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Jose Manuel Olivares,1 Manickam Thirunavukarasu,2 Jayashri Kulkarni,3 Hong Yan Zhang,4 Mingyuan Zhang,5 Fan Zhang61Department of Psychiatry, Hospital Meixoeiro, Complejo Hospitalario Universitario de Vigo, Vigo, Spain; 2Department of Psychiatry, SRM Medical College Hospital and Research Center, Tamil Nadu, India; 3Department of Psychiatry, Monash University and the Alfred Hospital, Prahran, Vic, Australia; 4Department of Psychiatry, Peking University Institute of Mental Health, Beijing, People's Republic of China; 5Department of Psychiatry, Shanghai Mental Health Center, Shanghai, People's Republic of China; 6Medical Affairs, Xian Janssen Pharmaceutical, Beijing, People's Republic of ChinaBackground: Nonadherence is a well-known problem among schizophrenia patients, among whom relapse is fivefold more likely, adversely affecting health, employment, and social functioning. The Spanish Adherencia Terapéutica en la Esquizofrenia (ADHES) survey was developed to determine the scope and causes of medication nonadherence in schizophrenia.Methods: The 20-question ADHES survey was distributed to 19,370 psychiatrists in 13 Asia–Pacific countries in January–April 2012, to ascertain psychiatrists' perceptions of antipsychotic medication adherence levels among their schizophrenia patients, reasons for partial/nonadherence, their preferred methods of assessing adherence, and strategies to improve adherence. Responses are reported as mean and range across countries.Results: Four thousand, six hundred sixty one psychiatrists (24% of recipients) completed the survey (highest contributors: People's Republic of China, 1854; India, 1616). Psychiatrists perceived that 56% (range, 30%-71%) of schizophrenia patients were non- or partially adherent to medication. Patients discontinue medication primarily due to lack of insight into their condition (mean, 37%; 1%–65%) and because patients consider medication unnecessary when feeling better (mean, 27%; 15%–68%). Over half of psychiatrists (mean, 55%; 42%–99%) assess medication adherence at every visit, almost exclusively (81%) by asking their patients, versus quantitative measures. One in three psychiatrists expressed their preference to switch to or add a long-acting antipsychotic to improve adherence (15%–82%).Conclusions: The substantial prevalence of partial/nonadherence to medication demonstrates that more proactive management of patients with schizophrenia is needed to improve adherence and thereby treatment outcomes.Registration: Registration of this study was not required.Keywords: schizophrenia, antipsychotic, APAC, survey, adherence

Oxygen evolution reaction is the essential anodic reaction for water splitting. Designing tunable electronic structures to overcome its slow kinetics is an effective strategy. Herein, the molecular ammonium iron sulfate dodecahydrate is employed as the precursor to synthesize the C, N, S triatomic co-doped Fe(Al)OOH on Ni foam (C,N,S-Fe(Al)OOH-NF) with asymmetric electronic structure. Both in situ oxygen vacancies and their special electronic configuration enable the electron transfer between the d-p orbitals and get the increase of OER activity. Density functional theory calculation further indicates the effect of electronic structure on catalytic activity and stability at the oxygen vacancies. In alkaline solution, the catalyst C,N,S-Fe(Al)OOH-NF shows good catalytic activity and stability for water splitting. For OER, the overpotential of 10 mA cm -2 is 264 mV, the tafel slope is 46.4 mV dec -1 , the HER overpotential of 10 mA cm -2 is 188 mV, the tafel slope is 59.3 mV dec -1 . The stability of the catalyst can maintain ≈100 h. This work has extraordinary implications for understanding the mechanistic relationship between electronic structure and catalytic activity for designing friendly metal (oxy)hydroxide catalysts., (© 2024 Wiley‐VCH GmbH.)

Systematically orchestrating fundamental building blocks into intricate high-dimensional molecular assemblies at molecular level is imperative for multifunctionality integration. However, this remains a formidable task in crystal engineering due to the dynamic nature of inorganic building blocks. Herein, we develop a multi-template-guided strategy to control building blocks. The coordination modes of ligands and the spatial hindrance of anionic templates are pivotal in dictating the overall structures. Flexible multi-dentate linkers selectively promote the formation of oligomeric assembly ([TeO3(Mo2O2S2)3O2(OH)(C5O2H7)3]4- {TeMo6}) into tetrahedral cages ([(TeO3)4(Mo2O2S2)12(OH)12(C9H9O4P)6]8- {Te4Mo24} and [(AsO4)4(Mo2O2S2)12(OH)12(C9H9O6)4]12- {As4Mo24}), while steric hindrance from anionic templates further assists in assembling cages into an open quadruply twisted Möbius nanobelt ([(C6H5O3P)8(Mo2O2S2)24(OH)24(C8H10O4)12]16- {P8Mo48}). Among these structures, the hydrophilic-hydrophobic hybrid cage {Te4Mo24} emerges as an exemplary molecular model for proton conduction and serves as a prototype for humidity gradient-based power generators (HGPGs). The Te4Mo24-PVDF-based HGPG (PVDF = Poly(vinylidene fluoride)) exhibits notable stability and power generation, yielding an open-circuit voltage of 0.51 V and a current density of 77.8 nA cm-2 at room temperature and 90% relative humidity (RH). Further insights into the interactions between water molecules and microscale molecules within the generator are achieved through molecular dynamics simulations. This endeavor unveils a universal strategy for synthesizing multifunctional integration molecules., (© 2024 Wiley‐VCH GmbH.)

Multifunctional flexible electronics present tremendous opportunities in the rapidly evolving digital age. One potential avenue to realize this goal is the integration of polyoxometalates (POMs) and ionic liquid-based gels (ILGs), but the challenge of macrophase separation due to poor compatibility, especially caused by repulsion between like-charged units, poses a significant hurdle. Herein, the possibilities of producing diverse and homogenous POMs-containing ionohydrogels by nanoconfining POMs and ionic liquids (ILs) within an elastomer-like polyzwitterionic hydrogel using a simple one-step random copolymerization method, are expanded vastly. The incorporation of polyzwitterions provides a nanoconfined microenvironment and effectively modulates excessive electrostatic interactions in POMs/ILs/H 2 O blending system, facilitating a phase transition from macrophase separation to a submillimeter scale worm-like microphase-separation system. Moreover, combining POMs-reinforced ionohydrogels with a developed integrated self-powered sensing system utilizing strain sensors and Zn-ion hybrid supercapacitors has enabled efficient energy storage and detection of external strain changes with high precision. This work not only provides guidelines for manipulating morphology within phase-separation gelation systems, but also paves the way for developing versatile POMs-based ionohydrogels for state-of-the-art smart flexible electronics., (© 2024 Wiley‐VCH GmbH.)

