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For high reactivity but poor stability of homogeneous metal complexes in CO2 photoreduction, development of durable systems is still a big challenge. Herein, pentanuclear Co(II) complex [Co5(btz)6(NO3)4(H2O)4] (1, btz = benzotriazolate) is explored for converting CO2 to syngas which shows high stability and reactivity in both pure and diluted CO2. Compared with mononuclear structure, multinuclear complex exhibits 212-fold enhancement in reactivity, up to ~2748 TONs, with wide adjustability of H2/CO ratio from 16:1 to 2:1. This reactivity could be maintained over 200 h which is an order of magnitude higher than the durability of mononuclear complex and exceeds most reported homogeneous molecular catalysts. High reactivity is also achieved in extreme low CO2 content (5%). Structural analysis and density functional theory (DFT) calculations support that multinuclear structure and the low energy barrier for photocatalytic intermediate may account for the durable and efficient performance of complex 1. The multinuclear strategy is also adopted to nickel complex. This work probes origin of metal-node-dependent performance for CO2 photoreduction, providing new insights in design of durable and efficient metal complexes for photocatalysis and other applications.

Three nanoscale Nb/W mixed-addendum polyoxometalates, Cs14K4[(Si4W36Nb12O156)Cu(H2O)2]·47H2O, Cs10K8[(Si4W36Nb12O156)Zn(H2O)2]·28H2O, and Cs16[(H2Si4W36Nb12O156)Cd(H2O)2]·75H2O involving [SiNb3W9O40]7− fundamental building unit, have been synthesized, which all show photocatalytic hydrogen evolution activities. Furthermore, molecules 1, 2, and 3 are stable in the photocatalytic hydrogen evolution system. The embedding transition-metal cations into Nb/W mixed-addendum POMs can improve the photocatalytic H2 evolution activity.

A novel porous triazine-based metal-organic framework, ([Cd (Ligand)]∙2DMF) (1) with strong luminescence, has been constructed via multi-carboxyl ligand 5,5′,5''-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))tris(3-methylbenzoic acid) under solvothermal conditions. Structural analysis revealed that MOF1 has a three-dimensional (3D) framework which is crystallized in the monoclinic system bearingC2/c space group. The high chemical and thermal stability of synthesized MOF1 has been predicted by powder X-ray diffraction and thermogravimetric analysis techniques. Higher selectivity and sensitivity of MOF1 towards Cu2+ions is remarkable with an adsorption capacity of 90.5 mg/g compared with Mg2+, Mn2+, Ni2+, Co2+, Zn2+, Fe2+ and Cr3+ ions. Results reveal that strong emission of MOF1 can be quenched effectively by a trace amount of copper (3 ppm) and nitrobenzene (0.6 ppm), even in the vapor phase. The extraordinary solvatochromic phenomenon of MOF1 is observed by incorporating acetonitrile guest molecules due to host-guest interactions provided by the carboxyl groups of ligand and imino triazine backbone. Thus, owing to the highly selective and sensitive quenching effect in fluorescence and solvatochromic behavior, MOF1 can be used as a potential sensor for Cu2+, NB, and acetonitrile.

Nine multifarious new meroterpenoids, cochlearols E-M (1-9), along with seven known meroterpenoids 10-16, were isolated from the fruiting bodies of Ganoderma cochlear. Racemic 1, 6-8, 10 and 13 were separated by chiral HPLC. The structures were elucidated based on detailed spectroscopic analyses (HRESIMS, 1D/2D-NMR) and calculated electronic circular dichroism (ECD). Their biological activities against renal fibrosis were evaluated by using rat normal and diseased renal interstitial fibroblast cells (NRK49F). The results show that compounds 7a, 7b, and 10a exhibit potent proliferation inhibition in TGF-β1-induced NRK-49F cells.

Development of efficient, selective and low-cost photocatalysts, ideally constructed from Earth-abundant elements, is still a big challenge for CO2 photoreduction. Herein, adopting mixed halides strategy, the activity of all-inorganic perovskites toward CO2 reduction is enhanced sharply under simulated sunlight without photosensitizer, meanwhile maintaining high selectivity of CO and CH4 production. Via regulating ratio of Br and Cl, the yield of CO and CH4 changes obviously and the optimized catalyst is CsPb(Br0.5/Cl0.5)3 with a total yield of CO and CH4 up to 875 μmol/g (selectivity of 99%) which outperforms any other reported halide perovskites and is 4.5 and 9.1 folds higher than that of CsPbBr3 and CsPbCl3 under the same condition. The efficient charge separation and moderate stability in mixed-halide perovskites may account for the excellent performance in CO2 reduction. This study may provide a new strategy in design of high performance and low-cost halide perovskite materials for photocatalysis.

