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Three pargyline-phosphine copper(I) clusters, [Cu4(C≡C–C9H12N)3(PPh3)4](PF6) (1) and [Cu6(C≡C–C9H12N)4(dppy)4](X)2 (dppy = diphenyl-2-pyridylphosphine; X = PF6 for 2 and X = ClO4 for 3), were synthesized. Their structures were fully characterized using various spectroscopic methods and X-ray crystallography, which showed that the stoichiometry and nature of pargyline and phosphine ligands play an important role in tuning the structure and photophysical features of Cu(I) clusters. Interestingly, clusters 1, 2 and 3 exhibited red, orange and yellow phosphorescence with high quantum yields of 88.5%, 22.0% and 40.2%, respectively, at room temperature. Moreover, clusters 1–3 show distinct temperature-dependent emissions. The excellent luminescence performance of 1 and 3 was designed and employed for the construction of monochrome and white light-emitting devices (LEDs). [ABSTRACT FROM AUTHOR]

A multicolor electrochromic material based on polyoxometalate and a dye with pH and voltage dual-adjustment was studied. The material (PEI/[PEI/P2W18/PEI/AR]30/PEI (P2W18-AR) film) was prepared by a simple layer-by-layer method and tested in several solutions of different pH (pH 2.00, pH 4.00, and pH 6.00), referred to as F1, F2, and F3, respectively. By applying different voltages, the color of the film could change from yellow to blue-green (F1), pink-orange to blue-violet (F2), and dark pink to violet (F3), while maintaining good electrochromic performance and stability. Among them, F1 showed the best optical contrast up to 39.71%, and the optical contrast retention rate of F3 was 90.71% after 1000 cycles. Simultaneously, the fabricated electrochromic devices also showed color adjustments. This film was controlled by pH and voltage, providing a new method for the preparation of multicolor electrochromic composite materials. [ABSTRACT FROM AUTHOR]

Gyroid materials have received considerable attention from scientists due to their beautiful structures and advanced functions. On the other side, metal–organic frameworks are inorganic–organic hybrid crystalline porous materials with atomic precision, and can provide good structural models and rich topologies for gyroid materials. In this review, we will briefly introduce the structures of gyroid metal–organic frameworks and their topologies. In addition, their applications in gas adsorption, catalysis, sensors, and luminescent materials are also discussed in detail. [ABSTRACT FROM AUTHOR]

As a photophysical phenomenon, aggregation-induced emission (AIE) was proposed by Tang in 2001. Due to their excellent fluorescence emission performance, AIEgens and AIE-based fluorescence materials have shown great application potential in a wide range of science fields. Hence, exploring new AIEgens and construction of novel AIE materials are especially vital. In addition, as a new class of macrocyclic hosts, pillararenes have shown excellent performance in supramolecular chemistry. Interestingly, pillararenes also exhibited fairly bright application prospects in the AIE area: firstly, some research studies suggested that pillararenes could serve as a novel AIEgen with considerable fluorescence emission in the aggregated state; moreover, they could also participate in the construction of AIE materials and have potential application in various areas. In this review, we summarised the recent development of pillararene-based AIE materials from the following aspects: pillararenes as novel AIEgens, the TPE functionalized pillararene-based AIE materials, the pillararene-based AIE materials constructed by supramolecular assembly, and the functionalized pseudo-pillararene-based AIE materials. It is hoped that this feature article will attract increasing attention and pave a new way for the development and application of pillar[n]arene-based AIE materials in more fields. [ABSTRACT FROM AUTHOR]

The development of molecularly imprinted membranes (MIMs) has promoted applications of membrane-based separation technology, which has shown considerable advantages in water treatment, chemical separation and drug purification. Herein, imitated core–shell PEI@SiO2-based enoxacin-imprinted nanocomposite membranes (SPEIMs) were developed by mixing polyethylenimene-modified silica nanoparticles with polyvinylidene fluoride powder under freezing operation. As a typical and hazardous water pollutant, enoxacin was selected as the template molecule. Morphology and chemical characterizations were explored for an insightful analysis of the obtained membranes. Based on the organic–inorganic hybrid strategy, the as-prepared SPEIMs exhibited superior selectivity towards the target (enoxacin). Satisfactory adsorption performance (55.94 mg g−1), permeability (3.22 for norfloxacin/enoxacin and 7.07 for ciprofloxacin/enoxacin) and regeneration performance (90.31%) were achieved onto SPEIMs. The products and methods obtained in this work would potentially enrich the applications of MIMs in pollution control and biochemical separation. [ABSTRACT FROM AUTHOR]

A calix[4]pyrrole strapped by benzenebistriazole has been prepared as an artificial anion binding receptor. This neutral anion receptor shows high sulfate binding affinity and selectivity in an aqueous solution. In solid state, the receptor binds the sulfate anion in a chair-like 3D cavity via multiple N–H and C–H hydrogen bonds. [ABSTRACT FROM AUTHOR]

