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Two Zn2+-based luminescent metal–organic frameworks containing the same components, {[Zn(TIPA)pim0.5]2H2O·NO3}n (1) and {[Zn(TIPA)(pim)]3H2O}n (2) have been synthesized based on a π-electron rich semi-rigid triangular ligand TIPA (TIPA = tris(4-(1H-imidazol-1-yl)-phenyl)amine and H2pim = pimelic acid). 1 is a two-fold interpenetrating 3D framework containing four chiral (10,3)-a subnets, and 2 is merely a 2D + 2D → 2D entangled network, although they were synthesized from the same starting materials. A photoluminescence investigation revealed that the emissions of 1 and 2 entirely originate from the intraligands charge transfer transitions (π→π*). Metal–organic framework 1 can be applied as a dual functional chemical sensor for nitroaromatic (NAC) compounds and antibiotics detection with a high sensitivity and quick response. In addition, the effective detection of nitroaromatic compounds and antibiotics was rationalized by the density functional theory (DFT) calculation of the energy bands of the NAC compounds and antibiotics, which revealed that a photoinduced electron transfer mechanism is largely responsible for the sensing of nitroaromatic compounds, and the resonance energy transfer is largely responsible for the exclusive sensing of ofloxacin (OFX). [ABSTRACT FROM AUTHOR]

Graphitic carbon nitride (g‐C3N4) has been widely explored as a photocatalyst for water splitting. The anodic water oxidation reaction (WOR) remains a major obstacle for such processes, with issues such as low surface area of g‐C3N4, poor light absorption, and low charge‐transfer efficiency. In this work, such longtime concerns have been partially addressed with band gap and surface engineering of nanostructured graphitic carbon nitride (g‐C3N4). Specifically, surface area and charge‐transfer efficiency are significantly enhanced through architecting g‐C3N4 on nanorod TiO2 to avoid aggregation of layered g‐C3N4. Moreover, a simple phosphide gas treatment of TiO2/g‐C3N4 configuration not only narrows the band gap of g‐C3N4 by 0.57 eV shifting it into visible range but also generates in situ a metal phosphide (M=Fe, Cu) water oxidation cocatalyst. This TiO2/g‐C3N4/FeP configuration significantly improves charge separation and transfer capability. As a result, our non‐noble‐metal photoelectrochemical system yields outstanding visible light (>420 nm) photocurrent: approximately 0.3 mA cm−2 at 1.23 V and 1.1 mA cm−2 at 2.0 V versus RHE, which is the highest for a g‐C3N4‐based photoanode. It is expected that the TiO2/g‐C3N4/FeP configuration synthesized by a simple phosphide gas treatment will provide new insight for producing robust g‐C3N4 for water oxidation. A single step for g‐C3N4, a giant leap for water splitting: A simple phosphide gas treatment of g‐C3N4 coated TiO2‐nanorod configuration not only narrows the band gap of g‐C3N4 by 0.57 eV into visible range but also generates a metal phosphide (M=Fe, Cu) water oxidation cocatalyst in situ. This TiO2/g‐C3N4/FeP configuration significantly improves charge separation and transfer capability, resulting in an enhanced photoelectrochemical water oxidation. [ABSTRACT FROM AUTHOR]

Constructing isotype g‐C3N4/g‐C3N4 heterojunction is an approach to improve the efficiency of g‐C3N4 towards solar‐assisted oxidation of water. Such functional configuration can effectively overcome the intrinsic drawback of rapid charge recombination of g‐C3N4. Here, a modified g‐C3N4, with homogeneous phosphorus doping, is prepared in this work through a phosphide‐involved gas phase reaction. The resulting P‐g‐C3N4 displays altered electronic structure, including upshifted band edge potential, narrowed band gap and improved electronic conductivity. These features allow P‐g‐C3N4 as an outstanding candidate to form isotype junction with pristine g‐C3N4. As expected, the accelerated charge separation and migration in target junction is validated by various measurements. The optimized isotype g‐C3N4/P‐g‐C3N4 heterojunction achieves a photocurrent as high as 0.3 mA cm−2 at 1.23 V vs RHE (AM 1.5G, 100 mW cm−2), representing 8‐fold's enhancement compared with pristine g‐C3N4. The present strategy for constructing g‐C3N4‐based isotype heterojunction networks is found effective for large‐scale manufacturing. Isotype photoanode: A phosphorus‐doped g‐C3N4 with suitable electronic structure was explored to construct metal‐free isotype photojunction in large‐scale manufacturing. The percolated networks exhibit largely increased photocurrent than its single component as a result of efficient charge transfer being qualitatively identified. [ABSTRACT FROM AUTHOR]