A novel porous coordination polymer compound [Cd0.5(tpy)]∙0.75H2O was prepared by hydrothermal synthesis, which exhibits excellent chemical stability under various organic solvents and aqueous solution with different pH values range from 3 to 13. Benefiting from guest water molecules existing in the crystal structure, this compound shows water-mediated proton (H+) ion-conducting with conductivity of 6.03 × 10−6 S·cm−1 under 97% relative humidity at 95 °C. The calculated thermal activation energy (1.09 eV) and strong dependency on the humidity indicates a vehicle mechanism in the proton conduction process.

Developing new materials that can efficiently reduce the level of sulfur contents in fossil oils is a pressing issue due to environmental problems. Polyoxometalates (POMs) have been used as catalysts to remove organosulfur compounds via the process of oxidative desulfurization for a long time. Here, a new catalytic material, POMs@MIL-101(Cr)-diatomite, has been obtained by restricting MIL-101(Cr) encapsulating Keggin POMs into mesoporous diatomite, which can overcome the obstacle about the poor solubility of POMs in the overall nonpolar environment. The catalyst was characterized by N2 adsorption-desorption, SEM, XRD, IR and XPS. The desulfurization rate could be up to 98.6%, using H2O2 as the oxidant. Furthermore, the catalyst was reused three times with no structure change under crystal analysis.

By altering auxiliary N-donor ligands, three ZnII compounds, [Zn(HL)(biz)] (1), [Zn2(μ3-OH)(L)(bpy)]·2H2O (2) and [Zn2(HL)2(bimb)2]·H2O (3) (H3L = 5-(4-carboxybenzyloxy)isophthalic acid, biz = benzimidazole, bpy = 2,2′-bipyridine, bimb = 1,4-bis((1H–imidazol-1-yl)methyl)benzene), were obtained under hydrothermal conditions. Compound 1 and 3 are 2D layer 4-connected net. Compound 2 is a 2D sheet structure and (3,6)-connected net with (43)(46·66·83) topology. In addition, compound 3 demonstrates high sensitivity in the detection of nitroaromatic explosives as a fluorescent sensor.

Herein, we reported a pair of di-nuclear europium enantiomers [Eu2(PO4)6(R-/S-HL)6(MeOH)4]•2MeOH (R-complex(1a) and S-complex(1b)) constructed from chiral ligands (R)-/(S)-(+)-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate (R-/S-HL) and europium (III) nitrate by solvothermal method. The structure of the complexes was characterized by single-crystal X-ray diffraction, powder X-ray diffraction and Fourier transform infrared spectroscopy. It was found that R-complex(1a) and S-complex(1b) were chiral enantiomers with a zero-dimensional chiral cluster structure. The circular dichroism studies further revealed the chiral properties of R-complex(1a) and S-complex(1b). Moreover, fluorescence sensing tests demonstrated that R-complex(1a) and S-complex(1b) possessed high enantioselectivity for axially chiral BINOL racemates.

As is well known, carbon dioxide (CO2) reduction reaction (CO2 RR) by photocatalytic technology is a means with great promise to alleviate the crises on the global energy and the environmental fronts. It is critical to design and construct photocatalysts with high performance as catalysts are the core of the photocatalytic process. Recently, polyoxometalates (POMs) have aroused wide research interest as CO 2 photoreduction-related catalysts because they possess tunable compositions, thermal stability, redox reaction and tailorable light-absorption capabilities. This review has discussed the recent progress of POMs and POM-based photocatalysts for CO 2 reduction focusing on the roles of POMs as photocatalysts, cocatalysts, photocatalytic hosts (photosensitizers), and multi-electron donors in systems of CO2 photoreduction, which can provide important guides for the design of high-efficiency photocatalysts. In the end, based on summarizing the previous work, we make a prospect to the future research direction, key challenges, and possible solutions in this field.

A novel metal-organic framework (MOF) with a π-conjugated porous condition is reported to sensor fused aromatic hydrocarbons molecules. This MOF assembled by N-heterocyclic multi-carboxyl ligands and Cd ions shows hexagonal hydrophobic channels along [100] and [010] directions with size 18.4 × 15.5 A2. Under the excitation of 338 nm, this MOF emits blue light peaking at 397 nm. Under immersing this MOF in the solutions containing aromatic hydrocarbon, including naphthalene, anthracene and phenanthrene within different time, the luminescent intensity of MOF enhanced different degree upon encapsulating aromatic hydrocarbons guest molecules. Therefore, this material shows favourable property of recognition for aromatic hydrocarbons molecules via solid-state photoluminescence.

A novel 3D coordination polymer [Zn2.5(L)(trz)2(H2O)2]·2H2O (1) (H3L = 5-(4-carboxybenzyloxy)isophthalic acid, trz = 1,2,4-triazole) has been synthesized hydrothermally. Compound 1 displays a 3D (3,8)-connected net with (53)2(58·64·78·84·94) topology. The luminescent property of 1 dispersed in different solvents as well as nitro compounds have been investigated systematically, demonstrating high detection sensitivity via a fluorescence quenching mechanism.