Porous aromatic frameworks (PAFs) show promising potential in anionic conduction due to their high stability and customizable functionality. However, the insolubility of most PAFs presents a significant challenge in their processing into membranes and subsequent applications. In this study, continuous PAF membranes with adjustable thickness were successfully created using liquid-solid interfacial polymerization. The rigid backbone and the stable C-C coupling endow PAF membrane with superior chemical and dimensional stabilities over most conventional polymer membranes. Different quaternary ammonium functionalities were anchored to the backbone through flexible alkyl chains with tunable length. The optimal PAF membrane exhibited an OH - conductivity of 356.6 mS ⋅ cm -1 at 80 °C and 98 % relative humidity. Additionally, the PAF membrane exhibited outstanding alkaline stability, retaining 95 % of its OH - conductivity after 1000 hours in 1 M NaOH. To the best of our knowledge, this is the first application of PAF materials in anion exchange membranes, achieving the highest OH - conductivity and exceptional chemical/dimensional stability. This work provides the possibility for the potential of PAF materials in anionic conductive membranes., (© 2024 Wiley-VCH GmbH.)

Efficient construction of proton transport channels in proton exchange membranes maintaining conductivity under varied humidity is critical for the development of fuel cells. Covalent organic frameworks (COFs) hold great potential in providing precise and fast ion transport channels. However, the preparation of continuous free-standing COF membranes retaining their inherent structural advantages to realize excellent proton conduction performance is a major challenge. Herein, a zwitterionic COF material bearing positive ammonium ions and negative sulphonic acid ions is developed. Free-standing COF membrane with adjustable thickness is constructed via surface-initiated polymerization of COF monomers. The porosity, continuity, and stability of the membranes are demonstrated via the transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM) characterization. The rigidity of the COF structure avoids swelling in aqueous solution, which improves the chemical stability of the proton exchange membranes and improves the performance stability. In the higher humidity range (50-90%), the prepared zwitterionic COF membrane exhibits superior capability in retaining the conductivity compared to COF membrane merely bearing sulphonic acid group. The established strategy shows the potential for the application of zwitterionic COF in the proton exchange membrane fuel cells., (© 2023 Wiley‐VCH GmbH.)

Materials with high proton conductivity have attracted significant attention for their wide-ranging applications in proton exchange membrane fuel cells. However, the design of new and efficient porous proton-conducting materials remains a challenging task. The structure-controllable and highly stable metal phosphates can be synthesized into layer or frame networks to provide proton transport capabilities. Herein, we have successfully synthesized three isomorphic metal phosphovanadates, namely, H 2 (C 2 H 10 N 2 ) 2 [M II (H 2 O) 2 (V IV O) 8 (OH) 4 (PO 4 ) 4 (HPO 4 ) 4 ] (C 2 H 8 N 2 = 1,2-ethylenediamine; M = Co, Ni, and Cu), by the hydrothermal method employing ethylenediamine as a template. These pure inorganic open frameworks exhibit a cavity width ranging from 6.4 to 7.5 Å. Remarkably, the proton conductivity of compounds 1 - 3 can reach 1 × 10 -2 S·cm -1 at 85 °C and 97% relative humidity (RH), and they can remain stable at high temperatures as well as long-term stability. This work provides a novel strategy for the development and design of porous proton-conducting materials.

The assembly of [Mo 2 O 2 S 2 ] 2+ units depends on the configuration of polydentate phosphonic acid templates, leading to novel topologies with enhanced nuclearity and complexity. The variation of the assembled structures also gives rise to distinct proton-conducting properties.

Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions provides an intriguing pathway to convert N 2 into NH 3 . However, significant kinetic barriers of the NRR at low temperatures in desirable aqueous electrolytes remain a grand challenge due to the inert N≡N bond of the N 2 molecule. Herein, we propose a unique strategy for in situ oxygen vacancy construction to address the significant trade-off between N 2 adsorption and NH 3 desorption by building a hollow shell structured Fe 3 C/Fe 3 O 4 heterojunction coated with carbon frameworks (Fe 3 C/Fe 3 O 4 @C). In the heterostructure, the Fe 3 C triggers the oxygen vacancies of the Fe 3 O 4 component, which are likely active sites for the NRR. The design could optimize the adsorption strength of the N 2 and N x H y intermediates, thus boosting the catalytic activity for the NRR. This work highlights the significance of the interaction between defect and interface engineering for regulating electrocatalytic properties of heterostructured catalysts for the challenging NRR. It could motivate an in-depth exploration to advance N 2 reduction to ammonia., (© 2023 Wiley-VCH Verlag GmbH.)

Polyoxometalates (POMs) are considered as promising catalysts with unique redox activity at the molecular level for energy storage. However, eco-friendly iron-oxo clusters with special metal coordination structures have rarely been reported for Li-ion storage. Herein, three novel redox-active tetranuclear iron-oxo clusters have been synthesized using the solvothermal method with different ratios of Fe 3+ and SO 4 2- . Further, they can serve as anode materials for Li-ion batteries. Among them, cluster H 6 [Fe 4 O 2 (H 2 O) 2 (SO 4 ) 7 ]⋅H 2 O, the stable structure extended by SO 4 2- with a unique 1D pore, displays a specific discharge capacity of 1784 mAh g -1 at 0.2 C and good cycle performance (at 0.2 C and 4 C). This is the first instance of inorganic iron-oxo clusters being used for Li-ion storage. Our findings present a new molecular model system with a well-defined structure and offer new design concepts for the practical application of studying the multi-electron redox activity of iron-oxo clusters., (© 2023 Wiley-VCH GmbH.)

Inorganic salts usually demonstrate simple phasal behaviors in dilute aqueous solution mainly involving soluble (homogeneous) and insoluble (macrophase separation) scenarios. Herein, we report the discovery of complex phase behavior involving multiple phase transitions of clear solution - macrophase separation - gelation - solution - macrophase separation in the dilute aqueous solutions of a structurally well-defined molecular cluster [Mo 7 O 24 ] 6- macroanions with the continuous addition of Fe 3+ . No chemical reaction was involved. The transitions are closely related to the strong electrostatic interaction between [Mo 7 O 24 ] 6- and their Fe 3+ counterions, the counterion-mediated attraction and the consequent charge inversion, leading to the formation of linear/branched supramolecular structures, as confirmed by experimental results and molecular dynamics simulations. The rich phase behavior demonstrated by the inorganic cluster [Mo 7 O 24 ] 6- expands our understanding of nanoscale ions in solution., (© 2023. The Author(s).)

