Selenium catalysis has become an exciting area in organic synthesis. In various selenium-catalyzed reactions, different substrates have been utilized. However, alkynes as substrates have received much less attention than other substrates such as alkenes although the triple bond of alkynes possesses versatile reactivities. This review summarizes the progress of selenium-catalyzed alkyne functionalization

Herein reported is a dehydrative/decarboxylative coupling reaction of carboxylic acids with allylic alcohols, which is co-catalyzed by photoredox and palladium catalysts. α-Hetero- or aryl-substituted carboxylic acids and allylic alcohols, which are both readily available, directly participate in C–C bond formation without any functional group transformation.

A morphological transition was observed in the drying of an aqueous solution containing glucose and starch, which are the monomer and polymer of the same chemical composite. With an increase in the glucose content, the sample exhibits a change from cracking of a 2-dimensional (2D) layer to peeling from the bottom layer. With a further increase in glucose, a 2D homogenous layer is generated. A chemical

The carboxylation of propargylic alcohols containing a silyl group at the terminal position was conducted in a CO2 atmosphere at atmospheric pressure in the presence of a nickel catalyst and diethylzinc. Here, CO2 was used as not only the C1 source but also the promoter of the C–OH cleavage processes for the oxidative addition of propargylic alcohols.

The single-crystal-to-single-crystal (SCSC) transformation is a fascinating and valuable outcome of topochemical reactions. Not like the solution-state reactions, the movement and transformation of the molecule in single-crystal state is such a mysterious and attractive research topic. The molecular packing of the monomers prior to the reaction could provide many possibilities for the formation of

Because of their unique structures and properties, self-assembled bilayer lipid membranes are a subject of intense interest. In this Highlight Review, we summarize recent progress made in research related to bilayer lipid membranes, including the formation of stable free-standing lipid membranes, applications of artificial lipid bilayers as a model cell membrane to study biological processes, and new

The study for the development of the nickel-catalyzed highly enantioselective propargylic amination of propargylic carbonates with aniline derivatives is described. The reaction of internal alkyne-substituted propargylic carbonates with a series of aniline derivatives smoothly proceeded in DMSO using a combination of Ni(cod)2 and (R)-SEGPHOS as the catalyst to give the corresponding chiral propargylic

Chlorophyll pigments often assemble in a poor solvent to form less-ordered amorphous aggregates, despite the in vitro self-aggregation observed with chemically modified chlorophyll derivatives biomimicking a chlorosome. Chlorophyll dimer linked with a terephthalamide formed well-defined fiber shaped aggregates in hexane. The nanofiber was constructed by columnar self-aggregation via hydrogen bonding

The alkylation of heteroaryl chlorides through a homolytic aromatic substitution (HAS) mechanism was achieved by the use of alkyl formates as alkylating agents in the presence of a tert-butoxy radical precursor, where alkyl radicals are generated from alkyl formates through hydrogen abstraction followed by β-scission with decarboxylation.

The electrolyte solution of lithium tetrafluoroborate dissolved in sulfolane is applied in dual-ion batteries. Graphite positive electrode in this solution delivers the reversible anion storage capacity over 80 mAh g−1 at potentials over 4.5 V vs. Li/Li+. The structures of anion-graphite intercalation compounds are investigated in detail by the combination of in situ X-ray diffraction (XRD) and in

Machine learning using descriptors suggested for “electronic-structure informatics (ESI)” is carried out to establish a regression model for antibacterial activity of 60 natural products. The obtained model is used for the in-house data containing 175 molecules. The screening result is justified through literature survey in which, at least, 13 compounds listed in the top 20 compounds are shown to have

Heme is involved in signal transduction by either acting as a cofactor of heme-based gas/redox sensors or binding reversely to heme-responsive proteins. Bacteria respond to low concentrations of nitric oxide (NO) to modulate group behaviors such as biofilms through the well-characterized H-NOX family and the newly discovered heme sensor protein NosP. NosP shares functional similarities with H-NOX as

Density functional theory calculations with plane-wave basis sets are often used for theoretical investigations of solid materials; nevertheless, analysis techniques for open shell structures are insufficient. In this study, we established an electron density-based estimation scheme for the diradical character (y). The values estimated by the proposed and conventional schemes are consistent. Additionally