Covering: 2000 to 2019 Natural products (NPs) are important sources of human therapeutic agents and pesticides. To prevent self-harm from bioactive NPs, some microbial producers employ self-resistance genes to protect themselves. One effective strategy is to employ a self-resistance enzyme (SRE), which is a slightly mutated version of the original metabolic enzyme, and is resistant to the toxic NP but is still functional. The presence of a SRE in a gene cluster can serve as a predictive window to the biological activity of the NPs synthesized by the pathway. In this highlight, we summarize representative examples of NP biosynthetic pathways that utilize self-resistance genes for protection. Recent discoveries based on self-resistance gene identification have helped in bridging the gap between activity-guided and genome-driven approaches for NP discovery and functional assignment. [ABSTRACT FROM AUTHOR]

A novel nanoarchitecture (MSN-Tb-UbR) was prepared by modifying rhodamine B-labelled Ubs (Ub-Rs) on the surface of mesoporous silica nanoparticles (MSNs) loaded with Tb3+-complexes. The MSN-Tb-UbR exhibits ratiometric sensing ability for DUB (UCH-L1) with good sensitivity and selectivity. [ABSTRACT FROM AUTHOR]

In this paper, a two-dimensional (2D) photocatalyst by the BiOCl ultrathin nanosheet modification of biochar (derived from biomass bamboo leaves) was successfully prepared via a facile one-pot hydrothermal process. The synthesized C/BiOCl photocatalysts showed a satisfactory performance on the degradation of tetracycline hydrochloride (TC-HCl). The enhanced photocatalytic activity originating from the introduction of biochar facilitated the rapid transfer of electrons generated from the defect states of the BiOCl ultrathin nanosheets. Moreover, the more the photo-electrons transferred in biochar, the more the quantities of active ˙O2− generated during the photocatalytic reaction, which was confirmed from the free radical capture tests. This work can be extended to the modified routes of BiOCl in the further applications of environmental wastewater treatments. [ABSTRACT FROM AUTHOR]

The rational design and synthesis of low-dimensional chalcogenides with desired properties is vital but still an enormous challenge. Herein, a novel quaternary sulphide, Ba8Zn4Ga2S15 (FJ-2), has been designed by a cation regulation strategy and successfully prepared. It comprises a one-dimensional (1D) {[Zn4Ga2S15]16−}∞ anion chain constructed from supertetrahedron [Zn4S10] clusters. The structure of FJ-2 is unique, as in the literature there are no other 1D structures of the type X/Zn/Ga/Q (X = cations; Q = chalcogen). Moreover, FJ-2 exhibits strong yellow photoluminescence emission at room temperature. DFT calculations using the VASP software package have aided the understanding of the relationship between the optical properties and electronic structure. [ABSTRACT FROM AUTHOR]

A gold(i)-catalyzed highly efficient kinetic resolution of indole–allene derivatives has been demonstrated, providing enantiomerically enriched polycyclic indolines possessing four stereogenic centers including an all-carbon quaternary center in a spirocyclic framework and β-substituted tryptamine derivatives in good to excellent ee values and high s selectivities with good functional group tolerance under mild conditions in an atom-economical way. [ABSTRACT FROM AUTHOR]

A boron doped carbon–sulfur (BCS) aerogel with consecutive “core–shell” structures, acting as a binder free cathode for lithium–sulfur batteries, has achieved a high specific capacity of 1326 mA h g−1, long cycling lifespan and a high areal capacity of 12.3 mA h cm−2. [ABSTRACT FROM AUTHOR]

A series of novel similar lanthanide metal–organic frameworks, namely, [Ln2L12L2(4−x−y)L3xL4y]·nH2O (LnMOF-1–13) (LnMOF-1: Ln = La, x = 0.7, y = 1.3, n = 4.7; LnMOF-2: Ln = Ce, x = 0.7, y = 1.3, n = 4.7; LnMOF-3: Ln = Pr, x = 1, y = 1, n = 5; LnMOF-4: Ln = Sm, x = 1, y = 1, n = 2.5; LnMOF-5: Ln = Eu, x = 1, y = 1, n = 3; LnMOF-6: Ln = Tb, x = 0, y = 2, n = 2; LnMOF-7: Ln = Dy, x = 1, y = 1, n = 3; LnMOF-8: Ln = Er, x = 0, y = 1, n = 3; LnMOF-9: Ln = Nd, x = 1.4, y = 1.4, n = 3.6; LnMOF-10: Ln = Gd, x = 1, y = 1, n = 3; LnMOF-11: Ln = Ho, x = 1.6, y = 0, n = 3; LnMOF-12: Ln = La0.44Eu0.10Tb0.46, x = 1, y = 1, n = 7; LnMOF-13: Ln = La0.66Eu0.11Tb0.23, x = 1, y = 1, n = 7; L1 = 5-((4-formylphenoxy)methyl)isophthalic acid anion, L2 = C3H7ON, L3 = H2O, L4 = HCOOH), have been prepared using a solvothermal method and characterized by single crystal and powder X-ray diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis. All structures are similar and possess a 3D binodal (3,6)-connected net with the point symbol (42·6)2(44·62·87·102). Furthermore, the luminescence measurements indicate that compounds LnMOF-5 and LnMOF-6 display intense characteristic red and yellowish-green emission with quantum yields of 23.30% & 28.25%, respectively. And the three-component La:Eu,Tb-doped compounds exhibit white emission under UV irradiation, especially the compound LnMOF-12 which exhibits the Commission International de l'Eclairage (CIE) chromaticity coordinate (0.332, 0.333) with pure white light emission (Φ = 11.22% at 345 nm). Additionally, the magnetic properties of LnMOF-10 are also investigated. [ABSTRACT FROM AUTHOR]

