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The development of stable, Earth-abundant, and high-activity molecular water oxidation catalysts under acidic and neutral conditions remains a great challenge. Here, the use of N-heterocyclic carbene (NHC)-based iron(III) complex 1 {[phenyl(tris(3-methylimidazol-1-ylidene))borate]2Fe(III)}+ as a catalyst for water oxidation under acidic and neutral conditions was investigated. Two iron(II) carbene complexes, 2 {[2,6-bis(3-methylimidazolium-1-yl)pyridine]2Fe}2+ and 3 {[2,6-bis(3-methylimidazolium-1-yl)pyridine-4-carboxylic acid]2Fe}2+, were also used for comparison. A series of experiments demonstrate that complex 1 has excellent performance in terms of both catalytic activity and stability. In addition, the faradaic efficiency and turnover frequency (TOF) reach 95.0% and 2.8 s−1, respectively. An overpotential of ca. 490 mV is obtained at pH 1.5. Density functional theory (DFT) calculations indicate that dehydrogenation is the potential-determining step (PDS) in water oxidation. Complex 1 has a lower free energy barrier in this process than 2 and 3. High-valent Fe species are further proven in 1 by spectroelectrochemical measurements, which are crucial in promoting water oxidation. This study is expected to contribute to the development of homogeneous water oxidation catalysis under acidic and neutral conditions. [ABSTRACT FROM AUTHOR]

A new vanadate SrMn2(VO4)2(H2O)2 was synthesized and characterized by single-crystal X-ray analysis. It crystallizes in the monoclinic system with space group C2/m, and exhibits a quasi-one-dimensional (1D) structure. The Mn2+ ions form infinite linear-chains along the b-axis through edge-sharing oxygen atoms and further the linear-chains are connected by VO4 polyhedra into a layer in the ab-plane with Sr2+ ions residing in the space between the layers. Magnetic measurement results show that SrMn2(VO4)2(H2O)2 possesses two spin-canted antiferromagnetic orderings at ∼45 K and ∼7 K. The first ordering at ∼45 K possibly corresponds to a small deviation of spins from a strictly antiparallel arrangement. As the temperature decreases, further spin rotations occur leading to a steadier noncollinear antiferromagnetic phase, leading to the second ordering at ∼7 K. Also, a field-induced transition is observed at a critical field (0.4 T) below ∼7 K. [ABSTRACT FROM AUTHOR]

Cu5(VO4)2(OH)4 (turanite) is a layered compound, exhibiting a copper(ii) oxide layer in the [0 1 1] plane composed of edge-sharing CuO6 octahedra. Each Cu–O layer is further separated by VO4 tetrahedra. Closer scrutiny found that the copper(ii) oxide layer in the compound represents a totally new geometrically-frustrated lattice, a 1/6 depleted triangular lattice. More specifically, the spin network in the [0 1 1] plane is formed by the alternate ranking of triangular and honeycomb strips. Magnetic measurements show that the Cu5(VO4)2(OH)4 behaves as a spin-1/2 ferrimagnet with a Tc = ∼4.5 K. It exhibits an unusual 1/5 magnetization plateau arising from the competition between antiferromagnetic and ferromagnetic interactions caused by the strong frustration. The possible spin-arrangements are also suggested. [ABSTRACT FROM AUTHOR]

Two windmill-like Ag3Cu5 alkynyl clusters were synthesized and characterized. They display novel PL and ECL properties, which could be modified by changing the substituent on the alkynyl ligands. According to the study of electrochemical behaviours, ECL behaviours and ECL emission spectra of the Ag3Cu5 clusters, a possible ECL mechanism was proposed. [ABSTRACT FROM AUTHOR]

An Ir/CeO2 composite catalyst with Ir nanorods (NRs) on amorphous CeO2 was synthesized through a facile one-pot hydrothermal method, which shows excellent activity towards hydrogen evolution and oxygen evolution in alkaline media, even superior to the performance of commercial Pt/C, IrO2 and RuO2 catalysts. The enhanced performance could be attributed to the interfacial electron synergistic effect between Ir and CeO2. [ABSTRACT FROM AUTHOR]

We report a water-soluble AIEgen (TPAL) that can self-assemble into fluorescent organic nanoparticles for the ratiometric detection of mitochondrial DNA (mtDNA) parallel G-quadruplexes (G4s) with high selectivity, a low detection limit and photodynamic therapy (PDT) potential. [ABSTRACT FROM AUTHOR]

We herein present a new family of crown ether-based covalent organic frameworks (CE-COFs) for the first time. The CE-COFs show excellent phase-transfer catalytic performance in various nucleophilic substitution reactions. [ABSTRACT FROM AUTHOR]

