The C–C bond located at the β-position of an alkoxy radical readily breaks to form an alkyl radical along with a carbonyl compound. Such processes are called β-scission or β-fragmentation. They possibly proceed without any assistance of ring strain, and have recently attracted renewed attention as the key elementary step to transform alcohols in a unique fashion. Summarized in this Highlight Review are synthetic transformations of alcohols through β-scission of alkoxy radical intermediates.

A practical oxidative homocoupling reaction of aryltrimethylsilanes has been achieved by Pd/o-chloranil catalytic system. The reaction shows the good functional group tolerability toward bromo, fluoro, ester, and methoxy groups to give a series of biaryls bearing electron-withdrawing and -donating groups. The boronate group is also retained on biaryls without any Ar–B bond cleavage, which is highly advantageous for orthogonal coupling.

The tailor-made nanospaces of porous coordination polymers (PCPs) allow us to control the assembly structures of guest species. Here, we report the accommodation of anthracene (ANT) in PCP nanochannels to study the effect of pore shape and surface environment on its assemblies. ANT forms herringbone structures in the bulk state. In contrast, the accommodation of ANT in the square nanopores formed π-stacked structure, resulting in a drastic change in the emission properties.

Metal-free oxidative bromination reactions in aqueous media were performed using tetrabutylammonium bromide, trifluoroacetic acid, and hydrogen peroxide under mild conditions. Oxidative bromination reaction of alkenes was found to afford the corresponding vic-bromides. Furthermore, this oxidative bromination system is applicable to the oxidative bromination of alkynes, arenes, and 3,4-dihydronaphthalen-1(2H)-one. A gram-scale bromination reaction was also performed successfully.

Fluorescence in situ hybridization (FISH) is a powerful tool to visualize nucleic acids in a sequence specific manner, although its sensitivity is dependent on wash procedures. In this study, we demonstrated wash-free RNA FISH using a photocrosslinkable beacon probe containing 3-cyanovinylcarbazole (^CNVK). The probe visualized the 16S rRNA in E. coli by photoirradiation without any wash procedure. Moreover, this probe has high affinity to the target strand and can successfully detect RNA with a secondary structure.

B,B-Dimesityl-substituted dithieno-1,2-dihydro-1,2-diborin was synthesized and its properties and reactivity were studied. Owing to the noticeably electron-deficient and antiaromatic character of the 1,2-dihydro-1,2-diborin ring, this compound was found to homolytically cleave diatomic hydrogen (H₂) gas at ambient temperature under 1 atm to afford a hydrogen-bridged bis(borane). This reaction was accompanied by a dramatic color change from dark green to yellow in addition to a turn-on fluorescence response.

The oxa-Michael addition of Morita–Baylis–Hillman adducts and derivatives has been investigated for the first time to afford various types of polymeric and oligomeric products derived from Michael acceptors and aldehydes catalyzed by Cs₂CO₃/CuCl₂, t-BuOK, or an N-heterocyclic carbene. The reactions proceeded through multiple reaction modes, including dehydration polycondensation, selective oxa-Michael addition polymerization, and S_N2′ reaction, depending on the monomer structures.

Carbonylation of (2-pyridylmethylene)cyclobutanes in the presence of Rh(I) catalysts resulted in cleavage of cyclobutane C–C bonds to afford five-membered ring ketones and could be performed using paraformaldehyde as the CO source.

The separation ability of CHA-type and STT-type pure silica zeolite (Si-CHA and Si-STT) membranes for H₂ purification from H₂/toluene gas mixtures was investigated. When the feed mixture gas consisting of 98 mol % H₂ and 2 mol % toluene was supplied, corresponding to the gas-phase composition after removing toluene by condensation following methylcyclohexane dehydrogenation, both membranes showed good H₂-selective permeation, resulting in a hydrogen purity of above 99.9% on the permeate side.

The development of a disposable immunosensor based on a hybrid gold–carbon screen-printed electrode array is described. The electrodeposition of gold is shown to lead to a field of nanocrystals that facilitates antibody immobilization and enhances electron transfer. A label-free analysis protocol based on ferrocyanide has been developed for the detection of Prostate Specific Antigen in the fg mL⁻¹ range.

Three synthetic procedures have been developed for a new class of phosphorus ylide containing conjugate heterocycles, 3-oxo-λ⁵-benzophospholes. The key to the formation of the heterocycle is unusual intramolecular acylation of a phosphorus ylide forming an endocyclic ylide. Several types of 2-substituted benzophospholes are synthesized, some of which show fluorescence.

The copper-catalyzed cyanation of aryl iodides is described using nitromethane as a CN source. In situ generation of a “CN” species from nitromethane is plausible. This strategy is an advantageous synthetic method for the construction of an aromatic C–CN bond, because nitromethane is a common and easily handled compound that is readily available as a cyanation reagent, and its use allows the avoidance of using toxic metal cyanides.