Two hybrid compounds, namely [CuI4(3atrz)4][PMoVI11MoVO40] (1) and [CuI6(3atrz)6][PMo12O40]2 (2), were synthesized through hydrothermal reactions of 3-amino-1,2,4-triazole (3atrz), phosphomolybdic acid (PMA) and appropriate copper salts. Crystal structure analysis reveals that compound 1 contains one-dimensional Cu-3atrz chains. The unit of compound 2 contains a double calyx[3]arene-shaped hexamer, which is composed of six two-coordinated CuI atoms and six 3atrz ligands. Both compounds 1 and 2 present a three-dimensional hybrid structure, which is built by the self-assembly of Cu-3atrz clusters and Keggin-type PMA units. The resulting hybrid compounds can act as highly efficient heterogeneous catalysts for the selective oxidation of olefins with molecular oxygen as the oxidant in the presence of a trace amount of tert-butyl hydroperoxide (t-BuOOH). Their excellent catalytic properties can be mainly attributed to the existence of stabilized CuI complexes with an appropriate chemical environment and a spacious structure, which can interact with t-BuOOH to form catalytic sites for the direct activation of O2. This work demonstrates that the hybrid compounds assembled from copper-3atrz complexes and phosphomolybdic acid may have great potential in molecular O2-mediated catalytic oxidation reactions, which can certainly build a platform for deep insight into the biologically relevant catalytic oxidation processes. [ABSTRACT FROM AUTHOR]

In the process of recovering platinum group metals by extraction, separation of Pt and Ir is very difficult because Pt(iv) and Ir(iv) show similar chemical properties and extraction behaviours in hydrochloric acid medium. In this paper, a betaine-based ionic liquid [C6bet]Br was firstly applied to the separation of Pt(iv) and Ir(iv). [C6bet]Br showed remarkable precipitation performance of Pt(iv) and Ir(iv). The impactful extraction was realized by importing [C6mim][NTF2] as the hydrophobic phase with extraction efficiencies of ca. 99% and 88% under optimal conditions. A selective reduction process for Ir(iv) was firstly proposed for the separation of these two similar PGMs by using hydroxylamine hydrochloride (NH2OH·HCl). The mechanism of extracting Pt(iv)/Ir(iv) using [C6bet]Br was confirmed to be an anion-exchange process by spectroscopic analysis (UV-Vis, FT-IR, 1H NMR) and the method of continuous variation. The electrostatic potential map of [C6bet]Br was calculated for the first time to confirm the anion-exchange mechanism. 8 M HCl was effective for the back extraction of Pt(iv) and Ir(iv). [ABSTRACT FROM AUTHOR]

Dual C–H thiolation reactions using elemental sulphur remain a challenge. This communication discloses an oxidative radical dual sp2/sp3 C–H thiolation strategy for the coupling of imidazopyridines with ethers or alkanes using elemental sulphur. [ABSTRACT FROM AUTHOR]

The Langlois reagent was found to be effective for the isothiocyanation of primary amines in the presence of copper iodide and diethyl phosphonate. [ABSTRACT FROM AUTHOR]

A Pt(ii)-catalyzed cyclization of (hetero)aryl-allenes has been developed, providing controllable synthesis of substituted 2,3-dihydropyrroles and polyheterocyclic skeletons. Another notable feature of this method is the dual-role of the Pt(ii) catalyst: initiation of the migration of the (hetero)arylmethylene group and the subsequent Friedel–Crafts type annulation. [ABSTRACT FROM AUTHOR]

Three novel zero-dimensional quaternary chalcohalides, Ba4Ge3S9Cl2, Ba4Si3Se9Cl2 and Ba4Ge3Se9Cl2, which crystallize in the polar noncentrosymmetric space group P63 (no. 173), have been rationally synthesized by a tailored approach on the basis of unique [M3Q9]6− (M = Ge, Q = S; M = Ge/Si, Q = Se) units with Ba2+ cations and Cl− anions occupying the interspaces. The [M3Q9]6− units which consist of three Q-corner-sharing [MQ4]4− tetrahedra, are arranged along the 63 screw axis. Remarkably, Ba4Ge3S9Cl2 exhibits a strong powder second harmonic generation (SHG) response that is 2.4 times that of benchmark AgGaS2 at a laser radiation of 2.05 μm in the same particle size range of 46–74 μm. Furthermore, theoretical studies based on the density functional theory helped to gain insight into the origin of the SHG. [ABSTRACT FROM AUTHOR]