Salt cavern redox flow batteries with a large salt-cavern storing electrolyte are a promising large-scale energy storage technology. Here a low-cost iron/organic redox material system was proposed to explore salt cavern redox flow batteries. To avoid the formation of ferric hydroxide, ligand threonine was used to enhance the stability of the ferric ion in aqueous solution. Paired with a two electron

The PdAu random alloy nanoparticle catalyst shows excellent catalytic activity for heterogeneous molecular formations, whereas monometallic Pd or Au catalysts were ineffective. The Pd/Au ratio in the alloy had a significant impact on its catalytic performance, and the catalyst with a low Pd concentration exhibited excellent activity. The concerted catalysis of Pd and Au adjacent on the alloy surface

Electrolytic deoxygenation devices have been fabricated using SiC, SWCNT, graphene, and PEDOT*PSS for the electrodes. Characteristics of devices were studied by measuring currents, O2 and H2 concentrations, and humidity during deoxygenation in a closed container. Performances of the devices being composed of cation or anion exchange membrane are discussed comparing with the standard catalyst of Pt-black

Chemosensor arrays are useful analytical methods in supramolecular analytical chemistry, which discriminate molecular information such as species and their concentrations based on pattern recognition. Molecular self-assembled systems can provide not only the multi-optical response patterns but also easy preparation of chemosensors. In this regard, dynamic covalent-bonds play key roles in competitive

Bioinorganic chemistry is a broad field with multiple branches. In this Highlight Review, the newest excitements in the branch of Bioinorganic Platforms are reviewed. Artificial bioinorganic platforms come in mesmerizing flavors, in particular the following 5 types are the major focus of this Highlight Review. First, single-stranded and double-stranded DNA, RNA, PNA, and their hybrids can be attached

Considering the drawbacks associated with the fossil-based molecules, polymers and materials, lignin has acquired immense popularity owing to its distinct advantages. However, till date it has not been widely commercialized to produce fossil replacements mainly due to its complex structure and purification hassle. Constant research is going on to discover ways to depolymerize lignin to produce various

Transient absorption spectroscopy is one of the most widely used experimental techniques for time-resolved studies of ultrafast phenomena. Recent advances in the generation of short-wavelength pulses of ultrashort duration have made transient absorption probing of atomic core level transitions possible. In this Highlight Review, we introduce our recent work on using extreme ultraviolet (XUV) transient

Soft X-ray absorption spectroscopy (XAS) determines element-specific intermolecular interactions of light elements in liquid phase since it is related to a core electron excitation. We have newly developed liquid cells and devices with the precise photoabsorbance control technique. We demonstrate here their applications to XAS in transmission measurement with aqueous acetonitrile solutions and XAS

Nanoscale Ag2Bi3I11 photosensitizer was prepared on mesoscopic TiO2 film (~1 μm thick) by spin-coating of its low-concentrated precursors. The as-prepared Ag2Bi3I11-sensitizer was tested in the form of solid-state dye sensitized solar cell. When combined with a molecular dye, the hybridized Ag2Bi3I11/dye-sensitized cell showed enhanced characteristics with overall power conversion efficiency of 1.50%

Harvesting of excited spin-triplet states as light is essential to realize highly efficient electroluminescence (EL) in organic light-emitting devices. In recent years, thermally activated delayed fluorescence (TADF) has attracted much attention as a novel electronic transition process, since it enables harvesting electrically generated triplet energy as EL without the utilization of rare metals such

Here, we used a fluorophore-bound, porphyrin-targeted DNA aptamer to increase the sensitivity of capillary electrophoresis for the detection of a model porphyrin. The complex of the DNA aptamer with the porphyrin induced the transfer of energy from the fluorophore to the porphyrin, resulting in the quenching of fluorescence. Monitoring of the quenching of fluorescence by capillary electrophoresis allowed

The rates of chemical expansion for 20 at% yttrium-doped barium zirconate upon hydration at 100–900°C under water partial pressures of 0.008 and 0.023 atm have been studied using combined thermogravimetry and high-temperature X-ray diffractometry. Non-linear behavior for the rates of expansion as a function of proton concentration under equilibrium conditions was observed, suggesting that defect interactions