A shape-persistent macrocycle (SPM) consisted of three 2,6-pyridylene and three 2,6-pyrazylene rings alternately linked with acetylene bonds was prepared by Sonogashira reactions. X-ray crystallography revealed the planar macrocyclic structure, and intermolecular π-stacking was observed at the sides of the hexagon. An AFM measurement of the sample prepared by drop-casting on a mica substrate showed a reticulate fibril.

A facile and efficient synthesis of silylated 4,5-disubstituted phthalates through the inverse electron-demand [4+2] cycloaddition of 2-pyrone-4,5-dicarboxylate with various silylacetylenes has been developed. The reaction was promoted by 4A molecular sieves (MS 4A) to afford the corresponding polysubstituted arenes with functionalizable silyl groups in good to high yield, thus providing versatile access to a wide variety of functionalized phthalates that represent promising intermediates for the synthesis of fine chemicals, particularly photochemically active compounds.

Enantioselective heteroatom-directed C(sp³)–H borylation reactions of 2-aminopyridines and 2-alkylpyridines with Rh- and Ir catalytic systems using commercially available chiral monophosphine ligands, respectively, were developed. This methodology provides an innovative example of a homogeneous catalytic system for C(sp³)–H borylation, and allows the direct synthesis of optically active alkylboronates with a moderate level of enantioselectivity.

Inductively coupled plasma optical emission spectrometry (ICP-OES) operated in axial-view mode and cold plasma conditions was investigated as a strategy for the measurement of rubidium to suppress the spectral interferences from argon emission lines. Dependences of the rubidium signal and the argon interferences on the radio frequency power and the carrier gas flow rate were studied. At the non-robust condition, signal-to-background ratio was improved by around 20-fold in comparison to that obtained at conventional robust condition.

A series of meso-tetraphenylporphyrins bearing four primary-amine-terminated oligo(ethylene oxide) chains have been synthesized from meso-tetrakis(4-carboxyphenyl)porphyrin. All the porphyrins with different lengths of oligo(ethylene oxide) chains accumulate in cells more efficiently than meso-tetrakis(N-methylpyridinium-4-yl)porphyrin, TMPyP. The porphyrin having the shortest ethylene oxide chains was found to accumulate the most within cells among the series, and exhibit phototoxicity under red light irradiation.

The coupling reaction of aryl iodides with arenes was found to proceed under mild conditions to give biaryls through a homolytic aromatic substitution mechanism, using potassium tert-butoxide and di-tert-butyl hyponitrite as a stoichiometric promoter and a radical initiator, respectively.

Dimerization of [2,5-bis(fluorodimethylsilyl)phenyl]lithium (8) afforded 9,10-dihydro-9,10-disilaanthracene 9 bearing fluorodimethylsilyl groups at the 2- and 6-positions. Tetrahydrotetrasilapentacene compound 11 was also obtained.

Treatment of 2-bromo-4,6-dimethylphenylisocyanide (1a) with 1.2 equiv of n-BuLi in THF at −78 °C provided an o-isocyanoaryllithium intermediate, which reacted with aldehydes, nitroalkenes, and trimethylchlorosilane to give the corresponding products in good yields. Asymmetric conjugate addition to nitroalkenes in the presence of (−)-sparteine in toluene gave the products with good stereoselectivities up to 85% ee.

Here, we propose a facile method for the synthesis of metal–formate frameworks. The synthetic procedure is simple, reactions are solvent-free, and conditions are mild, which is definitely suitable for large-scale synthesis. More importantly, the synthesized nickel frameworks show as highly superior performance to many other well-known adsorbents for adsorptive separation of methane from nitrogen, as the products obtained from other higher-demanding methods.

Effect of MnO₂ type on catalytic phenol removal in bioelectrochemical systems (BES) was firstly investigated. Three MnO₂ types (namely α, β, and γ) were prepared via hydrothermal methods, and polypyrrole (PPy) was used as a conductive wrapping to anchor MnO₂ onto the surface of graphite felt (GF) electrodes. A BES equipped with GF/PPy/β-MnO₂ resulted in superior phenol degradation and power generation. High BET surface area and electrocatalytic activity of β-MnO₂ played a key role.

We demonstrated photocatalytic hydrogenation coupling of acetone into 2,3-dimethyl-2,3-butanediol with formic acid as a hydrogen source. In this synergetic system, the conversion of acetone and formic acid was dramatically increased than that in the individual reaction system. Consequently, the selectivity of 2,3-dimethyl-2,3-butanediol was relatively high over that of NaTaO₃ and Na₂Ti₃O₇ photocatalysts. Additionally, in this acetone–formic acid reaction system, the presence of acetone can effectively restrain the generation of CO during the decomposition of formic acid.