Two novel zinc metal–organic frameworks [Zn3(TPT)2(DMF)2]·0.5HNMe2 (1) and NH2Me2·[Zn(TPT)]·DMF (2) have been synthesized by using Zn(ii) ions and p-terphenyl-3,4′′,5-tricarboxylic acid (H3TPT). The structures of these two MOFs are dependent on the solvents used in the synthetic processes. Compound 1 was synthesized in a mixture of DMF and H2O, while compound 2 was obtained in the presence of DMF and ethanol. The three-dimensional (3D) framework of 1 is constructed by the connection of Zn–carboxylate chains and TPT3− linkers. The structure of 2 can be described as a 3,6-connected network based on the assembly of binuclear zinc clusters and TPT3− ligands. These two MOFs exhibit ligand-based photoluminescence at around 375 nm, as well as high efficiency for the recyclable detection of nitroaromatic explosives. [ABSTRACT FROM AUTHOR]

New borophosphates Li3Cs2M2B3P6O24 (M = Pb, Sr) have been synthesized by high-temperature solid-state reactions. The single-crystal X-ray diffraction data reveal their non-centrosymmetric cubic space group P213 and lattice parameters of a = 12.7246(3) Å and 12.687(2) Å and V = 2060.31(8) Å3 and 2042.3(4) Å3 for Li3Cs2Pb2B3P6O24 and Li3Cs2Sr2B3P6O24, respectively. They are three-dimensional (3D) [BP2O8]3−∞ anionic frameworks formed by a new double six-membered ring building unit consisting of BO4 and PO4 units joined alternately. Interestingly, such a double six-membered ring is regarded as the structural variation of the 12-membered ring in the known KSrBP2O8, fusing at the BO4 tetrahedron induced by the coexistence of the Li+ and Cs+ cations with their large size difference. The title compounds show weak SHG intensity and exhibit photoluminescence emissions at 410 nm for Li3Cs2Pb2B3P6O24 and 440 nm for Li3Cs2Sr2B3P6O24. [ABSTRACT FROM AUTHOR]

TiO2 photocatalysis can be performed for the addition of pyridines to vinylarenes in an anti-Markovnikov manner. Seven examples with considerable yields (56–91%) and selectivity were demonstrated. A comparative survey of the involved process through ESR revealed a novel concerted two electron transfer pathway for these photocatalytic bimolecular addition reactions. [ABSTRACT FROM AUTHOR]

Photothermal therapy as a physical therapeutic approach has greatly attracted research interest due to its negligible systemic effects. Among the various photothermal agents, CuS nanoparticles have been widely used due to their easy preparation, low cost, high stability and strong absorption in the NIR region. However, the ambiguous biotoxicity of CuS nanoparticles limited their bio-application. So it is highly desirable to develop biocompatible CuS photothermal agents with the potential of clinical translation. Herein, we report a novel method to synthesize biocompatible CuS nanoparticles for photothermal therapy using bovine serum albumin (BSA) as a template via mimicking biomaterialization processes. Owing to the inherent biocompatibility of BSA, the toxicity assays in vitro and in vivo showed that BSA–CuS nanoparticles possessed good biocompatibility. In vitro and in vivo photothermal therapies were performed and good results were obtained. The bulk of the HeLa cells treated with BSA–CuS nanoparticles under laser irradiation (808 nm) were killed, and the tumor tissues of mice were also successfully eliminated without causing any obvious systemic damage. In summary, a novel strategy for the synthesis of CuS nanoparticles was developed using BSA as the template, and the excellent biocompatibility and efficient photothermal therapy effects of BSA–CuS nanoparticles show great potential as an ideal photothermal agent for cancer treatment. [ABSTRACT FROM AUTHOR]

A microporous lanthanum metal–organic framework [La(TPT)(DMSO)2]·H2O (La-MOF (1)), has been synthesized using a rigid unsymmetrical tricarboxylate ligand of p-terphenyl-3,4′′,5-tricarboxylic acid (H3TPT). The structure of 1 is constructed by bi-nuclear lanthanum clusters and fully deprotonated TPT3− ligands, which can be simplified into a 3,6-connected flu-3,6-C2/c topology with a point symbol of (44·6)2(4·62·87·102). The π-electron rich ligand H3TPT enables 1 to have blue luminescence when excited at 342 nm at ambient temperature. Meanwhile, 1 exhibits the selective detection of picric acid (PA) and Fe3+ ions in ethanol solution over other nitroaromatic compounds and metal ions. The high quenching efficiency and selectivity of 1 makes it a potential bi-functional chemosensor for both PA and Fe3+ ions. [ABSTRACT FROM AUTHOR]