Solid-state vibrational circular dichroism (SD-VCD) spectra were measured on the ion-exchange adducts of sodium montmorillonite and [Cu(RR- or SS-oxa)]2+ as prepared in the presence of a substrate in Michael additions, (E)-2-butenoyl-2-oxazolidinone. Here RR- or SS-oxa denotes RR- or SS-2,2'-isopropylidene-bis(4-phenyl-2-oxazoline), respectively. By comparing the observed and theoretical VCD spectra

Artemisinin and its semi-synthetic derivatives have been the corner-stone of malaria chemotherapy. Their life-saving therapeutic effects and characteristic structure bearing a peroxide bridge in a sesquiterpene lactone framework have attracted the attention of both synthetic chemists and synthetic biologists. In this highlighted review, the engineered biosynthesis, chemoenzymatic synthesis, total synthesis

The design, synthesis, and optical characterization of refractive-index-contrast (RIC) triazine-based poly(phenylene sulfide)s (PPSs) are investigated. Indeed, novel PPSs with two pendant groups, either tert-butyl (tBu) ester or carboxylic acid groups, at each monomer repeating unit (PPS-2E or PPS-2CA, respectively) were successfully synthesized. PPS-2CA showed high refractive index (n) values of 1

Novel light sources have been new probes or “eyes” to develop our science and technology. Soft X-ray free-electron laser (SXFEL) is an ultrahigh brilliant soft X-ray source with ultrashort pulse-width, ultrahigh spatial coherence, and tunability of photon energy. Various experimental techniques are designed and examined with SXFEL. In this review, we focus on soft X-ray spectroscopies, such as magnetic

In this manuscript, we will illustrate a new idea for narrowing energy gaps between frontier molecular orbitals (FMOs) by selectively perturbing the levels of highest occupied molecular orbitals (HOMOs) and/or lowest unoccupied molecular orbitals (LUMOs). Initially, the basic concept of the isolated FMOs is explained by employing pentaazaphenalene (5AP) derivatives. It was found that electronic structures

A rotating gliding arc (RGA) reactor was investigated for conversion of multiple model tar compounds including toluene, naphthalene, and phenol in simulated synthetic gas, with special focus on the effects of steam concentration (0–20%) and preheating temperature (300–700 °C). The maximum conversions of toluene, naphthalene, and phenol were 89.3%, 84.6% and 95.5%, respectively, at a steam concentration

The superhydrophobic-conductive anti-corrosion mode has attracted much more attention due to the huge economic losses of stainless steel corrosion. Here, a brand-new strong superhydrophobic-conductive polyaniline-polysiloxane (PANIC-RA-POS) anti-corrosion coating was prepared. The internal conductive and dense interpenetrating network polyaniline layer can effectively reduce electrochemical corrosion

Spherical palladium nanoparticles between graphite layers were prepared by the intercalation of palladium chloride followed by its reduction between graphite layers. The palladium particles intercalated between graphite layers were more active for cinnamaldehyde hydrogenation to hydrocinnamaldehyde and hydrocinnamyl alcohol in n-heptane solvent than those supported on graphite surface.

Hairy particles consisting of polyisoprene-b-polystyrene (PI-b-PS) were synthesized by polymerization-induced self-assembly (PISA) based on living anionic polymerization method. The molecular aggregation state of the hairy particles in wet condition was investigated in detail. The hairy particles in wet state formed core-shell structure with PS core radii of 8.6 nm and PI shell thickness of 4.1 nm

A suitable microenvironment provided by artificial granules scaffold plays a critical regulatory role in bone repairing progression. Till now, it is still a challenge to prepare large hydroxyapatite granules (millimetre level) which provide beneficial physical and chemical stimulation for bone reconstruction. Herein, we developed a facile synthetic strategy for synthesizing hydroxyapatite granules

Ceria (CeO2) is a promising metal-oxide support that is used in three-way catalysis (TWC). The activity of ceria-supported TWC depends on the location and concentration of oxygen vacancies. Oxygen diffusion can occur once the oxygen vacancy was created, and it leads to enhanced catalytic activity. In this study, the density-functional tight-binding method was used to estimate the free-energy barriers

Mechanochromic luminescence (MCL) compounds exhibit change of their photoluminescent color in response to mechanical stimuli. The initial molecular alignment of a liquid-crystalline MCL compound was controlled by using an alignment layer. The rubbing method and rubbing direction were successfully determined. Influence of mechanical force on photoluminescent behavior was evaluated.