Two BODIPY-carbazole dye based fluorescent probes BCA and BCAS were designed, synthesized and encapsulated by liposomes to obtain fluorescent nanoparticles BCA-FNP and BCAS-FNP. The fluorescence imaging showed that BCA-FNP was membrane-permeable and capable of localizing lysosomes in living cells. [ABSTRACT FROM AUTHOR]

Two kinds of AIE-active fluorescent organic nanoparticles were designed and constructed as anti-counterfeiting photoresponsive materials. One is fluorescent organic nanoparticles (TPELs) based on a self-assembly strategy, which were self-assembled from novel amphiphilic tetraphenylethylene (TPE) molecules decorated with a lactose moiety and different photoresponsive tags. The other is polymeric fluorescent organic nanoparticles (F-TPEs) derived from the nanoprecipitation strategy, which utilized pluronic copolymer F127 to encapsulate hydrophobic TPEs without lactosyl modifications. Upon UV light irradiation, these AIE-active materials exhibit different photooxidation behaviors in an aqueous solution to give cyan, orange and green fluorescence emissions, and they were successfully used as an anti-counterfeiting fluorescent hydrogel and ink. [ABSTRACT FROM AUTHOR]

We report a water-soluble AIEgen (TYDL) to be self-assembled into fluorescent organic nanoparticles (TYDLs) for specific sensing of SO2 in living hepatoma cells. It is demonstrated that the TYDLs were suitable for ratiometrically detecting endogenous and exogenous SO2 in mitochondria with good selectivity, low detection limit (75 nM) and excellent photostability (>30 min). These findings imply the great potential applications of TYDLs for the diagnosis of SO2-related diseases in cell biology. [ABSTRACT FROM AUTHOR]

A novel copper compound, Cu13(VO4)4(OH)10F4, featuring two types of two-dimensional extended kagome-like and triangular lattices, exhibits long-range antiferromagnetic ordering at ∼3 K, a strong spin-frustration effect with f = 21 and a spin-flop transition at 5 T. [ABSTRACT FROM AUTHOR]

Based on a preactivation strategy using the (p-Tol)2SO/Tf2O system, a series of nucleosides were synthesized by coupling various thioglycosides with pyrimidines and purines under mild conditions. High yields and excellent β-stereoselectivities were obtained with either armed or disarmed N-glycosylation donors by tuning the amount of (p-Tol)2SO additive. [ABSTRACT FROM AUTHOR]

The first-order phase transition plays a pivotal role in material behaviors, yet that of carbides, a type of important material, has not been systematically studied. Herein, the melting process and structural properties of binary iron carbide (FexCy) nanoparticles are characterized by reactive molecular dynamics simulation. It was found that the melting point of FexCy nanoparticles decreased with the decreasing size and increased with the increasing Fe/C ratio, which were consistent with the experimental results. The melting process starts at the surface and proceeds inwards. The carbon atoms are fully activated before reaching the melting point and the iron core melts last. At high temperatures, carbon atoms exhibit significant outward diffusion behavior and form carbon deposition on the surface. When the temperature exceeds the pre-melting point, although the high temperature gives the nanoparticles more atomic active sites with low coordination, the surface carbon accumulation, such as C2, blocks the active sites leading to a lower turnover frequency of FexCy for CO dissociation. These findings provide an atomistic comprehension of the melting mechanisms and behaviors of binary FexCy nanoparticles, as well as a theoretical foundation for understanding their structural transformation as a catalyst, which is caused by the heat released from catalytic exothermic reactions. [ABSTRACT FROM AUTHOR]

A novel turn-on fluorogenic aldehyde-appended salamo-like copper(II) complex probe (ASC) was rationally designed and exploited for the two-pronged sensing of thiosulfate (S2O32−) ions and glutathione (GSH) based on an intramolecular charge transfer (ICT) process, which could be fully characterized by using various spectroscopic techniques. It is worth noting that the solid-state crystal structure of the Cu(II) complex is rarely different from its structure in solution (ASC) through a single-crystal X-ray diffraction experiment. Importantly, the developed probe exhibited good sensitivity in response to S2O32− and GSH in an aqueous DMF medium within a detection limit of 149 and 131 nM, respectively. Meanwhile, the designed complex probe could be capable of discriminatively detecting S2O32− ions over other sulfur-containing anions. The probe ASC was applied in real water samples utilizing tap water and rain water for the detection of the S2O32− ion. In addition, this probe could be successfully applied to test strips towards S2O32− and GSH. Finally, we unveiled the rationality of the fluorescence "off–on" responses of ASC to S2O32− and GSH by means of density functional theory (DFT) and time-dependent density functional theory (TD-DFT) computations. [ABSTRACT FROM AUTHOR]