Three novel 3D metal–organic frameworks, [Co2(butca)(o-bix)2·8H2O]n(1), [Co2(butca)(m-bix)2·2H2O]n(2) and [Co2(butca)(p-bix)2·3H2O]n(3) (butca = 1,2,3,4-butane-tetracarboxylic acid; o-bix = 1,2-bis(imidazol-1-ylmethyl)-benzene; m-bix = 1,3-bis(imidazol-1-ylmethyl)-benzene; and p-bix = 1,4-bis(imidazol-1-ylmethyl)-benzene), have been successfully synthesized from a 2D layer compound [Co2(butca)(H2O)5·2H2O]n(0) employing a three isomer pillars insertion reaction, and their structures were determined by single-crystal X-ray diffraction studies. Complexes 1and 2are isostructural. Interestingly, there exist metal-bix double-helical chains in these two 3D frameworks, which are arranged left- and right-handed alternately. Different from 1and 2which have only one coordination model, Co atoms in 3have two types of different coordination enviroments. The Co1 ions are exclusively bridged by cis-bix ligands to give one 26-number ring through spontaneous resolution. At the same time, the Co2 ions are wholely connected with tran-bix ligands to form a 1-D zigzag chain. Moreover, the relationship between a 2D layer structure and 3D metal–organic frameworks based on the pillared-layer motifs is discussed. This work has significant potential for the study of crystal engineering of transition metal coordination networks. [ABSTRACT FROM AUTHOR]

Anisotropic growth of nanomaterials enables advances in building diverse and complex architectures, which exhibit unique properties and enrich the choice of nano-building modules for electrochemical sensor devices. Herein, an anisotropic growth method was proposed to anchor gold nanoparticles (AuNPs) onto both ends of quasi-two-dimensional CdSe semiconductor quantum nanoplatelets (NPLs), appearing with a monodisperse and uniform nano-dumbbell shape. Then, these AuNPs were exploited as natural anchor points and further initiated self-assembly to create complex architectures via dithiol bridges. Detailed studies illustrated that the covalent Se-Au bonds facilitate effective charge transfer in the internal metal-semiconductor (M-S) electric field. The narrowed energy gap and up-shifted highest occupied molecular orbital were favored for electron removal during the electro-oxidation process. The ultrathin CdSe NPLs supplied a large specific surface area, carrying remaining holes and abundant active sites for target electro-catalysis. As a result, using the assembled complex as the electrode matrix with well-connected electronic circuits, a reliable electrochemical sensor was achieved for enrofloxacin detection. Under the optimal conditions, the current response exhibits two linear dynamic ranges, 0.01-10.0 µM and 10.0-250 µM, and the detection limit was calculated as 0.0026 µM. This work not only opens up broad application prospects for heterogeneous M-S combinations as effective electrochemical matrixes but also develops reliable antibiotic assays for food and environmental safety. [ABSTRACT FROM AUTHOR]

By employment of a new tripodal phosphoryl carboxylate ligand, tris(p-carboxyl-biphenyl)phosphine oxide (H3TBPPO), four novel coordination polymers, namely, Zn3(TBPPO)2 (1), Cd3(TBPPO)2 (2), Co3(TBPPO)2 (3) and In(TBPPO) (4), have been synthesized and characterized. Complexes 1, 2 and 3 are isostructural. Crystal structure analysis reveals that complexes 1–3 consist of trinuclear metal building units, which are further bridged by the tripodal phosphine oxide carboxylate ligands to give a (4,8)-connected 2-fold interpenetrating flu topological net with a point symbol of (412·612·84)(46)2, while complex 4 possesses a 3D 4-fold interpenetrating dia network with a point symbol of (66). Luminescence measurements indicate that complexes 1, 2 and 4 all show strong emission bands at around 378 nm in the solid state at room temperature. Furthermore, temperature-dependent magnetic susceptibility study shows that complex 3 exhibits antiferromagnetism properties. [ABSTRACT FROM AUTHOR]

A sensitive and selective strategy for the colorimetric visualization of the total monomeric Aβ down to 40 pg mL−1 based on dual-functionalized gold nanoplasmonic particles (GNPs) is developed and applied to evaluate Aβ levels in the AD cerebral system. [ABSTRACT FROM AUTHOR]

