Efficient Electrochemical Sensing of Chlorpromazine with a Composite of Multiwalled Carbon Nanotubes and a Thiacalix[4]arene-Based Metal-Organic Framework.

Chlorpromazine (CPMZ) is a representative drug for the treatment of psychiatric disorders. Excessive use of CPMZ could result in some serious health problems, and therefore, construction of a sensitive electrochemical sensor for CPMZ detection is greatly significant for human health. Herein, a feasible electrochemical method for the detection of CPMZ was provided. To design a suitable electrode surface modifier, a new two-dimensional (2D) thiacalix[4]arene-based metal-organic framework was designed and synthesized under solvothermal conditions, namely, [Co(TMPA)Cl2]MeOH·2EtOH·2H2O (Co-TMPA). Afterward, a series of composite materials was prepared by combining Co-TMPA with highly conductive carbon materials. Markedly, Co-TMPA/MWCNT-2@GCE (GCE = glassy carbon electrode, MWCNT = multiwalled carbon nanotube) exhibited the best electrocatalytic performance for CPMZ detection due to the synergistic effect between MWCNT and Co-TMPA. Particularly, it featured a low limit of detection (8 nM) and a wide linear range (0.05 to 1350 µM) in quantitative determination of CPMZ. Meanwhile, the sensor possessed excellent stability, selectivity, and reproducibility. Importantly, Co-TMPA/MWCNT-2@GCE was employed to analyze CPMZ in urine and serum with satisfactory recoveries (98.87-102.17%) and relative standard deviations (1.44-3.80%). Furthermore, the electrochemical detection accuracy of the Co-TMPA/MWCNT-2@GCE sensor was verified with the ultraviolet-visible spectroscopy technique. This work offers a promising sensor for the efficient analysis of drug molecules.

Medium entropy FeCoNi nanoalloy supported on reduced graphene oxide for efficient electrochemical detection of roxarsone in food samples.

Herein, a novel FeCoNi(b)-800 ternary metal nanoalloy was uniformly mixed with reduced graphene oxide (RGO) to synthesize the FeCoNi(b)-800@RGO(2:1) composite. The addition of RGO not only stopped the accumulation of FeCoNi(b)-800 alloy, but also heightened the electrocatalytic activity of composite. Particularly, the FeCoNi(b)-800@RGO(2:1) composite displayed the significantly strong electrocatalytic capacity for the reduction of roxarsone (ROX). Furthermore, the FeCoNi(b)-800@RGO(2:1) composite possessed enough porosity and metal catalytic sites, facilitating the transport and electrochemical reduction of the ROX. Thus, the FeCoNi(b)-800@RGO(2:1) composite modified glassy carbon electrode (FeCoNi(b)-800@RGO(2:1)/GCE) showed the superb electrochemical detection effect for ROX with relatively wide working range (0.1-1500 µM) and low detection limit (0.013 µM). Importantly, the FeCoNi(b)-800@RGO(2:1)/GCE sensor could accurately determine the contents of ROX in actual pork, chicken, duck and egg samples, indicating that it had good suitability in food safety monitoring.

A new thiacalix[4]arene-based metal-organic framework as an efficient electrochemical sensor for trace detection of Cd2+ and Pb2.

Heavy metal ions (HMIs) can lead to serious harm to human health and ecological environment. Thus, developing an efficient detection method for HMIs is extremely necessary. Herein, a new thiacalix[4]arene-based metal-organic framework (MOF) [Co2(L1)(TPA)2]·DMA·3CH3OH·H2O (Co-LTPA) (L1 = thiacalix[4]arene-based ligand and H2TPA = terephthalic acid) was successfully synthesized. The electrochemical detection platform (Co-LTPA/GCE) was acquired, and Co-LTPA/GCE featured ultrasensitive detection of HMIs with greatly low limits of detection (LODs) of 0.119 nM for Cd2+ and 0.279 nM for Pb2+ as well as wide linear ranges of 0.08-5.8 µM for Cd2+ and 0.01-6.0 µM for Pb2+. More importantly, the Co-LTPA/GCE sensor was employed to detect foods (milk, honey and orange juice) and water samples (tap water, lake water and drinking water) with satisfactory recoveries, proving the sensor reliability in practical applications. This work provided an example that the functional electrochemical Co-LTPA/GCE sensor was employed for Cd2+ and Pb2+ detection.

Composite of a thiacalix[4]arene-copper(I) metal-organic framework and mesoporous carbon for efficient electrochemical detection of antibiotics.