A 1:1 mixture of meso-tetrakis(4-dodecyl-3-hydroxyphenyl)porphyrin (1) or its Zn-porphyrin (1-Zn) and tetrakis(4-pyridylethynyl)cavitand (2) in C₆D₆ self-assembles quantitatively into the cavitand-capped porphyrin capsule 1·2 or 1-Zn·2 via quadruple ArOH•••Npy hydrogen bonds. It was revealed that a guest is encapsulated in 1-Zn·2 and regardless of molecular length, various pyridyl ligands selectively coordinate at the outer side of 1-Zn·2.

A stanosilicate IEZ-Sn-PLS-3 with an interlayer expanded structure of FER topology was developed by acid treatment including F⁻ and Sn⁴⁺ ions on layered precursor PLS-3. XRD and pyridine adsorption measurements confirmed that the resulting material possessed enlarged pore size and heteroatom Sn as the Lewis acid sites. IEZ-Sn-PLS-3 turned out to be an effective catalyst for the Baeyer–Villiger oxidation of 2-adamantanone with H₂O₂.

Gold nanorod dimers were prepared in aqueous solution. The nanorod dimers were separated from other nanorod assemblies by a stepwise density-gradient centrifugation using sucrose (20, 30, 40, 50, and 60% w/w). The centrifugation step (3400 × g, 20 min) produced two bands, a side-wall sediment, and a bottom precipitate. The topmost band contained nanorod monomers. The bottom precipitate was redispersed in water, and its surface plasmon band was consistent with that of a theoretical model of a nanorod dimer. Thus, density gradient centrifugation is effective in fractionizing nanorod dimers.

O-Acetyl-l-serine sulfhydrylase (OASS) from plants and bacteria synthesizes cysteine and unnatural amino acids that are important building blocks for active pharmaceuticals and agrochemicals. A thermostable O-phospho-l-serine sulfhydrylase from hyperthermophilic archaeon Aeropyrum pernix K1 (OPSSAp) exhibits a function similar to OASS. In the present study, we examined the synthesis of various unnatural amino acids using OPSSAp and demonstrated OPSSAp could efficiently synthesize various sulfur-containing amino acids. OPSSAp would be useful for industrial production of biologically important unnatural amino acids.

Acetylenedicarboxylates undergo trans-addition of tetraalkoxydiboron in THF at 60 °C in the presence of 4,4′-bipyridine (5 mol %) as a catalyst to give 2,3-diborylfumarates in good yields with high stereoselectivity.

We herein report the synthesis of a range of Cu-doped ZnS/zeolite composites and subsequent evaluation of their photocatalytic activities based on hydrogen production from an aqueous S²⁻/SO₃²⁻ solution under UV–visible light irradiation (λ > 250 nm). We found that the hydrogen production rate over CuZnS/zeolite composites was significantly higher than over the bulk ZnS. The obtained photocatalysts were also characterized by X-ray diffraction and UV–vis diffuse reflectance spectroscopy.

The first C–B bond-forming dearomative carboborylation of heteroaromatic compounds has been achieved using copper(I) catalysis. This reaction includes the regioselective addition of a borylcopper(I) intermediate to indoles, followed by the diastereoselective methylation of the resulting copper(I) enolate intermediate to afford the corresponding 3-boryl-2-methylindolines bearing a quaternary stereogenic center with excellent regio- and diastereoselectivity.

Intracellular delivery of oligonucleotides is essential not only for antisense- and RNAi-therapeutics, but also for live-cell RNA imaging with fluorescent nucleic acid probes. Herein, we developed oligonucleotide–peptide conjugates synthesized via Cu-catalyzed alkyne-azide cycloaddition between an exciton-controlled hybridization-sensitive oligonucleotide (ECHO) probe and linear or cyclic cell-penetrating peptides (CPPs). When lipofected to living HeLa cells, the CPP-conjugated ECHO probe showed enhanced cellular uptake efficiency compared with that of the unconjugated ECHO probe.

Cobalt(III) porphyrin-catalyzed oxygenation of disilanes is investigated. Five- and six-membered cyclic disilanes are readily oxygenated, providing the corresponding cyclic disiloxanes in 75%–quant yield. We propose a reaction mechanism involving intermediates with a Co(III)–Si bond based on spectroscopic analysis of the reaction mixtures.

Reaction development patterning (RDP) was applied to poly(lactic acid) (PLA) to realize formation of a fine pattern by a photolithography process. The RDP of PLA using an aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer gave a positive-tone fine pattern. It was also revealed that addition of polyfunctional aromatic acids such as 3,5-dihydroxybenzoic acid to the film of PLA largely shortened the development time. When an alcoholic solution of TMAH was used as a developer, a negative-tone fine pattern was obtained, and pattern formation was achieved by a very short-time development without adding an acidic compound to the film.