Four coordination polymers formulated as [Ni2(hfipbb)2(2,2′-bipy)2(H2O)4] (1), [Ni(4,4′-bipy)(hfipbb)(H2O)]·0.5DMF (2), [Ni2(hfipbb)2(BPE)1.5(H2O)(μ2-H2O)]·DMF·2H2O (3) and Zn(hfipbb)(2,2′-bipy)·0.5DMF (4) (H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid); 2,2′-bipy = 2,2′-bipyridine; 4,4′-bipy = 4,4-bipyridine; BPE = 1,2-di(4-pyridyl)ethane; DMF = N,N-dimethylformamide) have been synthesized under solvothermal conditions based on the V-shaped H2hfipbb ligand and different auxiliary linear N-containing ligands. Compound 1 exhibits a three dimensional (3D) supramolecular network built from 0D rings linked through hydrogen bonds and π–π packing interactions. Compound 2 displays a 3D 3-fold interpenetrating diamond network with a point symbol of (66). Compound 3 gives a double layer structure with (44·62)-sql topology built from {Ni2} clusters bridged by BPE and hfipbb2− ligands. Compound 4 is a 3D array formed by interdigitated 1D zigzag [Zn2(hfipbb)2]n ribbons, in which the Zn2(COO)4 paddle-wheel SBUs are linked by two hfipbb2− ligands. Compounds 2–4 exhibit hydrophobic properties which may have potential applications in hydrophobic materials. The temperature-dependent magnetic susceptibility study shows that compound 3 exhibits antiferromagnetism properties. The photoluminescence of 4 was studied in the solid state at room temperature, and it shows broad emission with a maximum peak at around 385 nm upon excitation at 335 nm. [ABSTRACT FROM AUTHOR]

Pharmaceutical cocrystals have been extensively investigated as a promising approach to improve drugs' physicochemical properties. Cocrystals are usually prepared using solution-mediated methods and grinding methods. In this study, a cocrystal of pimelic acid with poorly soluble melatonin was produced using a melt crystallization method by controlling the crystallization within a specific temperature range. The cocrystal was characterized by infrared spectroscopy, powder and single crystal X-ray diffraction. The binary phase diagram and the formation enthalpy established by differential scanning calorimetry provided the rationale for this spontaneous cocrystallization system. The cocrystal exhibited higher apparent solubility, a faster dissolution rate and acceptable stability as compared to the original melatonin. The study has shown that the melt crystallization method can be considered as a competitive route for producing pharmaceutical cocrystals with improved properties and the thermodynamic investigation can provide in depth understanding and guidance on the melt crystallization of cocrystals. [ABSTRACT FROM AUTHOR]

The self-assembly of Ru2(CO3)43- paddle-wheel precursors and Mn2+ ions in aqueous solution yields various carbonate complexes. With appropriate selection of the synthetic conditions, we are able to intentionally tune the composition and structure of Mn-Ru2-carbonate assemblies to form infinite chain structural complexes, e.g., K[{Mn(H2O)4}2Ru2(CO3)4Br2]·H2O (1) and H[{Mn(H2O)4}2Ru2(CO3)4Br2]·6H2O (2). Complexes 1 and 2 are obtained at different temperatures (25°C for 1 and 5°C for 2, respectively), and their crystal structures consist of brick-wall stacked chains, in which neighboring Ru2(CO3)4Br2 5- units are linked by two disubstituted octahedral Mn(H2O)4 2+ in a cis manner, resulting in two isomeric (twisted and zigzag) negative double-chain α- and β-{[Mn(H2O)4]2Ru2(CO3)4Br2}nn-. The magnetic properties of complexes 1 and 2 were highly characterized. The alternating current (AC) susceptibility analysis of complex 1 reveals a two-step magnetism transition at T1 = 5.0 K and T2 = 2.6 K, respectively. Complex 2 exhibits metamagnetism behavior, with a transition field HC = ~1.2 kOe at 2.0 K. [ABSTRACT FROM AUTHOR]

Uniform silica/ultrasmall silver composite microspheres have been prepared from [Ag(NH3)2]+ in the presence of silica microspheres via a hydrothermal process. The reaction temperature plays a critical role in the formation of the as-prepared SiO2/ultrasmall Ag composite microspheres. The as-prepared product was investigated by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM, JEOL-6700F) and transmission electron microscopy (TEM, JEOL 3010). The silica/ultrasmall silver composite microspheres are 200 nm in diameter and the silica microspheres decorated with ultrasmall Ag nanoparticles have an average diameter of 4 nm. As expected, the as-prepared silica/ultrasmall silver composite microspheres exhibit superior bacteriostatic and bactericidal activities and excellent photodecomposition towards Rhodamine 6G (R6G) dyes. [ABSTRACT FROM AUTHOR]

Four new indium-phosphite coordination polymers [C3H12N2][In2(HPO3)4] (denoted as InHPO-CJ11), [C3H12N2][InF(HPO3)2] (denoted as InHPO-CJ12), In2(HPO3)3 (denoted as InHPO-CJ13) and [C4H12N2][In4(HPO3)7(H2O)3] (denoted as InHPO-CJ14) have been solvothermally synthesized in the presence of mixed solvents. Single-crystal structure analysis reveals that InHPO-CJ11 displays a novel (3,6)-connected three-dimensional (3D) structure containing multi-directional intersecting 8-ring channels and unique left/right-handed helical chains. InHPO-CJ12 has a 1D chain-like structure constructed by InO6 and HPO3 units. Notably, the syntheses of these two compounds are similar except for the use of hydrofluoric acid. InHPO-CJ13 possesses a 3D inorganic framework with 12-ring channels without occluded organic templates, which is built up by connection of In2O10 face-shared dimers and pseudo pyramidal HPO3. InHPO-CJ14 exhibits a pillared-layer structure with intersecting 12-ring channels along [100], [010] and [110] directions. These compounds are further characterized by SEM, powder XRD, ICP, CHN, TGA and IR analyses. [ABSTRACT FROM AUTHOR]