Abundant use of nitrofurantoin (NFT) and metronidazole (MTZ) antibiotics has led to excessive residues in the environments and humans, resulting in serious damage to the human body and ecosystem. Therefore, effective detection of NFT and MTZ is exceedingly necessary. In this regard, metal-organic frameworks (MOFs) are promising materials as electrochemical sensors. Herein, we synthesized a new two-dimensional thiacalix [4]arene-copper (I) MOF (Cu-TC4A-M). This MOF was mixed with mesoporous carbon (MC) to a give Cu-TC4A-M@MC composite. In addition, the sensors of Cu-TC4A-M@MC(2:1)/GCE and Cu-TC4A-M@MC(1:2)/GCE were achieved (GCE = glassy carbon electrode), and then were applied for effectively detecting NFT and MTZ, respectively. Markedly, the two sensors exhibited satisfactory linear detection range, anti-interference, reproducibility and stability. When they were utilized in the real samples, such as human serum, urine, tap water and lake water, satisfactory recoveries were attained. The relative standard deviations (RSDs) were in the range of 1.16 % âˆ¼ 1.92 % for NFT and 0.95 % âˆ¼ 2.33 % for MTZ. This work provided a new application prospect for the thiacalix [4]arene-based MOFs as promising candidate materials for NFT and MTZ detection.

Thiacalix[4]arene-based metal-organic framework/reduced graphene oxide composite for electrochemical detection of chlorogenic acid.

A novel metal-organic framework [Co2LCl4]·2DMF (Co-L) based on thiacalix[4]arene derivative was synthesized using the solvothermal method. Then Co-L was respectively mixed with reduced graphene oxide (RGO), multi-walled carbon nanotubes (MWCNT) and mesoporous carbon (MC) to prepare corresponding composite materials. PXRD, SEM and N2 adsorption-desorption illustrated that composite materials have been successfully prepared. After optimizing experimental conditions for detecting chlorogenic acid (CGA), the Co-L@RGO(1:1) composite material showed the optimal electrocatalytic activity for CGA, which may be because RGO possessed large specific surface area and hydroxyl and carboxyl groups that could form hydrogen-bonding with the oxide of CGA. Benefiting from the synergetic effect of Co-L and RGO, the glassy carbon electrode modified with Co-L@RGO(1:1) (Co-L@RGO(1:1)/GCE) exhibited a low limit of detection (LOD) of 7.24 nM for CGA within the concentration of 0.1-2 µM and 2-20 µM. Co-L@RGO(1:1)/GCE also showed excellent selectivity, stability, and reproducibility for the CGA detection. Co-L@RGO(1:1)/GCE could detect the CGA in honeysuckle with satisfactory results. This work provided a great example for the thiacalix[4]arene-based MOF in the application of electrochemical sensors.

Electrochemical Detection of Flutamide by the Composite of Complex Based on Thiacalix[4]arene Derivatives and Reduced Graphene Oxide.

In this paper, a thiacalix[4]arene complex [Zn2(TIT4A)L2]·4DMF·2CH3OH (H2L = 4,4'-oxybisbenzoic acid) (Zn-TIT4A-L) was synthesized by a solvothermal method. The composites were prepared by combining Zn-TIT4A-L with reduced graphene oxide (RGO), mesoporous carbon (MC), and multi-walled carbon nanotubes (MWCNTs), respectively. Three representative composites are Zn-TIT4A-L@RGO(1:1), Zn-TIT4A-L@MC(1:2), and Zn-TIT4A-L@MWCNT(1:2). X-ray diffraction and scanning electron microscopy characterized their structures and morphologies. The results showed that three composites were successfully prepared, and the crystals of the complex remained in the composites. The electrochemical properties of the composites were characterized by electrochemical impedance spectroscopy and cyclic voltammetry. The results indicated that they had good electrocatalytic activity and conductivity. Among them, Zn-TIT4A-L@RGO(1:1) had the best performance and was used for the quantitative detection of flutamide (FTA). The linear range of detection is 0.1-200 µM, and the limit of detection is 0.015 µM. At the same time, the sensor also had good reproducibility, anti-interference, and stability. The sensor was also used for the detection of FTA in lake water, human urine, and serum with a satisfactory recovery rate. The possible mechanism of electrochemical detection of FTA was also discussed.

Efficient detection of metronidazole by a glassy carbon electrode modified with a composite of a cyclotriveratrylene-based metal-organic framework and multi-walled carbon nanotubes.