Xanthomonas spp. encompass a wide range of phytopathogens that brings great economic losses to various crops. Rational use of pesticides is one of the effective means to control the diseases. Xinjunan (Dioctyldiethylenetriamine) is structurally unrelated to traditional bactericides, and is used to control fungal, bacterial, and viral diseases with their unknown mode of actions. Here, we found that Xinjunan had a specific high toxicity toward Xanthomonas spp., especially to the Xanthomonas oryzae pv. oryzae ( Xoo ), the causal agent of rice bacterial leaf blight. Transmission electron microscope (TEM) confirmed its bactericidal effect by morphological changes, including cytoplasmic vacuolation and cell wall degradation. DNA synthesis was significantly inhibited, and the inhibitory effect enhanced with the increase of the chemical concentration. However, the synthesis of protein and EPS was not affected. RNA-seq revealed differentially expressed genes (DEGs) particularly enriched in iron uptake, which was subsequently confirmed by siderophore detection, intracellular Fe content and iron-uptake related genes transcriptional level. The laser confocal scanning microscopy and growth curve monitoring of the cell viability in response to different Fe condition proved that the Xinjunan activity relied on the addition of iron. Taken together, we speculated that Xinjunan exerted bactericidal effect by affecting cellular iron metabolism as a novel mode of action. IMPORTANCE Sustainable chemical control for rice bacterial leaf blight caused by Xanthomonas oryzae pv. oryzae need to be developed due to limited bactericides with high efficiency, low cost, and low toxicity in China. This present study verified a broad-spectrum fungicide named Xinjunan possessing a specific high toxicity to Xanthomonas pathogens, which were further confirmed by affecting the cellular iron metabolism of Xoo as a novel mode of action. These findings will contribute to the application of the compound in the field control of Xanthomonas spp.-caused diseases, and be directive for future development of novel specific drugs for the control of severe bacterial diseases based on this novel mode of action.

Smart molecular actuators have become a cutting-edge theme due to their ability to convert chemical energy into mechanical energy under external stimulations. However, realizing actuation at the molecular level and elucidating the mechanisms for actuating still remain challenging. Herein, we design and fabricate a novel nanoscaled polyoxometalate-based humidity-responsive molecular actuator { Bi 8 Mo 48 } through the assembly of [Mo 2 O 2 S 2 ] 2+ units, transition metals, and flexible phosphonic acid ligands. { Bi 8 Mo 48 } exhibits a semi-flexible cage-like architecture with oxygen-rich surfaces and highly negative charges 72-. The nanoscaled molecular actuator shows reversible expansion and contraction behavior under humidity variations due to lattice expansion and contraction induced by hydrogen bonding and solvation interactions between { Bi 8 Mo 48 } and water molecules. Molecular dynamics simulation was further employed to study these processes, which provides a fundamental understanding for the mechanism of humidity actuation at the molecular level.

Spatially confined assembly of semimetallic oxyanions (AsO 3 3- and SbO 3 3- ) within a [H 7 P 8 W 48 O 184 ] 33- (P 8 W 48 ) macrocycle has afforded three nanoscale polyanions, [{As III 5 O 4 (OH) 3 } 2 (P 8 W 48 O 184 )] 32- ( As 10 ), [(Sb III OH) 4 (P 8 W 48 O 184 )] 32- ( Sb 4 ), and [(Sb III OH) 8 (P 8 W 48 O 184 )] 24- ( Sb 8 ), which were crystallized as the hydrated mixed-cation salts (Me 2 NH 2 ) 13 K 7 Na 2 Li 10 [{As III 5 O 4 (OH) 3 } 2 (P 8 W 48 O 184 )]·32H 2 O ( DMA-KNaLi-As 10 ), K 20 Li 12 [(Sb III OH) 4 (P 8 W 48 O 184 )]·52H 2 O ( KLi-Sb 4 ), and (Me 2 NH 2 ) 8 K 6 Na 5 Li 5 [(Sb III OH) 8 (P 8 W 48 O 184 )]·65H 2 O ( DMA-KNaLi-Sb 8 ), respectively. A multitude of solid- and solution-state physicochemical techniques were employed to systematically characterize the structure and composition of the as-made compounds. The polyanion of As 10 represents the first example of a semimetal-oxo cluster-substituted P 8 W 48 and accommodates the largest As III -oxo cluster in polyoxometalates (POMs) reported to date. The number of incorporated SbO 3 3- groups in Sb 4 and Sb 8 could be customized by a simple variation of Sb III -containing precursors. Encapsulation of semimetallic oxyanions inside P 8 W 48 sets out a valid strategy not only for the development of host-guest assemblies in POM chemistry but also for their function expansion in emerging applications such as proton-conducting materials, for which DMA-KNaLi-As 10 showcases an outstanding conductivity of 1.2 × 10 -2 S cm -1 at 85 °C and 70% RH.

Alkaline water splitting is a highly efficient and clean technology for hydrogen energy generation. However, in alkaline solutions, most catalysts suffer from extreme instability. Herein, a cross-nanostructured N, F, and CO 3 2- codoped iron oxyhydroxide composite (N,F-FeO(OH)-CO 3 -NF) rich in oxygen defects is designed for water splitting in the alkaline solution. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations show that the introduction of F and CO 3 2- can induce electron redistribution around the active center Fe, accelerate the four-electron transfer process, and optimize the d-band center, thereby improving the efficiency and stability of HER and OER. In a 1 M KOH solution, N,F-FeO(OH)-CO 3 -NF only needs the overpotential of 248 mV for OER and the overpotential of 199 mV for HER to reach the current density of 10 mA·cm -2 . Meanwhile, it can reach 100 mA·cm -2 current density at 1.55 V vs RHE and maintains a current density of 10 mA·cm -2 for 120 h in a two-electrode electrolytic water device. Compared with bulk hydroxides, the heteroatom and anion codoped composite hydroxides are more stable and have dual functions in the electrolyte solution. This is of great significance for designing a new stable water-splitting electrocatalyst.