Salivary cortisol concentration and its circadian variation were detected by optimizing the ionic concentration of the solution during the immobilization of aptamers on a field-effect transistor biosensor. This was achieved by modifying our previously developed technique of detecting uncharged cortisol using the transformation of negatively charged aptamers by controlling the aptamer spacing. This

Hypervalent halogen species such as organoiodine(III and V) compounds have long been used as electrophiles/oxidants in organic synthesis, but recent years have seen the emergence of a new class of hypervalent halogen species, organobromine(III) and organochlorine(III) compounds (also termed organo-λ3-bromanes and λ3-chloranes). In this review, we will cover recent developments in the synthesis and

The impact of water vapor on the catalytic activities of CO oxidation over Cl-containing Pt/CeO2 was investigated by combining catalytic activity tests, X-ray fluorescence spectroscopy, in-situ Fourier-transform infrared spectroscopy, and low-energy ion scattering. Water vapor reduced the density of chlorine adsorbates near the Pt-CeO2 interface. The utilization of hydroxyl groups near the cleaner

Due to an intrinsically polar π-bond with a narrow π-π* gap, silenes (silicon-carbon doubly bonded compounds) should receive remarkable attentions as a member of π-conjugation units. We report herein synthesis, structure, and properties of an isolable bromosilene (1). Single-crystal X-ray diffraction analysis revealed the planar geometry around silene moiety with Z-configuration in 1. Substitution

We developed iridium-catalyzed 2-position-selective C–H borylation of indole derivatives by modifying the structure of a bipyridine-type ligand. The yields ranged from good to excellent, even on a gram scale, and were dramatically improved by the addition of a urea derivative catalyst. The introduced boryl group was converted to chloro, bromo, and phenyl groups without isolation of the borylated intermediate

This highlight review overviews recent progress in fluorescence imaging technology for the alkaline-earth metal ions calcium, and magnesium, by small molecule-based fluorescent probes. Fluorescent probes for Ca2+ using 1,2-bis-(o-aminophenoxy)ethane-N,N,N’,N’-tetraacetic acid (BAPTA) as a recognition unit are introduced. Focus is set on the fluorescence characteristics and intracellular dynamics of

The characteristics of loss on ignition (LOI) at 200–500 °C of three types of authentic organic biomolecules (monosaccharides: MSs, fatty acids: FAs, and amino acids: AAs) are evaluated and compared to those of reference organic natural samples. FAs and branched-chain AAs degraded almost completely by 300 °C, whereas MSs and unbranched AAs degraded at a slower rate. The exponential regression coefficients

Herein, we report the example of red-green-blue full-color magnetic circularly polarized luminescence (MCPL) from three inorganic luminophores in their solid powder form and upon embedding in poly(methyl methacrylate) films; they were examined in the photoexcited state under the Faraday geometry with a 1.6 T permanent magnet in the absence of chiral chemical influences. The MCPL signs associated with

Recent developments for ammonia (NH3) combustion catalysts are covered in this highlight review. NH3 has been proposed as a renewable and carbon-free energy source. However, use of NH3 fuel poses the problems of high ignition temperature and nitrogen oxide (N2O/NOx) production. In order to overcome these issues, a novel catalytic combustion system was probed, and high performance catalysts were developed

A photoalignable liquid crystalline (LC) polymer comprised of phenyl benzoate with a Schiff-base end moiety is synthesized and its thermally stimulated photoinduced reorientation behavior is investigated using linearly polarized (LP) 365 nm light. A significant in-plane reorientation (D>0.8) is achieved. The reoriented film exhibits a high birefringence (Δn=0.28) and a high thermal stability (~295

The reaction of 19-phenoxybilinones with Zn2+ caused ring-closure to afford the 5-oxaporphyrin zinc complex under ambient conditions. While bilinones are non-fluorescent, the 5-oxaporphyrin zinc complex fluoresced red light. 19-Phenoxybilinone can be employed as a fluorogenic zinc ion sensor. Among various metal ions, only Zn2+, Cu2+ and Co2+ can induce the ring closure reaction to yield 5-oxaporphyrin