Tungsten carbides materials exhibit highly efficient activity for hydrogen evolution reaction (HER) as promising non-precious electrocatalysts. Herein, a N-doped graphene (NG) supported tungsten carbides composite material (WxC/NG-10, x = 1, 2, x is stoichiometric number of W, 10 is the mole quantity of tungsten in the precursors, mmol) was directly synthesized with a simple method by two-step calcining the mixture of sodium tungstate dihydrate (Na2WO4·2H2O), dicyandiamide (DCDA) and glucose anhydrous (GA), which was characterized by HRTEM, FE-SEM, XRD, XPS, EDX, BET and Raman, and estimated the electrocatalytic activity by the LSV, Tafel curves, and electrochemical impedance spectrum (EIS). The investigations indicate that WxC/NG-10, as an electrocatalyst for HER, achieves a lower overpotential of only 77.82 mV at the current density of 10 mA cm−2 and a Tafel slope of 45.95 mV dec−1 in 0.5 mol L−1 H2SO4 aqueous. Additionally, the WxC/NG-10 has also possessed an electrocatalytic oxygen evolution reaction (OER) activity in 1.0 mol L−1 KOH aqueous with a lower overpotential of 467.6 mV and a Tafel slope of 36.2 mV dec−1. And after 10000 cycles the electrocatalytic active of WxC/NG-10 decrease 24.63% and 19.35% for HER and OER, respectively. The modification of WxC has improved the activity of NG materials in electrocatalytic applications.

By artificial mimic of the natural [FeFe]-hydrogenases, a series of polyoxometalate-based high-nuclear Ni clusters containing a varying number of {Ni 4 O 4 } cubane cores, K 1.5 Na 26.5 [{Ni 4 (OH) 3 (PO 4 )} 4 ( A- PW 9 O 34 ) 4 ]·62H 2 O ( 1 ), Na 28 [{Ni 4 (OH) 3 (PO 4 )} 4 ( A- PW 9 O 34 ) 2 ( B- PW 9 O 34 ) 2 ]·102H 2 O ( 2 ), and Na 28 [{Ni 4 (OH) 3 (VO 4 )} 4 ( B- PW 9 O 34 ) 4 ]·74H 2 O ( 3 ), were synthesized and systematically characterized. Compounds 1 − 3 contain {Ni 16 (XO 4 ) 4 (OH) 12 } (X = P, V) core encapsulated by the trivacant A- / B- {PW 9 O 34 } ligands. Compounds 1 − 3 as homogeneous catalysts for visible-light-driven H 2 evolution indicate that they not only show high photocatalytic performance (High TON of 578.8, 679.1, and 931.1 for 1 − 3 were achieved, respectively), but also their catalytic performance was improved with the increasing number of {Ni 4 O 4 } cubanes. Multiple stability experiments confirm that compounds 1 − 3 maintain their structure intact under the photocatalytic conditions. The above research provides a platform for mimicking the structures of natural hydrogenases to further explore more efficient and inexpensive H 2 evolution catalysts.

Luminescent sensors have received extensive attention due to their fast-response and easy-operation and when integrating multifunctions in a sensor, the cost will be reduced substantially. Covalent organic polymers (COPs) as multifunctional luminescent sensor with outstanding performance are still underexplored. In this work, a typical COP named as COP-2 show preponderant performance in the detection of Fe3+, MnO4−, and TNP. COP-2 has the highly efficient ability to selectively detect Fe3+ among the other metal ions, and the limit of the detection (LOD) is 0.89 ​μM, which outperforms the reported covalent organic materials. Anion sensing shows the COP-2 has the highly anti-interference ability and recyclicity to detect MnO4−. Explosive analogs sensing demonstrates that COP-2 owns the superior ability in sensing TNP in the knockdown concentration with 0.0067 ​ppm LOD, which superior to the values in the reported literature. In addition to the above superb sensing performance, COP-2 can be utilized as a white light-emitting diode (WLED) when combined with the commercial blue emission LED and presents a Commission Internationale de l’Eclairage (CIE) coordinate of (0.31, 0.32). These results show the COP-2 not only has an appealing performance in multifunctional luminescent sensing application, but also has a possible application in white light emitting.

A new zirconium-based metal-organic polyhedron (Zr-MOP-1) was successfully synthesized from Bis(cyclopentadienyl)zirconium dichloride and 2,5-pyridinedicarboxylic acid under solvothermal condition. It was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. Four trinuclear zirconocene building blocks as well as six linear carboxylate ligands give rise to its tetrahedral configuration. Interestingly, Zr-MOP-1 possesses considerable reversible iodine sorption performance in organic phase featuring an optimal adsorption capacity of 283 mg g−1. The related kinetics absorption and desorption process were fully explored in detail by multiple complementary experiments and the adsorbed iodine species (I− and I3−) in Zr-MOP-1 had been further identified through crystallographic analyses. This work provides new possibilities for developing new and functional zirconium-based molecular cages materials.