A partially amorphous palladium sulfide was synthesized by sulfurizing crystalline palladium nanosheets facilely, which shows excellent activity and stability towards hydrogen evolution in alkaline media, even superior to the performance of the commercial Pt/C catalyst. The enhanced performance could be attributed to the amorphization transformation and the nanosheet morphology. [ABSTRACT FROM AUTHOR]

Surfactants play important roles in chemical industries and have become well-known environmental pollutants owing to their extensive use in different fields. In this work, we reported a fluorescent probe, namely, BDP-Zn2+ for the discrimination of four kinds of surfactants and the determination of CMC values. BDP-Zn2+ was composed of covalently linked BODIPY, carbazole, N,N-bis(2-pyridylmethyl)ethylenediamine (BPEA) and zinc ions to fabricate a novel push–pull molecular structure. Upon the addition of surfactants, the probe exhibited a turn-on fluorescence response and the emission was enhanced on increasing the surfactant concentrations. This indicated that the fluorescence intensity and the ratios of the emission at 607 nm to that at 514 nm as fingerprints could be used to identify the CMC values of the surfactants. Our current work provides an alternative method to efficiently discriminate different surfactants for the further studies of their physical and chemical functions. [ABSTRACT FROM AUTHOR]

An amphiphilic tri-functional ligand (L1) containing a Lewis acidic phosphonium cation, a phosphino-fragment and a hydrophilic sulfonate anion (–SO3−) enabled Pd(OAc)2 to efficiently co-catalyze the hydroxycarbonylation of terminal alkynes towards α,β-unsaturated carboxylic acids. These incorporated functional groups synergistically promoted the reaction, which proved more effective than the ligands lacking –SO3− and/or phosphonium and the mechanical mixtures of the individual functional groups independently. The molecular structure of Pd-L1 indicated that –SO3− in L1 served as a secondary O-donor ligand with reversible coordinating ability, cooperating with the phosphino-fragment to stabilize the Pd-catalyst. The in situ FT-IR analysis verified that the formation and stability of Pd–H active species in charge of hydroxycarbonylation were dramatically facilitated by the presence of L1. It was believed that, over the L1-based Pd-catalyst, H2O was cooperatively activated by the Lewis acidic phosphonium via "acid–base pair" interaction (H2O → P(V)+) and by the hydrophilic SO3−via hydrogen bonding (SO3−⋯H2O), giving rise to the formation of dimeric and mono-nuclear Pd–H species driven by reversible SO3−-coordination. In addition, the L1-based Pd-catalyst could be immobilized in the ionic liquid [Bmim]NTf2 for six-run recycling uses without obvious activity loss and detectable metal leaching. [ABSTRACT FROM AUTHOR]

In this work, we designed and synthesized an aggregation-induced emission (AIE)-active tetraphenylethene-decorated pseudo-trisialic acid (TPE3S) and validated its high affinity for Siglecs using microscale thermophoresis techniques. TPE3S was a unique binding-on fluorescent trivalent sialocluster which was successfully utilized for the visualization of Siglecs expressed on the surface of mammalian cells. [ABSTRACT FROM AUTHOR]

We report a turn-on tetravalent sialic acid-coated tetraphenylethene luminogen (TPE4S) with excellent hydrophilicity, good stability, high sensitivity and unique selectivity towards sialidases, and the maximum fluorescence enhancement was ∼40 fold. More importantly, TPE4S was successfully utilized for the screening of sialidase inhibitors and diagnosis of bacterial vaginosis. [ABSTRACT FROM AUTHOR]

A dialdehyde–diboronate-functionalized tetraphenylethene (TPE-DABF) was reported as a H2O2-specific AIE luminogen. TPE-DABF, bearing multiple reductive units (aldehyde, boronate and fructose) in one molecule, afforded an excellent H2O2 selectivity over other ROS in biological buffer, and can be used for sensitive detection of glucose under neutral conditions. [ABSTRACT FROM AUTHOR]

A sugar epitope, α-(2,9)-trisialic acid, was synthesized and labeled by cyanine dyes through Cu(i)-catalyzed azide–alkyne cycloaddition (CuAAC). The cyanine tagged oligosialic acid can be utilized as an efficient fluorescent probe to image the glycan-binding receptors on PC-12 cells. The distribution of Sia-binding immunoglobulin-like lectins (Siglecs) for α-(2,9)-trisialic acid was visualized by Cy3/Cy5 or FRET channel fluorescence imaging. [ABSTRACT FROM AUTHOR]