The oxygen reduction reaction (ORR) is a key energy conversion process, which is critical for the efficient operation of fuel cells and metal-air batteries. Here, we report the significant enhancement of the ORR-performance of commercial platinum-on-carbon electrocatalysts when operated in aqueous electrolyte solutions (pH 5.6), containing the polyoxoanion [Fe 28 (μ 3 -O) 8 (L-(-)-tart) 16 (CH 3 COO) 24 ] 20- . Mechanistic studies provide initial insights into the performance-improving role of the iron oxide cluster during ORR. Technological deployment of the system is demonstrated by incorporation into a direct formate microfluidic fuel cell (DFMFC), where major performance increases are observed when compared with reference electrolytes. The study provides the first examples of iron oxide clusters in electrochemical energy conversion and storage., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Pomegranate crown rot caused by Coniella granati is one of the most severe diseases of pomegranate. No fungicides have been registered for controlling this disease in China. Pyraclostrobin, belonging to strobilurin fungicides, has a broad spectrum of activity against many phytopathogens. In this study, based on the mycelial growth and conidial germination inhibition methods, we investigated the biological activity of pyraclostrobin against C. granati in the presence of 50 μg/ml of salicylhydroxamic acid using 80 isolates collected from different orchards in China from 2012 to 2018. The EC 50 (50% effective concentration) values ranged from 0.040 to 0.613 μg/ml for mycelial growth and 0.013 to 0.110 μg/ml for conidium germination. Treated with pyraclostrobin, the hyphae morphology changed and conidial production of C. granati decreased significantly. The result of transmission electron microscope showed that treatment of pyraclostrobin could make the cell wall thinner and lead to ruptured cell membrane and formation of intracellular organelle autophagosomes. The pyraclostrobin showed good protective and curative activities against C. granati on detached pomegranate fruits. In field trials, pyraclostrobin showed excellent control efficacy against this disease, in which the treatment of 25% pyraclostrobin EC 1,000× provided 92.25 and 92.58% control efficacy in 2019 and 2020, respectively, significantly higher than that of other treatments. Therefore, pyraclostrobin could be a candidate fungicide for the control of pomegranate crown rot.

New fungicides are tools to manage fungal diseases and overcome emerging resistance in fungal pathogens. In this study, a total of 121 Fusarium fujikuroi isolates were collected from various geographical regions of China and their sensitivity to a novel succinate dehydrogenase inhibitor (SDHI) fungicide 'pydiflumetofen' was evaluated. The 50% effective concentration (EC 50 ) value of pydiflumetofen for mycelial growth suppression ranged from 0.0101 to 0.1012 μg/ml and for conidial germination inhibition ranged from 0.0051 to 0.1082 μg/ml. Pydiflumetofen-treated hyphae showed contortion and increased branching, cell membrane permeability, and glycerol content significantly. The result of electron microscope transmission indicated that pydiflumetofen damaged the mycelial cell wall and the cell membrane, and almost broke up the cells, which increased the intracellular plasma leakage. There was no cross-resistance between pydiflumetofen and the widely used fungicides such as carbendazim, prochloraz, and phenamacril. Pydiflumetofen was found safe to seeds and rice seedlings of four rice cultivars, used up to 400 μg/ml. Seed treatment significantly decreased the rate of diseased plants in the greenhouse as well as in field trials in 2017 and 2018. Pydiflumetofen showed superb results against the rice bakanae disease (RBD), when used at 10 or 20 g a.i./100 kg of treated seeds, providing over 90% control efficacy (the maximum control efficacy was up to 97%), which was significantly higher than that of 25% phenamacril (SC) at 10 g or carbendazim at 100 g. Pydiflumetofen is highly effective against F. fujikuroi growth and sporulation as well as RBD in the field.

As a new class of crystalline porous organic materials, covalent organic frameworks (COFs) have attracted considerable attention for proton conduction owing to their regular channels and tailored functionality. However, most COFs are insoluble and unprocessable, which makes membrane preparation for practical use a challenge. In this study, we used surface-initiated condensation polymerization of a trialdehyde and a phenylenediamine for the synthesis of sulfonic COF (SCOF) coatings. The COF layer thickness could be finely tuned from 10 to 100 nm by controlling the polymerization time. Moreover, free-standing COF membranes were obtained by sacrificing the bridging layer without any decomposition of the COF structure. Benefiting from the abundant sulfonic acid groups in the COF channels, the proton conductivity of the SCOF membrane reached 0.54 S cm -1 at 80 °C in pure water. To our knowledge, this is one of the highest values for a pristine COF membrane in the absence of additional additives., (© 2021 Wiley-VCH GmbH.)

Fabricating proton exchange membranes (PEMs) with high ionic conductivity and ideal mechanical robustness through regulation of the membrane microstructures achieved by molecular-level hybridization remains essential but challenging for the further development of high-performance PEM fuel cells. In this work, by precisely hybridizing nano-scaled bismuth oxide clusters into Nafion, we have fabricated the high-performance hybrid membrane, Nafion-Bi 12 -3 %, which showed a proton conductivity of 386 mS cm -1 at 80 °C in aqueous solution with low methanol permeability, and conserved the ideal mechanical and chemical stabilities as PEMs. Moreover, molecular dynamics (MD) simulation was employed to clarify the structural properties and the assembly mechanisms of the hybrid membrane on the molecular level. The maximum current density and power density of Nafion-Bi 12 -3 % for direct methanol fuel cells reached to 432.7 mA cm -2 and 110.2 mW cm -2 , respectively. This work provides new insights into the design of versatile functional polymer electrolyte membranes through polyoxometalate hybridization., (© 2020 Wiley-VCH GmbH.)

Lavender (Lavandula angustifolia Mill) is an ornamental plant and worldwidely grown for its aromatic and pharmacological qualities. In June 2020, the symptoms of blackleg disease on lavender plants were observed, with more than 50% incidence in Chaohu city (117°38'19.12″N, 31°47'18.94″W) of Anhui Province, China. The disease symptoms progressed from stem wilt and necrosis to prolonged necrosis and bending of leaves, and all infected lavender plants died eventually. Ten necrotic stem lesions werecollectedfrom ten independent plants for the isolation of pathogen. All samples were washed in 70% ethanol for 1 minute, rinsed twice in sterile distilled water and placed on water agar (WA) plates containing 30 mg/liter of kanamycin. All 16 fungal isolates were transferred onto potato dextrose agar (PDA) and incubated at 26°C for 5 days, and all fungal colonies were isolated consistently, which produced redish-gray mycelium at 26°C with a 12-h photoperiod on PDA media. They developed black pycnidia with abundant hyaline, unicellular, oval shaped conidia (4.5 to 5.9 × 2.1 to 2.5 μm) after 14 days. DNA was extracted (10-day-old culture) using the Fungal DNA Mini Kit (Omega Bio-tek, China), according to the manufacturer's protocol. The internal transcribed spacer (ITS), beta-tubulin (β-tub) and translation elongation factor 1-alpha (tef1-α) genes of three isolates were amplified using the primers: ITS1/ITS4 (White et al. 1990), Bt2a/Bt2b (Glass et al. 1995) and EF1-728F/EF1-986R (Carbone et al. 1999), respectively. The ITS(MT883331), β-tub(MT896891) andtef1-α (MT874165) genes were sequenced and analyzed through BLASTn. The ITS sequence showed 99.81% with Epicoccum sorghinum (GenBank Accession No. MK020690.1). The β-tub and tef1-α showed 100% homology with Epicoccum sorghinum (GenBank AccessionMN554062.1 and MN512426.1), respectively. To complete Koch's postulates, pathogenicity tests were performed by spraying the fungal spore suspension (1×105 CFU/ml) prepared from 14-day-old cultures onto needling wounded stems of 1-year-old potted healthy L. angustifolia plants. The healthy plants were sprayed with sterilized water onto needling wounded stems served as negative control. Wilting and stem necrosis were observed 5 days afterinoculation and incubation in a growth chamber at 26°C, with a 12-h photoperiod. All fungal infected plants died after 10 days, while, the control plants remained healthy. The fungus was re-isolated from the lesions of the inoculated plants and verified. Based on morphological characteristics, sequence analysis and pathogenicity test, the pathogen was identified as E. sorghinum. The pathogen has been observed previously on many plants such as tea (Bao et al. 2019) and taro (Liu et al. 2018), in China. To our knowledge, this is the first report of E. sorghinum causing blackleg disease of lavender in China and worldwide.