Laboratory experiments are performed in a large stratified fluid flume to examine the characteristics of the load on a submerged slender body that is exerted by a nonstationary internal solitary wave (ISW) from its interaction with a gentle slope. The nonstationary ISW over the slope and its load on the body are measured by using multi-channel conductivity-probe arrays and a specially designed force measurement device, respectively, and the body’s vertical and horizontal positions on the load are determined by analyzing the effects of the incident ISW’s amplitude. The experimental results show that the load on the slender body increases as the incident ISW’s amplitude increases; additionally, the effect of oscillations is enhanced because of the ISW’s distortion, breaking and fission. The oscillating action from fission waves becomes dominant as the amplitude reaches a certain value. Additionally, the load is correlated with body’s vertical position relative to the pycnocline. The magnitudes of the vertical and horizontal forces reach a maximum and minimum in the pycnocline, respectively, and the horizontal force in this direction is the opposite above and below the pycnocline. Compared to a case without a slope, the load on the slender body increases because of the nonstationary ISW, and its effect on the maximum force is transferred to the pycnocline. When the body’s horizontal position is located close to the top of the slope, the direction of the horizontal and vertical forces remains consistent, but its acting time becomes longer. In addition, high-frequency actions on the slender body are impacted by nonstationary ISWs near the slope’s top.

A stable, 3D supermolecular material, [Ag(H2O)(2,6-ndc)0.5(L)0.5]n (2,6-H2ndc = 2,6-naphthalenedicarboxylic acid; L = N,N′-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (dpndi)) with high electrical conducting ability was successfully synthesized under a solvothermal condition and characterized by single-crystal X-ray diffraction, IR spectroscopy and thermogravimetric analysis (TGA). The electrical conducting and photoluminescence properties were investigated.

The {Mn 4 O 5 Ca} cluster of photosystem II is a well-known cubane-like transition-metal (TM) cluster that plays important roles in solar energy conversion. The artificial synthesis of cubane-like TM clusters and their interesting potential applications have been widely studied. Most of them were isolated by use of organic ligands, and therefore their potential applications were essentially restricted to organic solvents because of their limited stability in aqueous solution. In recent decades, lacunary polyoxometalates (POMs) composed of W VI /Mo VI centers have been used to replace organic ligands as stable and oxidative-resistant pure-inorganic multidentate ligands to construct water-soluble and water-stable molecular clusters. In the course of the mimicking of the {Mn 4 O 5 Ca} subsite of photosystem II, significant advances have already been made in POM-assisted artificial synthesis of TM cubanes. Compared with classic cubane-like TM clusters, these POM-based TM cubane clusters can not only dissolve in organic solvents by virtue of a simple phase-transfer reaction but also display excellent aqueous stability. Consequently, the synthesis of these pure-inorganic cubane clusters offers a great opportunity for expanding the applications of cubane-like TM clusters. This review focuses on the synthetic strategies for, structures of, and applications of these POM-based TM cubane clusters, particularly highlighting how POMs can be used as the inorganic ligands to construct cubane-like TM clusters. The purpose of this review is to give a representative and comprehensive overview of the work done so far in this emerging field.

Metal-organic frameworks (MOFs) are being positively researched as potential materials in chemical, photo and biomimetic catalytic areas. Herein, we report a transition metal Co-containing MOF, namely CUST-501 {[Co2(H2O)(tfBDC)2(Phen)2]}, (tfBDC = Tetrafluoroterephthalic acid, Phen = 1,10-Phenanthroline monohydrate), synthesized via solvothermal method. CUST-501 was characterized by IR spectroscopy, powder X-ray diffraction (PXRD), X-ray single-crystal structure analysis and thermogravimetric analysis (TG). Furthermore, it can act as chemical catalysts, which shows fast activation of PMS for the RB degradation about 30 min in aqueous solution. In addition, the recyclability measurement reveals that CUST-501 is a stable, continuous and efficient catalyst which was used to activate PMS for achieving the purpose of degrading pollutants in water. This study indicates that CUST-501 can be used as efficient catalysts to produce radicals, further treating organic dyes and offering more options for future water treatment solutions.

Highly efficient phosphorescent organic light-emitting diodes (PHOLEDs) with simple configuration as well as low cost fabrication process have attracted much interest for both academic researches and commercial endeavors. This review provides an update on recent advances in the development Ir(III) complexes and their applications in nondoped PHOLEDs fabricated by both vacuum deposition and solution-processed approaches. The modification of chemical structures of the small molecular Ir(III) complexes and dendrimers through incorporating multiple functional moieties could effectively adjust the optical and electronic characters. These complexes typically possess reduced intermolecular aggregation, various hole and electron transporting abilities so that high-performance nondoped PHOLEDs can be developed. The corresponding structural, optical, electronic, photophysical as well as the EL properties in different colors over the whole spectral region are surveyed and highlighted. In the end, the perspectives of the development for the further trend are presented, hopefully to provide useful guidance for the research on highly efficient Ir(III) complexes and corresponding nondoped PHOLEDs.