Constructing a sensitive and efficient sensor for determination of metronidazole (MNZ) is crucial in food field. Herein, a new cyclotriveratrylene-based metal-organic framework (MOF), namely, [Cd6L2(cyclen)2(H2O)2] (1), was constructed by self-assembly of functionalized 5,6,12,13,19,20-hexacarboxy-propoxy-cyclotriveratrylene (H6L), 1,4,7,10-tetraazacyclododecane (cyclen) and Cd(II) cation under solvothermal condition. In 1, adjacent Cd(II) cations are linked by L6- to produce a 2D polymeric structure with carboxylate and phenolic oxygen atoms. To enhance conductivity of 1, it was combined with conducting carbon materials, including mesoporous carbon (MC), reduced graphene oxide (RGO) and multi-walled carbon nanotubes (MWCNT), respectively, producing a series of composite materials. Remarkably, electrochemical tests showed that 1@MWCNT(1:1) featured a much better electrochemical detection performance for metronidazole (MNZ) than 1@MC and 1@RGO. The linear range for the detection of MNZ is up to 0.4-500 µM and the limit of detection (LOD) for MNZ reached 0.25 µM. Importantly, the fabricated sensor 1@MWCNT(1:1) was employed for the detection of MNZ in honey and egg with satisfactory result. High-performance liquid chromatography (HPLC) validated the high accuracy of the electrochemical method for the determination of honey and egg.

Thiacalix[4]arene-based complex with Co(II) ions as electrode modifier for simultaneous electrochemical determination of Cd(II), Pb(II), and Cu(II).

A complex [Co4(TCTA)2(H2O)8]∙10H2O (Co-TCTA) based on thiacalix[4]arene derivative has been synthesized for the first time using the solvothermal method. The glassy carbon electrode (GCE) modified with Co-TCTA (Co-TCTA/GCE) could simultaneously determine Cd2+, Pb2+, and Cu2+ at around - 0.75 V, - 0.60 V, and - 0.10 V (vs. ref. Ag/AgCl) and had good stability, selectivity, and reproducibility with relative standard deviation (RSD) of 4.4% for Cd2+, 1.4% for Pb2+, and 5.4% for Cu2+. Co-TCTA/GCE showed wide linear range of 0.4-8.0 µM for Cd2+, 0.4-7.0 µM for Pb2+, and 0.6-6.0 µM for Cu2+ when three ions were determined simultaneously. The limits of detection (LODs) of Cd2+, Pb2+, and Cu2+ were 0.071 µM, 0.022 µM, and 0.021 µM, respectively. Moreover, the sensor was used to determine three ions in lake water sample with satisfactory recoveries of 93.6-93.8% for Cd2+, 93.8-103.3% for Pb2+ and 94.6-95.3% for Cu2+. The good adsorption capacity of Co-TCTA and Co(II)/Co(0) circular mechanism on the surface of the electrode were proposed to enhance the electrochemical signals. This work enriched the theoretical research on the complexes for the determination of heavy metal ions.

Single-Component White Light Emission from a Metal-Coordinated Cyclotriveratrylene-Based Coordination Polymer.

A coordination polymer, namely, [Cd3L(H2O)3]·DMA·4H2O (1) (DMA = N,N-dimethylacetamide), was prepared by the solvothermal reaction of cyclotriveratrylene-based ligand 5,6,12,13,19,20-hexacarboxy-methoxy-cyclotriveratrylene (H6L) and Cd(NO3)2·4H2O. In 1, a two-dimensional structure was constructed by the connection of hexanuclear Cd-O clusters and L6- anions. Photoluminescence measurements indicated that 1 displayed tunable photoluminescence through the variation of the excitation wavelength. Significantly, the white light emission of 1 can be observed with a broad excitation wavelength range from 320 to 385 nm. When 1 is excited by 385 nm light, its chromatic coordinate is (0.29, 0.34), which is located very close to the pure white light region (0.33, 0.33). Meanwhile, the color temperature (CCT) is 7994 K, which corresponds well to "cold" white light.

Simultaneous electrochemical detection of gallic acid and uric acid with p-tert-butylcalix[4]arene-based coordination polymer/mesoporous carbon composite.

Design and synthesis of an efficient electrocatalyst for simultaneous determination of gallic acid (GA) and uric acid (UA) is vital in the biological field. Herein, we synthesized a new p-tert-butylcalix[4]arene-based metal-organic electrocatalyst (Mn-L@MC) by combining Mn-L (H4L = tetrakis[(2-biphenylcarboxyl)oxy]-p-tertbutylcalix[4]arene) and mesoporous carbon (MC) via a simple mechanical grinding method. Synergistic effect between Mn-L and MC made the Mn-L@MC composite behave high-efficiency electrocatalytic performance toward simultaneous detection of GA and UA. Under optimal experimental conditions, the Mn-L@MC-2 electrode material featured relatively wide linear range (0.5-90 µM) for the two analytes, and low determination limits of 0.043 µM for GA and 0.059 µM for UA. The remarkable electrochemical detection behavior of Mn-L@MC-2 electrode material toward GA and UA are comparable to those known sensors containing precious metals. The Mn-L@MC-2 material exhibited high selectivity, superior reproducibility, and acceptable stability during the determination of the two analytes. The sensor was assembled to simultaneously detect GA and UA in healthy human urine with satisfactory recoveries.