Cell models based on human nasal epithelial stem/progenitor cells (hNESPCs) are developed to obtain functional ciliated cells on modified Transwell inserts. The live hNECs are integrated into microfluidic platforms to mimic the 3D features of the human upper airway for in vitro testing of gaseous formaldehyde toxicity via airway delivery. [ABSTRACT FROM AUTHOR]

Isostructural heterometallic diruthenium carbonates KM(H2O)6[M(H2O)2Ru2(CO3)4Cl2]·4H2O [M = Zn (1) and Mn (2)] were synthesized from the reaction of the precursors [Ru2(CO3)4Cl2]5− and transitional metal ions in aqueous solution. Complexes 1 and 2 show layered structures in which Ru2(ii,iii) units are linked by four octahedral environment M(H2O)22+ ions in a cross fashion and vice versa giving a negative bimetallic square grid layer {M(H2O)2Ru2(CO3)4Cl2}n3n−. M(H2O)62+ ions, linked by K+ forming zigzag chain {KM(H2O)6}n3+, are located in the void spaces between the layers. The adjacent bimetallic carbonate layers are connected with K–O and K–Cl bonds, and hydrogen bonding, forming a supramolecular 3D framework structure. Their magnetic properties were characterized in detail, and intralayer ferromagnetic coupling between the Ru2 dimer and Mn2+ ion, as well as long-range ordering (Tc = 5.2 K) coexistence of domain movement behavior were observed for complex 2. [ABSTRACT FROM AUTHOR]

Self-assembly of Ru2(CO3)43− units and Cu2+ ions in the presence of halogen (Cl− or Br−) has resulted in two novel isomeric layered structural heterometallic carbonates, K2Li[Cu(H2O)2Ru2(CO3)4X2]·5H2O [X = Cl (1), Br (2)]. X-ray structural analysis reveals that complexes 1 and 2 contain a similar square-grid negative layer [Cu(H2O)2Ru2(CO3)4X2]n5n−, in which each Ru2(CO3)4X25− unit is linked by four Jahn–Teller distorted Cu(H2O)22+ ions in a cross mode and vice versa. The adjacent negative layers are connected by K–O, Li–O bonds, and hydrogen bonding, which led to the formation of a supramolecular 3D network structure. The two complexes show ferromagnetic coupling between the Ru2 dimer and the Cu2+ ion. Detailed magnetism measurement demonstrates that complex 1 exhibits soft magnetic ordering below 2.9 K coexistent with domain movement, and complex 2 shows long-range ferromagnetic ordering below 3.8 K. [ABSTRACT FROM AUTHOR]

Three acyclovir complexes including one salt with maleic acid, and two cocrystals with fumaric acid and glutaric acid, were prepared. The results of powder dissolution and in vitro skin permeation experiments revealed that both solubility and permeability of acyclovir were enhanced after the formation of cocrystals. [ABSTRACT FROM AUTHOR]

Two hetero-metallic carbonates, namely KCd(H2O)3Ru2(CO3)4·4H2O (1) and KCd(H2O)3Ru2(CO3)4·3.5H2O (2), have been synthesized in a neutral aqueous solution. Both of the 3D dimensional structured complexes contain mixed-valent diruthenium(ii,iii) carbonate paddlewheel cores of Ru2II,III(CO3)43− that are connected to each other in trans- or cis-modes by carbonate oxygen atoms, forming rectangular square-grid and isomeric parallelogram layers [Ru2(CO3)4]n3n− in 1 and 2, respectively. The reaction temperature is found to play an important role in directing the final products with particular topologies and their layered structural diversity is due to the various linking modes between the Ru2(CO3)43− units. The magnetic studies show that ferromagnetic interactions are propagated between the diruthenium units in both complexes 1 and 2 but their magnetic properties differ at low temperatures, in which the trans linking mode parallelogram layer [Ru2(CO3)4]n3n− in complex 2 leads to long-range magnetic ordering below 4.0 K. However, no Curie ordering down to 1.8 K is detected for complex 1 containing the isomeric rectangle square-grid layer linking in the cis mode. [ABSTRACT FROM AUTHOR]

A new open-framework aluminophosphate Na6[(AlPO4)8(OH)6]·8H2O (JU103) has been synthesized by utilization of the organotemplate-free synthetic route in alkali metal-containing system. The as-prepared JU103 possesses two-dimensional intersecting 8-ring channels. Sodium ions and water molecules in the channels facilitates JU103 excellent proton conductivity up to 3.59 × 10−3 S cm−1 (293 K, 98% RH). [ABSTRACT FROM AUTHOR]