This paper reports the results of laboratory experiments on the coupling wave-flow structure of an oblique internal solitary wave (ISW) and the force it exerts on a submerged slender body in a large stratified fluid flume. Multiple experimental techniques were used to measure the wave-flow field as well as the force on the slender body. Reasonable analysis reveals the effects of the propagation directions and amplitudes of the oblique ISW on the dynamic characteristics of the slender body at different water depths. The experimental results show that there is a significant shear effect from the horizontal velocity near the envelope of the ISW and sinking (upwelling) current from the vertical velocity in front of (behind) the ISW packet. The direction of the horizontal velocity above (below) the envelope is consistent with (opposite to) the propagation velocity of the ISW, with the former having a larger magnitude. The horizontal force depends on the velocity field induced by the oblique ISW, and the vertical force is determined by the coupling velocity and density field. The horizontal and vertical wave forces are calculated using Morison's formula corresponding to the respective component of velocity, with the vertical dynamic pressure transformed into the reduced gravity.

A zirconium-based metal-organic polyhedron is decorated by Pt nanoparticles with different spatial locations for visible-light-driven H2 production, which makes photocatalytic efficiencies improved on different levels. This work delves into the affinity of electron-transfer path with photocatalytic reactivity and further broadens horizons for porous materials in photocatalysis.

The conversion of low-value natural environmental energy into the clean and high-value electricity provides a promising approach for solving the energy crisis and environmental pollution. Using one device to directly convert all-weather environmental energy into electricity is an ideal goal and still remains a great challenge. Here, we assembled a simple and multifunctional device with the polyoxometalate (POM)/ethyl cellulose composite film on metal substrate, which generates electricity from multiple low-value all-weather environmental energy, including sunlight, wind and raindrops. For example, the optimal Mo72Cr30/ethyl cellulose composite film (Mo72Cr30 wt% = 71.4%) exhibits remarkable output performance with the responsivity of 176.3 μA W−1 under AM 1.5 G solar light, an average output of 4.48 μW m−2 from wind at a speed of 10 m s−1, and an average output of 0.25 μW m−2 from raindrops at a dripping rate of 7 mL min−1, as well as the better output power density of 6.32 μW m−2, 0.54 μW m−2 and 8.71 μW m−2 simultaneously driven by sunlight and wind, sunlight and raindrops, wind and raindrops, respectively. It also achieves an average output power density of 17.7 μW m−2, as well as long-term durability when it is simultaneously driven by sunlight, wind and raindrops, which exhibits 4 and 70 times than single wind and raindrops condition. For this composite film, the maximum power density is achieved at a very low resistance load of about 10 Ω. The output power arises from the high efficient transport of photo-generated electrons and electrostatic charges from Mo72Cr30 to metal substrate.

Several Ganoderma fungi are well-known for their medical uses to treat cancer, insomnia and kidney disease in East Asia. Triperpenoids and polysaccharides have been considered for a long time to be the major active components of the genus Ganoderma. The present study is to examine the effects of lingzhilactones from G. lingzhi on adriamycin-induced nephropathy in mice.A combination of various chromatography led to the isolation of lingzhilactones A-C, their structures were identified by spectroscopic and computational methods. The intracellular reactive oxygen species (ROS) was detected with the carboxymethyl-H2-dichlorofluorescein diacetate fluoroprobe. The fibrotic markers were analyzed by real-time RT-PCR and Western blot analyses. Detection of SEAP was conducted with the chemiluminescent. Urine albumin was measured using an ELISA assay. Histology and immunohistochemical staining was used to assess fibrotic lesions in mice.Three new lingzhilactones A-C (1-3) containing a fused lactone moiety were isolated from G. lingzhi. We found that 2 could inhibit ROS generation in a dose-dependent manner, inhibit mRNA expression of collagen IV, fibronectin, IL-6 and increase expression of Nrf2 in rat tubular epithelial cells. Furthermore, we found that 2 could reduce urinary albumin levels, abrogate myofibroblastic activation and inhibit the phosphorylation of Smad3 in adriamycin-induced mice.The in vitro and in vivo results suggested that lingzhilactone B could protect against renal injuries by increasing the activities of antioxidants and inhibiting inflammation. The inhibition of Smad3 phosphorylation suggested that this substance displays in vivo antifibrotic activity by a mechanism that is dependent on disruption of Smad3. These results promote understanding of the traditional usage of G. lingzhi and provide promising findings which may be beneficial for anti-kidney disease drug design.