Angiotensin-converting enzyme polymorphisms AND Alzheimer's disease susceptibility: An updated meta-analysis.

BACKGROUND: Many studies among different ethnic populations suggested that angiotensin converting enzyme (ACE) gene polymorphisms were associated with susceptibility to Alzheimer's disease (AD). However, the results remained inconclusive. In the present meta-analysis, we aimed to clarify the effect of ACE polymorphisms on AD risk using all available relevant data. METHODS: Systemic literature searches were performed using PubMed, Embase, Alzgene and China National Knowledge Infrastructure (CNKI). Relevant data were abstracted according to predefined criteria. RESULTS: Totally, 82 independent cohorts from 65 studies were included, focusing on five candidate polymorphisms. For rs1799752 polymorphism, in overall analyses, the insertion (I) allele conferred increased risk to AD compared to the deletion (D) allele (I vs. D: OR = 1.091, 95% CI = 1.007-1.181, p = 0.032); while the I carriers showed increased AD susceptibility compared with the D homozygotes (II + ID vs. DD: OR = 1.131, 95% CI = 1.008-1.270, p = 0.036). However, none of the positive results passed FDR adjustment. In subgroup analysis restricted to late-onset individuals, the associations between rs1799752 polymorphism and AD risk were identified using allelic comparison (OR = 1.154, 95% CI = 1.028-1.295, p = 0.015, FDR = 0.020), homozygotes comparison, dominant model and recessive model (II vs. ID + DD: OR = 1.272, 95% CI = 1.120-1.444, p < 0.001, FDR < 0.001). Nevertheless, no significant association could be revealed after excluding studies not in accordance with Hardy-Weinberg equilibrium (HWE). In North Europeans, but not in East Asians, the I allele demonstrated increased AD susceptibility compared to the D allele (OR = 1.096, 95% CI = 1.021-1.178, p = 0.012, FDR = 0.039). After excluding HWE-deviated cohorts, significant associations were also revealed under homozygotes comparison, additive model (ID vs. DD: OR = 1.266, 95% CI = 1.045-1.534, p = 0.016, FDR = 0.024) and dominant model (II + ID vs. DD: OR = 1.197, 95% CI = 1.062-1.350, p = 0.003, FDR = 0.018) in North Europeans. With regard to rs1800764 polymorphism, significant associations were identified particularly in subgroup of European descent under allelic comparison (T vs. C: OR = 1.063, 95% CI = 1.008-1.120, p = 0.023, FDR = 0.046), additive model and dominant model (TT + TC vs. CC: OR = 1.116, 95% CI = 1.018-1.222, p = 0.019, FDR = 0.046). But after excluding studies not satisfying HWE, all these associations disappeared. No significant associations were detected for rs4343, rs4291 and rs4309 polymorphisms in any genetic model. CONCLUSIONS: Our results suggested the significant but modest associations between rs1799752 polymorphism and risk to AD in North Europeans. While rs4343, rs4291 and rs4309 polymorphisms are unlikely to be major factors in AD development in our research.

Two new calix[4]resorcinarene-based coordination cages adjusted by metal ions for the Knoevenagel condensation reaction.

Two new calix[4]resorcinarene-based coordination cages, namely, [Zn4(TPC4R)(PDC)4]·2DMF·6H2O (1-Zn) and [In11(TPC4R)2(PDC)16(µ2-OH)2(H2O)2]·[(CH3)2NH2]·8DMF·20H2O·EtOH (2-In), have been synthesized via solvothermal reactions (TPC4R = tetra(2-(4H-pyrazol-3-yl)pyridine)calix[4]resorcinarene, H2PDC = 3,5-pyridinedicarboxylic acid, DMF = N,N'-dimethylformamide). By carefully tuning different metal ions, two structurally different cages 1-Zn and 2-In were achieved. The former shows a bowl-shaped structure, while the latter features a dumbbell-like structure. After activation, they exhibited unsaturated Zn(ii) or In(iii) Lewis acid sites and the free nitrogen Lewis base sites of the PDC2-. Therefore, they were employed as catalysts for the Knoevenagel condensation reaction in the absence of a solvent. Particularly, 1-Zn featured high structural stability and enhanced the catalytic activity.