A copper-catalyzed Suzuki--Miyaura coupling of benzyl halides with arylboronates is described. Varieties of primary benzyl halides as well as more challenging secondary benzyl halides with β hydrogens or steric hindrance could be successfully converted into the corresponding products. Thus it provides access to diarylmethanes, diarylethanes and triarylmethanes. [ABSTRACT FROM AUTHOR]

Nitrogen heterocycles could be prepared in good yields via intramolecular cyclization of tertiary amines and alkenes promoted by KOt-Bu–DMF. [ABSTRACT FROM AUTHOR]

UiO-66 incorporated monoliths were fabricated to enhance the liquid chromatographic separation of small molecules with high column efficiency and good reproducibility. [ABSTRACT FROM AUTHOR]

A new open-framework zinc phosphate with 12-ring channels has been solvothermally synthesized by using the in situ generated methylviologen as the template, which exhibits multi-photoactive properties such as photochromism, photoelectricity and fluorescence. [ABSTRACT FROM AUTHOR]

Based on the K-doped graphene–CdS:Eu NC composites and the nicking endonuclease (NEase) assisted strand-scission cycle, we have developed an ultrasensitive and selective electrochemiluminescence (ECL) DNA biosensor using the G-quadruplex–hemin-based DNAzyme which acts as an electrocatalyst for the reduction of H2O2, the coreactant of CdS:Eu NCs ECL. [ABSTRACT FROM AUTHOR]

Two bilayered metal–organic frameworks with nanoporous channels were synthesized at different ligand-to-metal ratios, which demonstrated an interesting crystal-to-crystal transformation property and a special fluorescent response to the different guest molecules included. [ABSTRACT FROM AUTHOR]

Ordered mesoporous carbonaceous spheres with variable structures have been successfully prepared by using phenolic oligomers as a carbon precursor and amphiphilic triblock copolymers as a template via a one-step aerosol-assisted organic–organic self-assembly method. [ABSTRACT FROM AUTHOR]

As one of the highly crystalline porous materials, metal–organic frameworks (MOFs) have drawn immense attention due to their diverse structures and a wide variety of applications. In this study, [In3(ipbp)2(μ2-OH)(μ2-O)3] (1) that has a three-dimensional framework, including two types of cages with cuboctahedra and trigonal antiprism configurations, has been successfully synthesized based on the zwitterionic ligand 1-(3,5-dicarboxyphenyl)-4,4′-bipyridinium bromide (H2(ipbp)Br). Strikingly, a relatively rare trapeziform metal layer consisting of In3+, μ2-OH, μ2-O, carboxyl, and nitrogen from the ligand appears in the structure of 1. Benefitting from the formation of the ipbp radicals under UV light irradiation, compound 1 exhibits photochromic property that can transform the color from yellow to green. Moreover, it possesses commendable Cr(VI) removal capacity with the maximum adsorption amount of 74.4 mg·g−1 due to the surface electrostatic interaction between the crystal surface and Cr(VI) in the aqueous system. This work will promote the design of functional MOFs that show potential applications in UV light detection and removal of oxyanions. [ABSTRACT FROM AUTHOR]

Two unique windmill-like aziridine-containing indole alkaloids, possessing an unprecedented 6/5/5/6/6/5/3 rigid ring system and an unusual azabicyclo[3.1.0]hexane core, were isolated from Alstonia scholaris. Their structures were established by spectroscopy, X-ray diffraction, and electronic circular dichroism calculations. The novel compounds exhibited significant anti-inflammatory bioactivity in vitro and alleviated LPS-induced acute lung injury in mice. [ABSTRACT FROM AUTHOR]

A pair of chiral metal–organic frameworks based on enantiomers of chiral Zn(salen) ligands has been successfully obtained by solvothermal subcomponent self-assembly. Both chiral MOFs were characterized by infrared spectroscopy, UV-vis absorption spectroscopy, thermogravimetric analysis, and single-crystal/powder X-ray diffraction. They crystallize in the chiral space group I222 and possess an extended 2D network with a sql topology. Moreover, these MOFs exhibit circularly polarized luminescence (CPL) with a dissymmetry factor of about 3.7 × 10−3. This work provides a simple strategy to make CPL-active MOF materials based on salen ligands. [ABSTRACT FROM AUTHOR]

Veratrazine A (1), a steroidal alkaloid with a unique 6/5/5 triheterocyclic scaffold as the side chain, was isolated from Veratrum stenophyllum, and its structure was established via spectroscopic analyses and X-ray diffraction. A plausible biosynthetic pathway for 1 is proposed. Bioassy exhibits moderate anti-inflammatory activities in vitro and in vivo. [ABSTRACT FROM AUTHOR]