Circularly polarized luminescence (CPL) of unsubstituted helicenes is weak due to their low fluorescence quantum yield (Φf) and small dissymmetry factor (gCPL). In this study, we designed and synthesized a donor-acceptor type [5]helicene, 5,10-dicyano-2,13-bis(3,4,5-tris(n-octyloxy)phenyl)[5]helicene. This helicene showed high fluorescence quantum yield (Φf = 0.63) and good |gCPL| (4.2 × 10−3) due

A tetracene dimer, 5,5'-bitetracene (55BT), has successfully been synthesized for the first time and its structure was confirmed by X-ray single crystal analysis. The electrochemical and optical properties of 55BT were investigated and compared to those of tetracene. Although the photoluminescence quantum yield of 55BT was slightly higher than that of tetracene, the results of the transient absorption

This highlight review describes the recent development of an electrophile-triggered 1,2-metallate rearrangement of organoboronic ester ate-complex, which proceeds through 1,2-difunctionalization of carbon–carbon σ- and π-bonds, using strain energy as a driving force. Coupling reactions of small ring carbocyclic boronic esters, such as cyclopropyl-, bicyclo[1.1.0]butyl-, and cyclopropenyl-boronic ester

We revealed the effects of the substituents in ligands on properties of Phebox-aluminum complexes. The substituents at the 4-position of Phebox ligands effectively influenced the Lewis acidity via the conjugation between the vacant orbital on the Al atom and π* orbital of the benzene ring, which is supported by DFT calculation. The catalytic activity was also tuned, and series of substituted Phebox-Al(ClO4)2

We previously showed that the hybridization of water-insoluble 12-hydroxystearic acid (HSA) with water-soluble long-chain amidoamine derivatives yields hydrogels composed of self-assembled helical nanofibers. In this work, we investigated the effect of introducing an amide group into the alkyl chain of amidoamine derivatives on the helical structure of the nanofibers. We also demonstrated that improving

Boron-doped diamond powder (BDDP) and boron-doped nanodiamond (BDND) were developed with the aim of expanding the area of application of conductive diamond electrodes. BDDP and BDND are conductive diamond powders obtained by depositing a boron-doped diamond (BDD) layer on the surface of diamond powder (DP) and nanodiamond (ND) substrates, respectively, by using the chemical vapor deposition method

Diazocarbonyl compounds are versatile precursors of carbenes leading to various structures by using several metal catalysts, especially copper and rhodium salts. In this study, eight different diazocarbonyls having N-O moiety were used. The N-O tethered structures were preferred because they may allow some useful transformations of the final products into valuable compounds via N-O cleavage. In the

Even without external photon pumping, cavity vacuum fields can be strongly coupled with molecular transitions (electronic excitation and molecular vibration), resulting in the formation of polaritonic states. The energy states of molecular systems are altered under strong coupling, revealing intriguing phenomena, such as improvements in energy/exciton transfer and modulation of chemical reactions.

Surface oxygen vacancy, dynamically created and annihilated under the reaction conditions, may serve as a unique form of active site for heterogeneous catalysis. In this study, the mechanisms of selected reactions (i.e., CO oxidation, water-gas shift, CO2 hydrogenation, alcohol carbonation, and selective catalytic reduction of NO with NH3) proposed by in-situ spectroscopy characterizations were reviewed

The synthesis, structure, magnetic properties and magnetic structure of two molecular chiral magnets and one inorganic chiral magnet are presented. In magnetic crystals belonging to the Sohncke group, which includes the chiral group, the chiral non-collinear spin structure is achieved through Dzyaloshinsky-Moriya interactions in addition to the usual exchange spin interactions and dipole-dipole spin

To open up the possibility of synthesizing useful substances from CO2, we have developed new catalysts that hydrogenate CO2 to methanol with high yield at 300 °C and higher. In this study, methanol synthesis via CO2 hydrogenation at 250–350 °C and 10 bar was investigated using Zr-based metal oxide catalysts, MZrOx (M = Al, Mn, Cu, Zn, Ga, and In). The different metals (M) determined the suitable reaction

Metal organic framework materials (MOFs) have a drawback that limits its wider application: poor electrical conductivity. In this paper, some research advances in improving the conductivity of MOFs in recent years are reviewed. They are divided into two categories: intrinsical improvement of conductivity and extrinsic improvement of conductivity. The application of MOFs with improved electrical conductivity