Tubular hematite with high-concentration, uniform doping is regarded as a promising material for photoelectrochemical water oxidation. However, the high-temperature annealing commonly used for activating doped hematite inevitably causes deformation of the tubular structure and an increase in the trap states. In the present work, Sn-doped tubular hematite on fluorine-doped tin oxide (FTO) is successfully obtained at 750 °C from a Sn-coated FeOOH tube precursor. Sn/P codoping, which is rarely considered for hematite, is also achieved via a gas phase reaction in phosphide atmosphere. The tubular morphology allows the dopant to diffuse from both the inner and outer surfaces, thus decreasing the doping profile in the radial direction. The even distribution of Sn and P synergetically increases the carrier density of hematite by one order of magnitude, which shortens the width of the depletion layer to ca. 2.3 nm (compared with 19.3 nm for the pristine sample) and leads to prolonged carrier lifetime and efficient charge separation. In addition, this codoping protocol does not introduce additional surface trap states, as evidenced by the increased charge injection efficiency and surface kinetic analysis using intensity modulated photocurrent spectroscopy (IMPS). As a result, the morphology- and doping-engineered hematite exhibits photocurrents of 0.9 mA cm−2 at 1.23 V and 3.8 mA cm−2 at 2.0 V vs. RHE under AM 1.5 G illumination (100 mW cm−2) in 1.0 M NaOH, representing 4.5-fold and 4.8-fold enhancements, respectively, compared with the photocurrents of undoped hematite. The present method is shown to be effective for preparing multi-element-doped hematite nanotubes and may find broad application in the development of other nanotubular photoelectrodes with or without doping for efficient and robust water oxidation. [ABSTRACT FROM AUTHOR]

Developing high surface area nanostructured electrodes with fast charge separation is one of the main challenges for exploring cupric oxide (CuO)-based photocathodes in solar-driven hydrogen production applications. Herein, brand new 1D branched CuO nanowire arrays have been achieved on fluorine-doped tin oxide-coated glass (FTO) through a two-step wet chemical redox reaction. X-ray diffraction patterns, Raman spectra and X-ray photoelectron spectroscopy confirm the pure phase characteristic of the resulting branched CuO. In addition to the enlarged surface area of this advanced functional structure as compared with that of the 1D wire trunk, the charge injection and separation have been improved by rationally controlling the density of defects and size of branches. As a result, the optimized branched CuO exhibits photocurrent as high as 3.6 mA·cm−2 under AM 1.5G (100 mW·cm−2) illumination and 3.0 mA·cm−2 under visible light (λ ＞ 420 nm) at 0.2 V vs. RHE in 0.5 M Na2SO4, which are 2.8- and 3.0-fold greater than those of 1D wire samples, respectively. In addition, the solution-processed approach established herein seems quite favourable for large-scale and low-cost manufacturing. [ABSTRACT FROM AUTHOR]

One of the most interesting phenomena in coordination polymers (CPs) is the co-existence of different interlaced motifs. However, CPs having two different interlaced motifs at the same time are still rare. Colourless block-shaped crystals of the two-dimensional polymer poly[[aqua(μ2-naphthalene-2,6-dicarboxylato){μ2-4,4′-[oxybis(4,1-phenylene)]dipyridine}cadmium(II)] monohydrate], {[Cd(C12H6O4)(C22H16N2O)(H2O)]·H2O} n, (I), was synthesized under hydrothermal conditions by the self-assembly of 4,4′-[oxybis(4,1-phenylene)]dipyridine (OPY) with CdII in the presence of naphthalene-2,6-dicarboxylic acid (H2ndc). Each CdII ion is six-coordinated by two N atoms from the pyridine rings of two OPY ligands and by four O atoms, three of which are from two ndc2− ligands and one of which is from a water molecule. In (I), every two identical two-dimensional (2D) 63 layers are interpenetrated in a parallel fashion, resulting in an interesting 2D→2D framework with both polyrotaxane and polycatenane characteristics. The extension of these sheets into a three-dimensional supramolecular net is via O-H...O hydrogen bonds. The solid-state photoluminescence properties of (I) are also discussed. [ABSTRACT FROM AUTHOR]

