biphenylene-substituted di-tert-butylruthenocenylphosphine (R-Phos) was developed for performing Suzuki–Miyaura coupling reactions of (hetero)aryl, alkenyl, and benzyl bromides with (hetero)arylboronic acid pinacol esters. A variety of sterically and/or electronically diverse bromides and boronate esters were successfully coupled in good to excellent yields at room temperature using 0.1 mol % Pd and 5 mol % Cu.

We investigated the effect of fluorination on friction forces between polymer brushes in the dry state by means of an all-atom molecular dynamics simulation. An all-fluorinated brush produced less friction force than a non-fluorinated brush. In addition, a brush in which only the six monomers at the tips of the polymers were fluorinated produced a friction force comparable with that produced by the all-fluorinated brush. Fluorination was found to reduce the friction force by reducing entanglement between the brushes.

The enantioselective synthesis of silicon-stereogenic benzofuranylmethylidene-benzoxasiloles was achieved with moderate enantioselectivity by the cationic rhodium(I)/(S)-BINAP complex-catalyzed desymmetrization of symmetrical bis(2-ethynylphenol)silanes, possessing the tert-butyl and methyl groups on the silicon atom. This reaction involves 1,2-silicon/1,3-carbon migrations and oxycyclization, and the 1,2-silicon migration constructs the stereogenic silicon center. The thus obtained benzofuranylmethylidene-benzoxasiloles with the electron-donating methoxy, methyl, and phenyl groups on two benzene rings showed good fluorescence quantum yields in solution state, on the other hand, that with the electron-withdrawing trifluoromethyl groups on two benzene rings showed good fluorescence quantum yield in solid state.

Described herein is a catalytic system composed of an indium(III) compound, a hydrosilane and an easily handled form of elemental sulfur (S₈) that effectively and directly catalyzes the sulfidation of dibenzyl ethers to produce dibenzyl sulfides. This system could also be applied to selenium in a straightforward conversion to dibenzyl selenides.

Anionic HA nanofibers incorporated with cationic fluorescent dyes of pyrene and porphyrin have been prepared by electrospinning in the presence of polyethylene oxide. The emission spectra of fluorescent nanofibers reveal an energy transfer from pyrene to porphyrin with high FRET efficiency of 96% upon light excitation at 342 nm.

The stickiness of acacia gum was used to assist in the ball milling of graphite in aqueous media. Graphite is successfully exfoliated through a “sticky tape” mechanism, to give a 2.06 mg mL⁻¹ aqueous dispersion of graphene. PEG₆₀₀₀ doped with 0.4 wt% of as-prepared graphene nanosheets (GN) exhibited obviously growing enthalpies and increasing thermal conductivity by 260% over pure PEG₆₀₀₀.

(R,S_S)-Sulfoxide-MOP (L2) and (R,R_S)-sulfoxide-MOP (L3) were developed as a diastereomeric pair of sulfoxide-containing chiral MOP-type ligands. These two ligands also represent the first monosulfoxide analogues of BINAP. The chiral ligand L2 was successfully applied to the highly enantioselective rhodium-catalyzed 1,4-addition between α,β-unsaturated ketones or esters and arylboronic acids, and exhibited a broad substrate scope when the reaction was performed using 1.5 mol% Rh in cyclohexane/H₂O (10:1) at 40 °C under mild basic conditions.

A photoelectrode composed of Zn-porphyrin dye and semiconductor titania nanosheets (TNS, Ti_0.89O₂) where Zn-porphyrin was densely adsorbed without aggregation was fabricated. Efficient electron injection from excited Zn-porphyrin to TNS was observed under the irradiation of visible light. The absorbed photon to current conversion efficiency (APCE) was estimated to be 31%. Action spectra for the current coincided well with the absorption spectrum of Zn-porphyrin. These results indicate that TNS could act as an efficient n-type semiconductor.

The asymmetric synthesis of configurationally stable oxygen-linked Geländer-type p-terphenyls has been achieved via the rhodium-catalyzed diastereoselective intramolecular double [2+2+2] cycloaddition of chiral propargylic alcohol-derived hexaynes. Centrochirality of the chiral hexaynes induced the axial chirality to give the Geländer-type p-terphenyls as single stereoisomers. Photophysical and chiroptical properties of the thus synthesized Geländer-type p-terphenyls were examined, which revealed that the di-n-butyl- and diphenyl-substituted one shows efficient ultraviolet emission and a relatively large absorption dissymmetry ratio.

1-(Perfluoroalkylethyl-X)-4-alkoxybenzenes (X = thio for 1-m,n and X = sulfonyl for 2-m,n) were synthesized as a new class of rod-shaped organic gelators without hydrogen-bonding groups. Compounds 1-m,n and 2-m,n form gels in several polar solvents to give physical gels. The gel-sol transition temperatures of propylene carbonate gels were about 30 °C–80 °C, depending on the chemical structures of the compounds. The formed gels consist of fibrous structures.

Thermal stability of perovskite solar cells is crucial for their practical use. In this report, we show good 74% stability retention after a thermal stress test at 85 °C for 350 h) with high efficiency (>18%) using Rb modified perovskite absorber layers. It is posited that the mechanism of the thermal stability improvement is due to the formation of RbPbl₃ which suppresses Pbl₂ growth. This facile way for improving thermal stability is promising for realizing solar cells with high efficiency and stability.

The hole extraction layer (HEL) plays a critical role in determining the charge extraction in inverted perovskite solar cells (PSCs) besides affecting the perovskite crystallization. Herein, we demonstrate efficient inverted perovskite solar cells based on solution-processed kesterite Cu₂ZnSnS₄ (CZTS) as the HEL for the first time. We achieved CZTS HEL with desired phase purity and optimal film coverage by optimizing the spin-coating process. Moreover, photoluminescence (PL) studies indicate that the CZTS HEL developed in this work provides superior hole extraction in comparison with the widely reported NiO_x. This ultimately results in a respectable power conversion efficiency of 13.75% for the proof-of-concept device, reaching a level that is comparable to that of the NiO_x-based device.