A wide range of benzyl carbonates reacted with dimethyl phosphonate or diphenylphosphine oxide in the presence of the palladium catalyst, [Pd(η³-allyl)Cl]₂–DPEphos, to give dimethyl benzylphosphonates and benzyldiphenylphosphine oxides in high yields. The catalytic phosphonylation was applied to the one-pot synthesis of alkenes from the benzyl esters.

Horseradish peroxidase apoprotein (apoHRP) was immobilized on a heme-modified polythiophene film, which was electropolymerized on an indium tin oxide surface to yield immobilized and reconstituted HRP. The HRP-immobilized electrode exhibits a 6-fold enhanced electrochemical response toward hydrogen peroxide reduction relative to having the protein randomly immobilized on the polythiophene electrode. This indicates that the insertion of the heme moiety into the heme pocket of HRP leads to an increase in the electrocatalytic current.

The performance of quantum dots light-emitting diodes (QLEDs) was enhanced by incorporating Au into NiO hole injection layer (HIL). Highly bright green QLEDs, with a maximum luminance of 31210 cd m⁻² and a current efficiency of 6.5 cd A⁻¹, exhibit 50% improvement compared with device without Au NP. The improved performance may be attributed to the significant increase in the hole injection rate, which occurs due to the introduction of Au NPs and the good matching between the resonance frequency of the localized surface plasmon resonance (LSPR) generated by Au NPs and QDs, as well as the suppressed Auger recombination of QDs layer due to the LSPR-induced near-field enhanced radiative recombination rate of excitons.

Fine sodium titanate nanowires were fabricated easily from TiAl₃ alloy grains via alkaline treatment at room temperature. The resulting materials were identified to have lepidocrocite-type layered structure consisting of TiO₆ and Na⁺ ion layers. The materials exhibited remarkable ion-exchange with Sr²⁺ ions even in the presence of a large amount of Na⁺ ions.

A stable single-phase mixed electron/proton conductor with excellent capacitance from oxygen-functionalized porous carbon (OPC) has been presented herein. Electrochemical study suggested that at room temperature and 90% RH the values of electronic and protonic conductivity of OPC are 1.68 × 10⁻³ and 3.14 × 10⁻⁵ S cm⁻¹, respectively. Moreover, the specific capacitance of 204 F g⁻¹ at 10 mV s⁻¹ is observed. The improved electrochemical performance of OPC mostly associated with transformation of high temperature treated inert carbon into an electrochemically active substance and ionic movement associated with oxygen functional groups on the carbon surface during oxidation.

Significant improvement in cycling endurance and operating voltage dispersion has been accomplished by the addition of Cu-doped triglyme (G3) to the HfO₂ film of the Cu/HfO₂/Pt-type conducting-bridge random access memory (CB-RAM); both the V_set distribution and the charge-transfer resistance (R_ct) values were significantly reduced.

A cyclic compound consisting of four 10-mesityl-1,8-anthrylene units and four (E)-ethenylene linkers was synthesized by alkene metathesis, the Mizoroki–Heck reaction, and the Suzuki–Miyaura coupling reaction as a new macrocyclic π-conjugated compound. X-ray analysis and DFT calculations revealed that this molecule had a relatively rigid square-prism structure with two pairs of well-separated anthracene planes. Remarkable solvent effects on the UV–vis and fluorescence spectra of this compound were noted.

Liposomes have been used as carriers of nucleic acid drugs. In this study, we demonstrated the transportation of DNA into liposomes using ultrafast photocrosslinking for delivery of nucleic acid drugs. The cohesion of DNA on the surface of liposomes induced transformations in the liposomes and enabled phototriggered, sequence-specific DNA transportation into liposomes by hybridization chain reactions.

Microporous titanoaluminosilicate with MSE topology was synthesized by the addition of titanium tetrabutoxide diluted with aqueous H₂O₂ into the aluminosilicate gel containing a bulky structure-directing agent. The acid treatment of this titanoaluminosilicate resulted in selective dealumination to give an efficient titanosilicate catalyst for the selective oxidation of phenol using H₂O₂.

Titanium dioxide nanoparticles (TiO₂ NPs) are an emerging environmental concern, considering their proven toxicity and wide commercial application nowadays. Once entering natural water bodies, they might become a challenge to conventional water treatment techniques. In this pioneering study, coagulation was found to achieve 86% of concentration removal and 74% of turbidity removal of TiO₂ NPs in natural lake water, when the initial concentration was 1 mg L⁻¹ and the corresponding turbidity was 2.3 NTU. Furthermore, the zeta potential seemed not to be the only decisive factor in the coagulation effect. Further studies on the clarification of the mechanisms involved are hence recommended.