In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. N-Donor ligands with diverse coordination modes and conformations have been employed to assemble metal-organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds and are thus good candidates for the construction of supramolecular architectures. Two new transition metal complexes, namely poly[diaqua(μ4-1,4-bis{[1-(pyridin-3-ylmethyl)-1 H-benz[ d]imidazol-2-yl]methoxy}benzene)bis(μ2-isophthalato)dicobalt(II)], [Co(C8H4O4)(C34H28N6O2)0.5(H2O)] n, (1), and poly[diaqua(μ4-1,4-bis{[1-(pyridin-3-ylmethyl)-1 H-benz[ d]imidazol-2-yl]methoxy}benzene)bis(μ2-isophthalato)dicadmium(II)], [Cd(C8H4O4)(C34H28N6O2)0.5(H2O)] n, have been constructed using a symmetric N-donor ligand and a carboxylate ligand under hydrothermal conditions. X-ray crystallographic studies reveal that complexes (1) and (2) are isostructural, both of them exhibiting three-dimensional supramolecular architectures built by hydrogen bonds in which the coordinated water molecules serve as donors, while the O atoms of the carboxylate groups act as acceptors. Furthermore, (1) and (2) have been characterized by elemental, IR spectroscopic, powder X-ray diffraction (PXRD) and thermogravimetric analyses. The UV-Vis absorption spectrum of complex (1) has also been investigated. [ABSTRACT FROM AUTHOR]

A series of mononuclear Ni(II), Co(III), and Zn(II) complexes based on a Schiff base ligand, 4-chloro-6-[2-(pyrazin-2-ylmethylene)hydrazinyl]pyrimidine (HL), have been synthesized and characterized by physicochemical and spectroscopic methods. The complexes were found to have superior radical scavenging potency against DPPH, superoxide anion, hydroxyl, and ABTS radicals than free HL. The antibacterial effects of the complexes against Gram-positive and Gram-negative bacteria were also higher than that of free HL. [ABSTRACT FROM AUTHOR]

Two Zn(II) coordination polymers, {[Zn3(L)2(bipy)2(H2O)4}n(1) and {[Zn(HL)(4,4′-bibp)}n(2), were obtained from Zn(II) nitrate, a tricarboxylate ligand (H3L) and different N-containing ligands with hydrothermal conditions, where H3L = 4-((6-carboxynaphthalen-2-yl)oxy)phthalic acid, bipy = 4,4′-bipyridine, and 4,4′-bibp = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl. Single-crystal X-ray analysis reveals that1has a 2-D layer framework formed by L3−and bipy and2has an infinite 1-D structure with Zn2units built by 4,4′-bibp ligands. The phase purity, IR spectra, thermal stabilities, and fluorescence properties in the solid state of1and2were investigated. Moreover,1and2were chosen as fluorescent probes to sense different metal ions, showing selective response to Fe3+ion through luminescence quenching. The possible sensing mechanism to Fe3+ion is also discussed. [ABSTRACT FROM AUTHOR]

A C2 symmetric small molecule composed of l-phenylalanine and isophthalamide was found to function as a Cl−/HCO3− dual transporter and self-assemble into chloride channels. In Ussing-chamber based short-circuit current measurements, this molecule elicited chloride-dependent short-circuit current (Isc) increase in both Calu-3 cell and CFBE41o-cell (with F508del mutant CFTR) monolayers. [ABSTRACT FROM AUTHOR]