Ganoderma lingzhi is a valuable, edible and medicinal fungus that has been widely used for the prevention and treatment of a broad range of diseases. In this study, spirolingzhines A-D, four meroterpenoids with a spiro[benzofuran-2,1'-cyclopentanel motif, lingzhines A-F, six meroterpenoids with diverse ring systems, along with two known compounds were isolated from the fruiting bodies of this fungus. The structures and stereochemistry of these substances were determined by using spectroscopic, X-ray crystallographic and computational methods. Chiral HPLC was used to separate (-)- and (+)-antipodes of seven of ten meroterpenoids, which were isolated from the fungus as racemic mixtures. Several of the metabolites were found to promote proliferation of neural stem cells (NSCs) and, as such, they constitute a class of NSC stimulators. The most potent member of this series, (-)-spirolingzhine A, was shown to affect NSC cell cycle progression using the 5-bromo-2-deoxyuridine (BrdU) incorporation assay. (C) 2015 Elsevier Ltd. All rights reserved.

Three silver(Ι) alkynyl compounds, [Ag 5 (C C t Bu)(CF 3 COO) 7 ( n Bu 4 N) 3 ·H 2 O] ( 1 ), [Ag 8 (C C t Bu) 2 (CF 3 COO) 10 (Et 3 N) 4 ] ( 2 ), and [Ag 12 (C C t Bu) 6 (CF 3 COO) 8 ( n Bu 4 N) 2 (Et 3 N) 2 (CF 3 COO) 2 ] ( 3 ), have been obtained. Concomitantly, isolated [Ag 5 (C C t Bu)(CF 3 COO) 7 ] 3– , [Ag 8 (C C t Bu) 2 (CF 3 COO) 10 ] 4– and [Ag 12 (C C t Bu) 6 (CF 3 COO) 8 ] 2– clusters ( Ag 5 , Ag 8 and Ag 12 for short) appear in 1 – 3 , respectively. The synthesis of 1 – 3 demonstrates silver(I) alkynyls are better systems for the study of the template effect. ESI-MS analysis indicates compounds 1 – 3 can stably exist in methanol, and they have been proved to be potential wide gap semiconductor materials by the reflectance spectra. Notably, the second hyperpolarizabilities ( γ values) of Ag 5 , Ag 8 and Ag 12 have been studied by using time-dependent density functional theory (TDDFT) calculations and the finite filed (FF) approach combining CAM-B3LYP. The calculated results show that they can be applied as potential third-order nonlinear optical (NLO) materials owing to their second hyperpolarizabilities rising from 39.1 × 10 −36 , 60.3 × 10 −36 to 97.7 × 10 −36 esu with the growth of the number of Ag atoms and C C groups.

The fruiting bodies of Ganoderma lucidum have been used in China for the prevention of a wide range of diseases including diabetic nephropathy. Our current investigation with this mushroom led to the isolation of six new and two known phenolic meroterpenoids. The structures and absolute configurations at all stereogenic centers in these substances were assigned by using spectroscopic and computational methods. The new meroterpenoids, chizhines A-F (1-6), are isolated as racemic mixtures. Chiral HPLC was utilized to obtain the individual (-)- and (+)-antipodes of these substances. The renoprotective effects of the selected members of the series, were evaluated by using the ELISA technique and high-glucose-induced rat mesangial cells. The results show that the individual enantiomers of these substances significantly inhibit monocyte chemotactic protein 1 (MCP-1) and fibronectin production in a dose-dependent manner. (C) 2014 Elsevier Ltd. All rights reserved.

Recent studies focusing on unveiling the biological agents of Aspongopus chinensis have led to the identification of four new norepinephrine derivatives (1-4), three new sesquiterpenoids (5-7), and one new lactam (8). In addition, twenty-three known compounds have been identified, most of which were isolated from this insect for the first time. Selected members of insect-derived substances were evaluated for their biological activities against renal protection in high-glucose-induced mesangial cells and COX-2 inhibition. (C) 2014 Elsevier Ltd. All rights reserved.

A new 3D inorganic–organic hybrid based on polyoxometalates (POMs), [Ag4(pz)6(SiW12O40)·H2O] (1), (pz = pyrazine) 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, TG, and UV–vis absorption spectra. In compound 1, there are two identical interpenetrating 3D frameworks containing deca-nuclear silver circles and pz ligands, which are further linked by [SiW12O40]4 − anions to exhibit an entangled architecture. Additionally, its optical band gap, photocatalytic performance and electrochemical behavior at room temperature have been investigated in detail.

Two new inorganic–organic hybrid compounds based on well-defined Keggin-type polyoxometalates and copper–bis(triazole) assemblies, namely, [Cu3(L)3(PMo12O40)2] · 9H2O (1) and [Cu3(L)3(PW12O40)2] · 9H2O (2) [L = 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene], have been obtained under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR, and TG. To the best of our knowledge, compounds 1 and 2 represent rare 2D structural examples with POM clusters as pendants. In addition, the diffuse reflectivity spectra of these two compounds show that they can be regarded as a wide gap semiconductor. The photocatalytic experiments indicate that both 1 and 2 exhibit high catalytic activity for photodegradation of Rhodamine B (RhB) with UV irradiation.