Two new cucurbit[6]uril (CB[6])-based metal-organic rotaxane networks (MORNs) were successfully obtained by tuning the coordination sphere of metal copper clusters. Compounds 1 and 2 exhibited relatively high proton conductivity at 85 °C and 97% relative humidity (RH), providing great promise for fuel cell electrolyte materials.

Objective: This study aimed at exploring the role of α-enolase (ENO1) in proliferation, invasion, and cell apoptosis in MDA-MB-231 and MCF-7 breast cancer human cells, to provide a theoretical basis for the clinical treatment of breast cancer., Materials and Methods: MDA-MB-231 and MCF-7 cells were randomly divided into five groups: normal control group (Control group), negative control group (negative control virus, NC group), and shENO1 (sh1, sh2, and sh3) group, respectively. The expressions of ENO1 mRNA and protein were measured by Quantitative Real Time-Polymerase Chain Reaction (qRT-PCR) and Western blot, respectively. Cell proliferation, cell invasion ability, and cell apoptosis rate were detected by methyl thiazolyl tetrazolium (MTT) assay, transwell invasion assay, and flow cytometer, respectively. The expressions of the proteins correlated with phosphatidylinositol 3-kinase (PI3K)/protein kinase B (Akt) signaling pathway were analyzed by Western blot., Results: In MDA-MB-231 and MCF-7 cells, the gene and protein expressions of ENO1 in the three sh groups in MDA-MB-231 and MCF-7 cells were significantly lower than those in control group and NC group. In MDA-MB-231 and MCF-7 cells, the gene and protein expressions of ENO1 in the three sh groups were significantly lower than those in control group and NC group. Compared with NC group, the proliferation activity, invasion ability, and apoptosis rate of shENO1 group were significantly decreased (p < 0.01). PI3K and Akt protein levels in shENO1 group were significantly downregulated (p < 0.01). Bcl-2 protein expression was markedly upregulated (p < 0.01), meanwhile Bax protein revealed a significant reduction (p < 0.01)., Conclusions: The results revealed that silencing ENO1 reduced proliferation activity, invasion ability, and apoptosis rate of breast cancer cells by decreasing the phosphorylation of PI3K and Akt pathway. Our results suggested that ENO1 may be a potential therapeutic target in breast cancer.

Alternaria species are the most important fungal pathogens that attack various crops as well as fruit trees such as pear and cause black spot disease. Here, a loop-mediated isothermal amplification (LAMP) assay is developed for the detection of Alternaria species. A. alternata cytochrome b ( cyt-b ) gene was used to design two pairs of primers and amplified a 229-bp segment of Aacyt-b gene. The results showed that LAMP assay is faster and simpler than polymerase chain reaction (PCR). LAMP assay is highly sensitive method for the detection of about 1 pg of genomic DNA of A. alternata by using optimized concentration of MgCl 2 (4 mM) in final LAMP reaction. In contrast, the limit of detection was 1 ng of target DNA via conventional PCR. Among the genomic DNA of 46 fungal species, only the tubes containing DNA of Alternaria spp. except A. porri , A. solani , and A. infectoria changed color from orange to yellowish green with SYBR Green I including the main pathogens of pear black spot. The yellowish green color was indicative of DNA amplification. Moreover, LAMP assay was used for testing infected tissues among 22 healthy and diseased pear tissues; the orange color changed to yellowish green for infected tissues only. Altogether, we conclude that cyt-b gene can be used for the detection of Alternaria spp. via LAMP assay, which is involved in pear black spot disease.

OER is the key step to increase the rate of water-splitting reaction. Design and construction of appropriate defects is an effective strategy to enhance catalytic activity. Mn has stronger e - -e - repulsion by the local influence of its 3d orbital electrons. When Mn(iii) was successfully introduced into two dimensional F-doped Ni(OH) 2 , it can tune the surface electronic structure of the F-doped Ni(OH) 2 to increase its oxygen deficiency content. In this work, the as-synthesized Mn and F co-doped Ni(OH) 2 -NF on Ni foam (Mn-F/Ni(OH) 2 -NF) shows remarkable oxygen evolution performance, exhibiting 233 mV overpotential at 20 mA cm -2 , and the Tafel slope is 56.9 mV dec -1 in 1 M KOH. The performance is better than that of the same loading of IrO 2 on Ni foam. Density functional theory (DFT) calculations further show that the introduction of oxygen defects can significantly improve the OER catalytic performance of Mn-F/Ni(OH) 2 -NF., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The objective of this work was to analyze four essential oils (EOs) from Rhododendron species in China and evaluate their repellent activity against Tribolium castaneum, Lasioderma serricorne, and Liposcelis bostrychophila adults. These four EOs from Rhododendron species, including R. capitatum, R. przewalskii, R. mucronulatum, and R. micranthum, were obtained by hydrodistillation. Major components of four EOs were identified as sesquiterpenoids by GC-MS. The relatively high components included cedrene (22.20%), borneol (36.64%), 4-(2,3,4,6-tetramethylphenyl)-3-buten-2-one (27.74%), and germacrene D (27.60%). Repellent activity of EOs from Rhododendron species was investigated against T. castaneum, L. serricorne, and L. bostrychophila adults for the first time. In this study, EOs had demonstrated their repellent activities against three stored-product insects in 2- and 4-h exposure. The above results can not only provide comprehensive utilization of plant resources of Rhododendron genus but also establish a very good perspective of novel application to control stored-product insects.