Four novel cobalt(ii) complexes {[Co3(L)2(dib)3(H2O)2]·2H2O}n (1), {[Co3(L)2(4,4′-bibp)3(H2O)4]·2H2O}n (2), {[Co(HL)(bidpe)]·H2O}n (3) and {[Co2(L)(bib)0.5(μ3-OH)]·2H2O}n (4) have been prepared by employing Co(ii) nitrate, a tricarboxylate ligand (H3L) and different N-containing ligands under hydrothermal conditions, where H3L = 3-((6-carboxynaphthalen-2-yl)oxy)phthalic acid, dib = 1,4-di(1H-imidazol-1-yl)benzene, 4,4′-bibp = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl, bidpe = 1,1′-(oxybis(4,1-phenylene))bis(1H-imidazole), bib = 4,4′-bis((2-methyl-1H-imidazol-1-yl)methyl)-1,1′-biphenyl. Single crystal X-ray analysis reveals that complex 1 exhibits an infinite 2D framework formed by the L3− and dib ligands, complex 2 displays a 3D supramolecular architecture linked by hydrogen bonds, complex 3 features a 1D chain in which lattice water molecules locate with the help of hydrogen bonds, complex 4 is a homochiral 3D network with right-handed 43 and 21 helices. The phase purity, IR spectra and thermal stabilities of 1–4 have been investigated. Additionally, the magnetic behaviors for 1–4 have also been studied, revealing antiferromagnetic interactions between Co(ii) ions in them. [ABSTRACT FROM AUTHOR]

This highlight discusses the structures and functions of W–Cu–S cluster polymers divided into different multinuclear cluster units. Great strides have been made in the potential applications of W–Cu–S cluster polymers in advanced materials, including third-order non-linear optics (NLO), gas absorption and solvatochromic effects, in the past few years. Finally, we suggest some opportunities to further improve the depth of the related research. [ABSTRACT FROM AUTHOR]

The self-assembly reaction of a multinodal preformed cluster with 1,2-di(pyridin-4-yl)ethane as the organic ligand afforded the 2D cluster polymer (1), {[(WS4Cu4)I2(dpe)2](DMF)4}n. There is a cavity between each two nearby dpe ligands in 1. The [WS4Cu4]2+ units are fixed by I− ions, which is attributed to the multinodal feature of the W–S–Cu secondary building units, and therefore, the cavities in 1 are settled. The NLO properties show that 1 exhibits an optical self-focusing behavior and reverse saturable absorption effects. This work provides us with useful clues to further explore the 2D W–Cu–S-based cluster polymer with cavities. [ABSTRACT FROM AUTHOR]

In the title compound, [Ni(C12H6O4)(C22H16N2O)2(H2O)2] n, the Ni2+ cation resides on a centre of inversion in a slightly distorted octahedral [N2O4] environment. The two carboxylate groups of each naphthalene-2,6-dicarboxylate (NDC2−) ligand, which reside on centres of inversion, link the NiII cations into a one-dimensional chain. Identical chains are linked by intermolecular hydrogen bonds between coordinated water molecules and the uncoordinated N atoms of 4-{4-[4-(pyridin-4-yl)phenoxy]phenyl}pyridine ligands to form (4,4)-topological sheets, and then the different sheets are interlocked in an inclined fashion to give a three-dimensional polycatenation network. The stability of the structure is further enhanced by π-π stacking interactions between pyridine and benzene rings. [ABSTRACT FROM AUTHOR]