Three metal-organic frameworks (MOFs), [Co{sub 2}(BPDC){sub 2}(4-BPH){center_dot}3DMF]{sub n} (1), [Cd{sub 2}(BPDC){sub 2}(4-BPH){sub 2}{center_dot}2DMF]{sub n} (2) and [Ni{sub 2}(BDC){sub 2}(3-BPH){sub 2} (H{sub 2}O){center_dot}4DMF]{sub n} (3) (H{sub 2}BPDC=biphenyl-4,4 Prime -dicarboxylic acid, H{sub 2}BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N Prime -dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has 'single-pillared' MOF-5-like motif with inner cage diameters of up to 18.6 A. Framework 2 has 'double pillared' MOF-5-like motif with cage diameters of 19.2 A while 3 has 'double pillared' 8-connected framework with channel diameters of 11.0 A. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework. - Graphical abstract: By insertion of flexible BPH pillars based on 'pillaring' strategy, three metal-organic frameworks are obtained showing that the porous frameworks can be constructed in a much greater variety. Highlights: Black-Right-Pointing-Pointer Frameworks 1 and 2 have MOF-5 like motif. Black-Right-Pointing-Pointer The cube-like cages in 1 and 2 are quite large, comparable to the IRMOF-10. Black-Right-Pointing-Pointer Framework 1 is 'single-pillared' mode while 2 is 'double-pillared' mode. Black-Right-Pointing-Pointer PXRD and gas adsorption analysis show that 3 is a dynamic porous framework.

One novel metal–organic framework, namely, [Cd2(ndd)2(tib)2·H2O]n (1), [H2ndd = 2,2′-(naphthalene-1,5-diylbis(oxy))diacetic acid, tib = 1,3,5-tri(1H-imidazol-1-yl)benzene] has been prepared under hydrothermal condition and characterized by elemental analyses, infrared spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analyses. Compound 1 presents a 3D 3-fold interpenetrated (3,5)-connected network with the point symbol of (42·65·83)(42·6) topology. Furthermore, the thermal stabilities and luminescent properties of compound 1 were studied.

Three coordination polymers, i.e. [Co(HL)(HBDC)]n (1), [Co(HL)(BDC)0.5]n (2) and {[Zn2(H2L)(BTC)2](H4L)(H2O)2}n (3) (L = 2, 2′-(ethanediyl)bis(1H-benzimidazole), H2BDC = 1, 4-benzenedicarboxylic acid, H3BTC = 1, 3, 5-benzene tricarboxylic acid), have been synthesized under hydrothermal conditions based on bis(2-benzimidazole) and two multi-dentate carboxylate ligands, with different metal ions such as ZnII and CoII. The structures of these coordination polymers have been determined by X-ray single‐crystal diffraction. The diverse coordination modes of the H2L ligand and the varying geometries of multi-dentate carboxylate ligands play an important role in the construction of coordination polymers. Various assembly patterns have been observed, including one-dimensional (1D) chain (1), two-dimensional (2D) 3-connected network structure with honeycomb topology (2), and three-dimensional (3D) 3,4-connected porous structure with (63)(65,8) topology (3). Thermal analyses of the three polymers have been performed and discussed. Furthermore, strong room temperature photoluminescence of compound 3 was observed.

Three coordination polymers, namely, [Zn2(ndd)2(2,2′-bpy)2·2H2O]n (1) [Cd(ndd)(2,2′-bpy)]n (2), and [Cd(ndd)(1,4-pyb)]n (3), where H2ndd = 2,2′-(naphthalene-1,5-diylbis(oxy))diacetic acid, 1,4-pyb = 1,4-bis(pyridin-4-ylmethoxy)benzene and 2,2′-bpy = 2,2′-bipyridine, have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses, powder X-ray diffraction and thermogravimetric analysis. Compound 1 can be considered as a 1D chain, which is further linked through the strongly multiple π–π interactions into a 3D supramolecular structure. By changing the metal ions, compound 2 is the 2D square structure (10.96 × 15.20 A) with the 44·62 topology. By changing the auxiliary ligand, compound 3 presents a new (4,5)-connected 3D network with the point symbol of (42·65·83)2·(66). Furthermore, compounds 1–3 show good fluorescence properties in the solid state at room temperature.

A new two-dimensional (2D) inorganic–organic hybrid compound H2{[Ni6(μ3-OH)3(H2O)4(en)(CH3COO)(IN)(B-PW9O34)]}·2H2O (en = ethylenediamine; HIN = isonicotinic acid) (1) has been hydrothermally synthesized and characterized by IR spectrum, electrochemical measurements, diffuse reflectance UV–vis spectrum and single-crystal X-ray diffraction. Compound 1 contains a nanometer-scale secondary building unit (SBU) [Ni6(μ3-OH)3(B-α-PW9O34)]2 ({Ni6PW9}2), in which two {Ni6PW9} units are linked together through Ni–O–W linkages. The adjacent SBUs are connected by IN and forming a 2D layer network. 1 exhibits semiconducting properties with the band gap Eg at 1.98 eV.