Proton exchange membrane fuel cells are still limited as state-of-art proton exchange membranes perform poorly at high and low temperature and are easily damaged by harsh electrochemical conditions such as reactive peroxide species. One effective solution to this issue is to develop new types of proton conductive materials that are capable of working in a broad temperature range. A simple vacuum-assisted filtration method is employed to obtain a well-ordered new proton-conducting membrane by immobilizing nanosized bismuth oxide clusters [H 6 Bi 12 O 16 ] (NO 3 ) 10 ·6(H 2 O) {H 6 Bi 12 O 16 } onto graphene oxide (GO) supports (named as {H 6 Bi 12 O 16 }/GO). {H 6 Bi 12 O 16 }/GO is stable in acidic media and has high proton conductivity over the temperature range from -40 to 80 °C. The proton conductivity of the {H 6 Bi 12 O 16 }/GO membrane is 0.564 S cm -1 at 80 °C in aqueous solution (in plane), and 0.1 S cm -1 at 80 °C and 97% RH (out of plane), respectively. Without loss of high proton conductivity, the membrane also exhibited 100-fold lower methanol permeability than a Nafion 117 membrane. Moreover, {H 6 Bi 12 O 16 }/GO displayed good catalytic decomposition of hydrogen peroxide and superior humidity response and recovery properties. These advantages mean that {H 6 Bi 12 O 16 }/GO holds great promise as a solid-state electrolyte that can potentially be applied in energy conversion devices in the future.

Ustilaginoidea virens is an important fungus that causes rice false smut disease. This disease significantly reduces both grain yield and quality. Various methods have been developed for the detection of U. virens but most of these methods need sophisticated equipment such as a thermal cycler. Here, we present a loop-mediated isothermal amplification (LAMP) assay for the specific detection of U. virens. This assay used a specific region of the UvG-β1 gene (212-bp region) to design six LAMP primers. The LAMP assay was optimized by the combination of rapidity, simplicity, and high sensitivity for the detection of about 1 pg of target genomic DNA in the reaction whereas, with polymerase chain reaction (PCR), there was no amplification of DNA with concentrations less than 1 ng. Among the genomic DNA of 22 fungus species and two strains of U. virens, only the tube containing the DNA of U. virens changed to yellowish green with SYBR Green I. The color change was indicative of DNA amplification. No DNA was amplified from either the other 22 fungus species or the negative control. Moreover, 20 spikelets and 22 rice seed samples were used for the detection of rice false smut via LAMP. The results were comparable with conventional PCR. We conclude that gene UvG-β1 coupled with LAMP assay, can be used for the detection and identification of U. virens gene via LAMP.

A luminescent MOF with rectangular channels was synthesized and characterized. It is capable of showing a high proton conductivity up to 0.95 × 10 -2 S cm -1 at 60 °C and 97% RH, and sensing metal ions (particularly Cr 3+ ions), through fluorescence quenching in presence of mixed metal ions.

Herein, we show the controlled generation of multi-component libraries based on the [MoS 2 O 2 ] 2+ /Mo VI O 4 2- /Se IV O 3 2- /C 4 O 4 2- system leading to the formation of a whole new family of nanosized molecular chalcoxides, {Se 8 Mo 36 } 1, {Se 8 Mo 40 } 2, {Se 8 Mo 56 } 3, {Se 20 Mo 56 } 4 and {Se 26 Mo 68 } 5, of the general formula {(MoO 2 S 2 ) a (OH) b (Se IV O 3 ) c (C 4 O 4 ) d (MoO 7 ) e } n- , where a, b, c, d, e, n = [16, 20, 8, 6, 2, 20] for 1, [18, 24, 8, 6, 2, 20] for 2, [24, 32, 8, 8, 4, 24] for 3, [28, 32, 20, 8, 0, 32] for 4 and [34, 36, 26, 8, 0, 36] for 5. The coordination modulation effect offered by the Se IV O 3 2- and the C 4 O 4 2- anions lead to the generation of new building blocks, [(MoO 2 S 2 ) 3 (OH) 6 (C 4 O 4 ) (MoO 7 )] 4- , and the discovery of a new family of clusters of increasing nuclearity and complexity.

During the exploration of highly efficient noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER), a promising and challenging strategy is to fabricate composite nanocatalysts by finely tuning metal and/or nonmetal element components. Herein, we report a new HER electrocatalyst, which is composed of molybdenum phosphide and molybdenum carbide composite nanoparticles (NPs) coated by few-layer N-doped graphitic carbon shells (denoted as MoP/Mo 2 C@C). Such a new combination mode of electrocatalysts is realized by a one-step annealing route with the mixture of a Mo/P-based polyoxometalate (POM) and dicyandiamide. On the basis of this method, the simultaneous phosphorization and carbonization in a nanoscale confined space can be easily achieved by the use of POM as the molecular-element-regulating platform. MoP/Mo 2 C@C exhibits more remarkable HER performance over the whole pH range than those of MoP, Mo 2 C, and the physical mixture of MoP and Mo 2 C. The low overpotentials of 89, 136, and 75 mV were obtained at a current density of 10 mA cm -2 in the media of pH = 0, 7, and 14, respectively. Furthermore, MoP/Mo 2 C@C shows a long-term durability for 14 h over the entire pH range (0-14). Because of the protection of carbon shells, such composite electrocatalyst also possesses better transition-metal tolerance exemplified by Fe 2+ , Co 2+ , and Ni 2+ than that of 20% commercial Pt/C. This work demonstrates the advantage of POM precursors in adjusting the component and properties of nanoscale composite electrocatalysts for HER, which may suggest new options for the fabrication of highly efficient composite electrocatalysts.

We have demonstrated for the first time that isostructural homochiral metal-organic frameworks (MOFs) can be synthesized directly from chiral ligands and indirectly from achiral ligands via spontaneous resolution combined with cooperative chirality induction, respectively. Moreover, the usage of different ligands leads to distinct proton conduction behaviors.

Pilidiella granati, a causal agent of twig blight and crown rot of pomegranate, is an emerging threat that may cause severe risk to the pomegranate industry in the future. Development of a rapid assay for the timely and accurate detection of P. granati will be helpful in the active surveillance and management of the disease caused by this pathogen. In this study, a nested PCR method was established for the detection of P. granati. Comparative analysis of genetic diversity within 5.8S rDNA internal transcribed spacer (ITS) sequences of P. granati and 21 other selected fungal species was performed to design species-specific primers (S1 and S2). This primer pair successfully amplified a 450 bp product exclusively from the genomic DNA of P. granati. The developed method can detect 10 pg genomic DNA of the pathogen in about 6 h. This technique was successfully applied to detect the natural infection of P. granati in the pomegranate fruit. The designed protocol is rapid and precise with a high degree of sensitivity.