Aims Intracellular Ca2+ ([Ca2+]i) regulation in endothelial cells depends on transient receptor potential channels (TRPs), and the role of canonical TRPs (TRPCs) during hypoxia–reoxygenation (H–R) is unclear. We hypothesized that TRPC3 contributes to endothelial nitric oxide (NO) release and that H–R may reduce TRPC3 activity and the associated endothelial function, including NO release. Methods and results Measurements of [Ca2+]i and patch-clamp study in primary cultured porcine coronary endothelial cells, measurements of NO and endothelium-dependent relaxation in porcine coronary arteries, and RT-PCR and western blot were conducted. Pre-treatment with SKF96365 (an inhibitor of TRPCs) or the selective TRPC3 inhibitor Pyr3 significantly decreased bradykinin-induced vasorelaxation. One hour of hypoxia followed by reoxygenation significantly reduced the vasorelaxation (70.3 ± 6.4 vs. 88.9 ± 3.5%) and NO concentration (24.0 ± 1.3 vs. 45.2 ± 2.8 nmol/L), and they were restored by pre-incubation with the TRPC3/6/7 activator 1-oleoyl-2-acetyl-sn-glycerol (96.4 ± 1.8% and 41.1 ± 4.7 nmol/L, respectively). In porcine coronary endothelial cells, H–R inhibited bradykinin-activated membrane current (8.6 ± 0.4 vs. 14.0 ± 1.5 pA/pF) and Pyr3-sensitive TRPC3 current (3.8 ± 0.3 vs. 6.3 ± 0.6 pA/pF; P< 0.01). H–R also inhibited bradykinin-induced Ca2+ influx and the Ca2+ influx via TRPC3. Cell surface expression of TRPC3 was decreased after H–R. Conclusions We have, for the first time, demonstrated that Ca2+ entry via endothelial TRPC3 contributes to NO release and have revealed that H–R is associated with inhibition of TRPC3 activity. Inhibition of channel trafficking to the cell surface is involved in the underlying mechanism of the decrease of TRPC3 current and the reduction in Ca2+ entry through TRPC3 during H–R. This study suggests that TRPC3 may have the potential to be a new target for endothelial protection during H–R. [ABSTRACT FROM PUBLISHER]

Four metal–organic coordination polymers, {[Cu2(4,4′-bibp)2(NO2)3)]·(NO2)(H2O)}n(1), [Cd(bdc)(4,4′-bibp)]n(2), {[Co2(bdc)2(4,4′-bibp)3(H2O)2]·(H2O)2}n(3), [Zn(Hbtc)(1,4-bix)]n(4) (4,4′-bibp = 4,4′-bis(1-imidazolyl)biphenyl; 1,4-bix = 1,4-bis((1H-imidazol-1-yl)methyl)benzene; H2bdc = 1,4-benzenedicarboxylate; H3btc = 1,3,5-benzenetricarboxylate) were obtained under hydrothermal conditions and characterized structurally. X-Ray diffraction analysis reveals that the four complexes exhibit new frameworks due to diverse coordination conformations. In copper compound 1, with mixed-valence copper(ii)–copper(i), rigid linear 4,4′-bibp ligands connect two adjacent layers and the whole structure is a three-dimensional 6,6-connected network. In cadmium compound 2, 4,4′-bibp and bdc anions as bidentate ligands coordinate to cadmium cations to form a three-dimensional 4,4-connected network with a 3-fold interpenetrating framework. In cobalt compound 3, 4,4′-bibp and bdc anions also act as bidentate ligands, and coordinate to cobalt cations to form a three-dimensional 4,6-connected network. Zinc compound 4shows that both the 1,4-bix ligand and btc anions act as bidentate bridging ligands, and connect the zinc cations to give a 2D polycatenated array structure. The magnetic properties for copper compound 1and luminescent properties for cadmium compound 2and zinc compound 4are also discussed in detail. [ABSTRACT FROM AUTHOR]

ABSTRACT Berberine, is an alkaloid from Hydrastis canadensis L., Chinese herb Huanglian, and many other plants. It is widely used in traditional Chinese medicine as an antimicrobial in the treatment of dysentery and infectious diarrhea. This manuscript describes cardiovascular effects of berberine and its derivatives, tetrahydroberberine and 8-oxoberberine. Berberine has positive inotropic, negative chronotropic, antiarrhythmic, and vasodilator properties. Both derivatives of berberine have antiarrhythmic activity. Some of cardiovascular effects of berberine and its derivatives are attributed to the blockade of K+ channels (delayed rectifier and KATP) and stimulation of Na+-Ca2+ exchanger. Berberine has been shown to prolong the duration of ventricular action potential. Its vasodilator activity has been attributed to multiple cellular mechanisms. The cardiovascular effects of berberine suggest its possible clinical usefulness in the treatment of arrhythmias and/or heart failure. [ABSTRACT FROM AUTHOR]

The self-assembly reaction of the preformed clusters with two extended linear and trigonal rigid ligands as organic linkers afforded two 2D and 3D Mo(W)/Cu/S-based cluster polymers. They show unprecedented structure types in Mo(W)/S/Cu chemistry and exhibit strong third-order nonlinear optical properties. [ABSTRACT FROM AUTHOR]