Four hybrid materials based on the Keggin polyanions and metal–salens, namely, [Mn(salen)(CH3OH)2]4[SiW12O40] (1), [Mn(salen)(H2O)]2[Mn(salen)(H2O)][PW12O40] (2), [NH(CH2CH3)3]2[Mn(salen)(CH3OH)]2[SiW12O40]·2CH3OH (3), and [(Cu(salen))2Cu(H2O)]2[SiW12O40] (4) (H2salen = N,N′-ethylenebis(salicylideneimine)) have been successfully synthesized. All the compounds are characterized by X-ray single-crystal diffractions, elemental analyses, IR spectra, and thermogravimetric analyses (TGA). Crystal structure analysis reveals that compound 1 exhibits a supramolecular structure containing one Keggin-type [SiW12O40]4− heteropolyanion and four MnIII–salen units. In compound 2, the [PW12O40]3− polyoxoanions and MnIII–salen complex cations are regularly arranged along the c-axis showing an alternating packing arrangement of anionic and cationic layers. While in compound 3, the polyoxoanion [SiW12O40]4− is covalently decorated by two [Mn(salen)(CH3OH)]+ fragments via two terminal oxygen atoms in the opposite sites, giving birth to an unusual Keggin anion supporting transition metal–salen complexes. Compound 4 represents the first example that POM supports trinuclear copper–salen complexes. Photocatalytic experiments of 1–4 indicate that they possess high catalytic activity for photodegradation of RhB under UV irradiation. In addition, the electrochemical behaviors of 1 and 2 are well investigated.

The reactions of N-donor ligands 2,2-bipyridine and 1,10-phenanthroline with Cd(NO3)2·4H2O or Zn(NO3)2·3H2O in N,N′-dimethylacetamide in the presence of H3PO3 or H3PO4 lead to the formation of Cd(HPO3)2(bpy) (1), [Zn4(HPO4)2(H2PO4)2(phen)4][(NO3)2]·4DMA (2), Cd(H2PO3)(phen)2(NO3) (3) complexes. The structure of complex 1 consists of chains resulting from the “head to tail” connection of 8-membered Cd2O4P2 rings, with two “hanging” pyridine groups attached to each CdII center. Complex 2 comes into being through the alternating arrangement of [Zn4(HPO4)2(H2PO4)2(phen)4]2+ cationic layers and the anionic layers constructed by isolated nitrate groups and DMA molecules. In complex 3, two phenanthroline moieties, a nitrate group, and one H2PO3 fragment appending to CdII centers generate a supramolecular aggregate. Luminescent properties of all complexes have been investigated. In particular, we present a rare example that supermolecular complex 2 is used as luminescent probes to detect small molecules.

Two metal–organic frameworks, namely, [Zn(L)(phen)(H 2 O)] n ( 1 ) and [Cd(L)(phen)] n ( 2 ), where H 2 L = 2,2′-(naphthalene-1,5-diylbis(oxy))diacetic acid and phen = 1,10-phenanthroline, have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction analyses, powder X-ray diffraction and thermogravimetric analysis. Compound 1 can be described as a 3D supramolecular architecture formed via the strong π–π interactions. While, compound 2 , obtained by changing the metal ions, exhibits a 3D metal–organic frameworks of PtS topology with the square window (the dimensions is 11.454 × 25.847 A). The different structures between 1 and 2 indicate that metal ions have significant effects on the final complexes. Moreover, compounds 1 and 2 show good luminescent properties in the solid state at room temperature.

Two new inorganic–organic hybrid supramolecular compounds based on Keggin-type polyoxoanions, namely [Mn(salen)(CH3OH)2]3[PMo12O40] (1) and [Mn(salen)(CH3OH)2]3[PW12O40] (2) (H2salen = N,N′-ethylenebis(salicylideneimine)) have been synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectroscopy, and TG analysis. Two compounds reported herein represent the first examples of integrating metal–Schiff-base segments with Keggin polyanions characterized via single-crystal X-ray diffraction. Such hybrid materials display photocatalytic and electrocatalytic bifunctional catalytic activities.

A non-interpenetrated 3D porous metal–organic framework [(CH3)2NH2]2[Cd(TATAT)2/3]·4DMF (1) (TATAT = 5,5′,5″-(1,3,5-triazine-2,4,6-triyl)tris(azanediyl)triisophthalate) has been successfully synthesized under solvothermal conditions and characterized by elemental analysis, TGA, and single-crystal X-ray diffraction analysis. Compound 1 exhibits α-Al2O3 (corundum) topology and represents the first metal–organic analog presently known with a natural material topology based on 6-connected organic ligand and tetrahedral metal ion. In addition, the thermal stabilities of the complex and the acid-treated product have been investigated and the results indicate that acid treatment is an efficient way for this compound to improve its thermal stability.