Background: This study aims to investigate the effects of recombinant human brain natriuretic peptide (rhBNP) on serum enzyme data, cardiac function parameters and cardiovascular events in patients with acute anterior myocardial infarction (MI)., Methods: A total of 421 patients with acute anterior or extensive anterior MI were collected from 20 hospitals. These patients were randomly divided into two groups: rhBNP and control groups. Both groups of patients received primary percutaneous coronary intervention (PCI) within the effective time window. In the rhBNP group, rhBNP administration (0.01 µg/kg/min, 48-72 successive hours) was performed as early as possible after hospital admission. Prior to and one or seven days after PCI, serum concentrations of cardiac troponin (cTnT), creatine kinase-MB (CK-MB) and N-terminal pro-brain natriuretic peptide (NT-proBNP) were measured. At seven days and 6 months after PCI, left ventricular ejection fraction (LVEF), left ventricular end-diastolic diameter (LVEDd) and stroke volume (SV) were measured using 2D Doppler echocardiography. MACEs that occurred during hospitalization and within 6 months after PCI were recorded., Results: At postoperative days one and seven, serum concentrations of cTnT were significantly lower in the rhBNP group than in the control group. At postoperative day one, serum concentrations of CK-MB were significantly lower in the rhBNP group than in the control group. At postoperative day seven, serum concentrations of NT-proBNP were significantly lower in the rhBNP group than in the control group, and LVEF was significantly greater in the rhBNP group than in the control group. At postoperative 6 months, LVEDd was significantly lower in the rhBNP group compared with the control group. In addition, SV and LVEF were significantly greater in the rhBNP group than in the control group. By postoperative month 6, the incidence of composite cardiovascular events (16.0% vs . 26.0%, P=0.012), cardiac death (7.0% vs .13.5%, P=0.030), and particularly cardiac death + re-hospitalization for congestive heart failure (13.1% vs . 25.5%, P=0.001) were significantly lower in the rhBNP group than in the control group., Conclusions: Early intravenous rhBNP administration after PCI significantly lowered the serum concentrations of cTnT and NT-proBNP, increased LVEDd, SV and LVEF, and reduced MACEs, including cardiac death, in patients with acute anterior MI undergoing PCI., Competing Interests: Conflicts of Interest: The authors have no conflicts of interest to declare.

A simple and rapid method for the detection of Tilletia horrida, the causal agent of rice kernel smut, in rice seeds is developed based on specific polymerase chain reaction (PCR). To design the specific primers for the detection of T. horrida, partial sequences of internal transcribed spacer (ITS) DNA region of T. horrida, T. controversa, T. walkeri, T. ehrhartae, T. indica and T. caries were analyzed and compared. A 503-bp fragment was amplified with the designed primers from the T. horrida genomic DNA. However, no PCR product was obtained from the DNA of other five Tilletia species and 22 fungal plant pathogens tested in the present work indicating the specificity of the primers for the detection of T. horrida. The PCR was performed by directly using the spores, isolated from the 21 different rice seed samples, as template DNA. The T. horrida was detected in 6 of the samples, indicating that 28.6% of the rice samples were contaminated with the kernel smut pathogen. This simple PCR based diagnostic assay can be applied for the direct and rapid detection and identification of T. horrida to screen large numbers of rice seed samples.

We describe how supramolecular assembly, mediated by control of the ratio of the hetero-atoms in the units [Mo 2 S 2 O 2 ] 2+ and SeO 3 2- leads to the formation of new types of building blocks, [(Mo 2 O 2 S 2 ) 3 (OH) 4 (H 2 O) 6 (SeO 3 )] = {Mo 6 } and [(Mo 2 O 2 S 2 ) 2 (OH) 2 (H 2 O) 4 (SeO 3 )] = {Mo 4 } which are linked in an type of inorganic 'panelling' to the assembly of a range of new clusters 1-3 with the general formula {(Mo 2 O 2 S 2 ) x (OH) y (SeO 3 ) z (H 2 O) w } n - , where x , y , z , w , n = [8, 0, 20, 8, 24] for 1 , [14, 14, 17, 8, 20] for 2 and [8, 8, 8, 0, 8] for 3 . Cluster 1 , a rare example of inorganic cryptand, exhibits an elliptical "endo" motif defining an anisotropic ellipse with the dimensions 1.7 × 1.0 nm, with pores ranging from 5.3 to 6.4 Å and site selective cation recognition properties; cluster 2 exhibits an "exo" structural motif constructed by 3 × {Mo 6 } and 2 × {Mo 4 } panels spanning a cross shape 2.4 × 2.0 nm and cluster 3 a ring shaped structure of a 1.5 nm in diameter. The control of endo vs. exo topology as a function of the Se : Mo ratio is reflected to the difference in surface area of ca. 500 Å 2 between clusters 1 and 2 intermolecular interactions and proton conduction properties, and this work shows that very simple synthetic parameters can critically change the structure and properties of all-inorganic nanoscale chalcogenide-polyoxometalates.

Mimicking proton conduction mechanism of Nafion to construct novel proton-conducting materials with low cost and high proton conductivity is of wide interest. Herein, we have designed and synthesized a cationic covalent organic framework with high thermal and chemical stability by combining a cationic monomer, ethidium bromide (EB) (3,8-diamino-5-ethyl-6-phenylphenanthridinium bromide), with 1,3,5-triformylphloroglucinol (TFP) in Schiff base reactions. This is the first time that the stable cationic crystalline frameworks allowed for the fabrication of a series of charged COFs (EB-COF:X, X = F, Cl, Br, I) through ion exchange processes. Exchange of the extra framework ions can finely modulate the COFs' porosity and pore sizes at nanoscale. More importantly, by introducing PW12O40(3-) into this porous cationic framework, we can greatly enhance the proton conductivity of ionic COF-based material. To the best of our knowledge, EB-COF:PW12 shows the best proton conductivity at room temperature among ever reported porous organic materials.

Assembly of cucurbit[6] and a {Cd2Ge8V12O48} cluster produced two rotaxane-shaped and polyrotaxane-shaped solids by changing the ratio of starting precursors in the system. The high oxygen density of the polyoxoanion surface provides active sites to extend a single rotaxane-shaped hybrid 1 to a 1D polyrotaxane-shaped hybrid 2. This construction strategy may afford an entirely new methodology for polyoxometalate-based hybrid chemistry.

Three hybrid coordination networks that were constructed from ɛ-Keggin polyoxometalate building units and imidazole-based bridging ligands were prepared under hydrothermal conditions, that is, H[(Hbimb)2 (bimb){Zn4 PMo(V8) Mo(VI) 4O40}]⋅6 H2O(1), [Zn(Hbimbp)(bimbp)3 {Zn4 PMo(V8) Mo(VI) 4O40}]⋅DMF⋅3.5 H2O(2), and H[Zn2 (timb)2 (bimba)2 Cl2 {Zn4 PMo(V8) Mo(VI) 4O40}]⋅7 H2O(3) (bimb=1,4-bis(1-imidazolyl)benzene, bimbp=4,4'-bis(imidazolyl)biphenyl, timb=1,3,5-tris(1-imidazolyl)benzene, bimba=3,5-bis(1-imidazolyl)benzenamine). All three compounds were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. The mixed valence of the Mo centers was analyzed by XPS spectroscopy and bond-valence sum calculations. In all three compounds, the ɛ-Keggin polyoxometalate (POM) units acted as nodes that were connected by rigid imidazole-based bridging ligands to form hybrid coordination networks. In compound 1, 1D zigzag chains extended to form a 3D supramolecular architecture through intermolecular hydrogen-bonding interactions. Compound 2 consisted of 2D curved sheets, whilst compound 3 contained chiral 2D networks. Because of the intrinsic reducing properties of ɛ-Keggin POM species, noble-metal nanoparticles were loaded onto these POM-based coordination networks. Thus, compounds 1-3 were successfully loaded with Ag nanoparticles, and the corresponding composite materials exhibited high catalytic activities for the reduction of 4-nitrophenol., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The reaction of Keggin-type polyoxometalate (POM) units, transition-metal (TM) ions, and a rigid bis(imidazole) ligand (1,4-bis(1-imidazolyl)benzene (bimb)) in a hydrothermal environment led to the isolation of four new POM-based metal-organic networks, [H2 L][CuL][SiW12 O40 ]⋅2 H2 O (1), [H2 L]2 [Co(H2 O)3 L][SiW11 CoO39 ]⋅6 H2 O (2), KH[CuL]2 [SiW11 CoO39 (H2 O)]⋅2 H2 O (3), and [CuL]4 [GeW12 O40 ]⋅H2 O (4; L=bimb). All four compounds were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Compounds 1 and 3 are new 3D networks with 1D channels. Compounds 2 and 4 contain 2D networks, which further stack into 3D supramolecular networks. The contributions of pH value, the negative charge of the POM, and the TM coordination modes to the construction of 3D networks were elucidated by comparing the synthetic conditions and structures of compounds 1-4. The photocatalytic properties of compounds 1-4 were investigated using methylene blue (MB) degradation under UV light. All compounds showed good catalytic activity and structural stability. The possible catalytic mechanism was discussed on the basis of active-species trapping experiments. The different photocatalytic activities of compounds 1-4 were explained by comparison of the band gaps of different POM species and different packing modes of POM units in these hybrid compounds., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A large lanthanide-containing tungstotellurites(iv) nanocluster Na18[Ce10Te8W88O298(OH)12(H2O)40]·54H2O () was synthesized by combining cerium linkers and TeO3(2-) heteroanion templates. The macroanion in consists of two identical [Te4W42O144(OH)6Ce4(H2O)13](14-) subunits and two triangle-shaped {W2O5Ce(H2O)7} linkers.

A series of polynuclear metal-oxo clusters have been constructed from the dynamic polyoxometalate (POM) building block {B-α-Sb(III)W9O33} and lanthanide (Ln) linkers via a stepwise synthetic strategy with the molecular formulas of [Ln2(H2O)4{WO2(pic)}2(SbW8O30)2](10-) (Na4Li6[La-1]·28H2O, Na3Li7[Pr-2]·30H2O) and [{Ln(H2O)}{Ln(pic)}(Sb3O4)(SbW8O31)(SbW10O35)]2(24-) (K2Na6Li16[Tb-3]·63H2O, Na9Li15[Dy-4]·61H2O, Na7Li17[Ho-5]·53H2O) (Hpic = picolinic acid). The five compounds have been characterized by FT-IR, elemental analysis, TG, powder X-ray diffraction (PXRD) and single crystal X-ray diffraction. In compounds 1-5, various POM moieties, such as {B-β-SbW8O30}, {B-α-SbW8O31} and {B-α-SbW10O35}, were formed through a series of disassembling and re-assembling processes of the dynamic {B-α-SbW9O33} precursor with specific pH, reaction temperature and time. Furthermore, the use of oxytropic Ln(3+) ions as linkers, together with auxiliary organic pic ligands and/or inorganic Sb(3+) ions, led to diverse connection modes between the POM building blocks and Ln linkers and the assembly of new polynuclear metal-oxo clusters. The polyoxoanions of La-1 and Pr-2 possess the same structural feature, which can be viewed as a sandwich-type cluster composed of two {B-β-SbW8O30} units connected by two {WO2(pic)} fragments and two hydrated Ln ions. These sandwich-type polyoxoanions are further linked by the hydrated Ln ions to form a 1-D helical chain. The polyoxoanions of Tb-3, Dy-4 and Ho-5 display the same structural features, although they contain different counter-cations and lattice water molecules. In the polyoxoanions of 3-5, one {B-α-SbW8O31} POM moiety and one {B-α-SbW10O35} POM unit are connected by one {Sb3O4} fragment and one {Ln(pic)} linker, forming an asymmetric sandwich-type metal-oxo cluster. Two of these sandwich-type clusters are further fused together by extra two hydrated Ln ions, leading to an isolated polynuclear metal-oxo cluster with a size of 16.4 × 28.5 Å. The photoluminescence properties of Tb-3 and Dy-4 were investigated. Both compounds exhibit characteristic Tb(3+) and Dy(3+) luminescence. The relationship between the luminescence properties and the crystal structure of the polyoxoanion was discussed.

The first polyoxometalate-based metal-organic nanotube constructed via covalent bonds has been synthesized. POM anions stick the metal-organic nanotubes to build 3D nanotubular arrays. The stability, magnetic and proton conducting properties are investigated.

A versatile one-pot strategy was used to synthesize two large, purely inorganic selenotungstates, nanocluster K(6)Na(16) [Ce(6)Se(6)W(67)O(230) (OH)(6) (H(2)O)(17)]⋅47 H(2)O (1) and layer K(9)Na(5) Ce(H(2)O)(4) [Ce(6)Se(10)W(51)O(187) (OH)(7) (H(2)O)(18)]⋅45H(2)O(2), by combining cerium centers and SeO(3) (2-) heteroanion templates. Compound 1 displays a Ce-stabilized hexameric nanocluster with one rhombus-like {W(4)O(15) (OH)(3)} unit in the center, whereas compound 2 is the first example of a Ce-bridged layer selenotungstate network based on linkage of the unusual {Ce(6)Se(10)W(51)O(187) (OH)(7) (H(2)O)(18)} clusters and additional Ce(H(2)O)(4) fragments via Ce-O-Se bridges. The compounds were characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, powder and single-crystal X-ray diffraction, and electrospray ionization mass spectrometry. Moreover, the electrochemical property of compound 1 was also investigated., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)