A Porous Metal-Organic Framework as an Electrochemical Sensing Platform for Highly Selective Adsorption and Detection of Bisphenols.

The design of artificial receptors with a specific recognition function and enhanced selectivity is highly desirable in the electrochemical sensing field, which can be used for detection of environmental pollutants. In this facet, metal-organic frameworks (MOFs) featured adjustable porosities and specific host-guest recognition properties. Especially, the large hydrophobic cavity formed in the porous MOFs may become a potential artificial receptor. We herein designed a new porous MOF [Zn2(L)(IPA)(H2O)]·2DMF·2MeOH·3H2O (Zn-L-IPA) by using a functionalized sulfonylcalix[4]arene (L1) and isophthalic acid (H2IPA) (DMF = N,N'-dimethylformamide). The specific pore size and pore shape of Zn-L-IPA made it efficiently selective for absorption of bisphenol A (BPA), bisphenol F (BPF), and bisphenol S (BPS). Therefore, a rapid, highly selective, and ultrasensitive electrochemical sensing platform Zn-L-IPA@GP/GCE was fabricated by using Zn-L-IPA as a host to recognize and absorb bisphenol guests (GP = graphite powder, GCE = glassy carbon electrode). Most strikingly, the extremely low detection limits were up to 3.46 and 0.17 nM for BPA and BPF, respectively, using the Zn-L-IPA@GP/GCE electrode. Furthermore, the "recognition and adsorption" mechanism was uncovered by density functional theory with the B3LYP function. This work offered a prospective strategy for selective absorption and detection of harmful bisphenols with the MOF-based porous material.

Macrocycle-Based Metal-Organic Frameworks with NO2-Driven On/Off Switch of Conductivity.

Conductive metal-organic frameworks (MOFs) have a wide range of applications in supercapacitors, electrocatalysts, and fuel cells, while gas-driven conductive MOFs have not yet been synthesized so far. Herein, we report a gas-driven conductive MOF (A) constructed from calix[4]resorcinarene macrocycle and Co(II) cations, which shows the conductivity enhancement by about eight orders of magnitude through NO2 adsorption. The conductivities of MOF A before and after the adsorption of NO2 were calculated to be about 1.3 × 10-11 and 8.4 × 10-4 S/cm, respectively. MOF A realizes the conversion from an insulator to a conductor by adsorbing NO2. When NO2 is evacuated, MOF A quickly changes from a conductor back to an insulator in 42 s. In the crystal structure of NO2-adsorbed MOF (termed as A-NO2), NO2 molecule connects Co(II) and uncoordinated carboxylate groups through hydrogen-bonding interactions to form a conductive pathway, greatly reducing the electron transmission distance between each two metal clusters. In addition, NO2 molecule and H3O+ may also form a conductive pathway by hydrogen-bonding interactions. This work presents an interesting macrocycle-based MOF with a NO2-driven on/off conductivity switch, proving the possibility for designing advanced gas-driven conductive systems.

Self-Assembly of Polyoxometalate-Resorcin[4]arene-Based Inorganic-Organic Complexes: Metal Ion Effects on the Electrochemical Performance of Lithium Ion Batteries.

With their adjustable structures and diverse functions, polyoxometalate (POM)-resorcin[4]arene-based inorganic-organic complexes are a kind of potential multifunctional material. They have potential applications for lithium ion batteries (LIBs). However, the relationship between different coordinated metal ions and electrochemical performance has rarely been investigated. Here, three functionalized POM-resorcin[4]arene-based inorganic-organic materials, [Co2 (TMR4 A)2 (H2 O)10 ][SiW12 O40 ]⋅2 EtOH⋅4.5 H2 O (1), [Ni2 (TMR4 A)2 (H2 O)10 ][SiW12 O40 ]⋅4 EtOH⋅13 H2 O (2), and [Zn2 (TMR4 A)2 (H2 O)10 ][SiW12 O40 ]⋅2 EtOH⋅2 H2 O (3), have been synthesized. Furthermore, to enhance the conductivities of these compounds, 1-3 were doped with reduced graphene oxide (RGO) to give composites 1@RGO-3@RGO, respectively. As anode materials for LIBs, 1@RGO-3@RGO can deliver very high discharge capacities (1445.9, 1285.0 and 1095.3 mAh g-1 , respectively) in the initial run, and show discharge capacities of 898, 665 and 651 mAh g-1 , respectively, at a current density of 0.1 A g-1 over 100 runs. More importantly, the discharge capacities of 319, 283 and 329 mAh g-1 were maintained for 1@RGO-3@RGO even after 400 cycles at large current density (1 A g-1 ).

Three Resorcin[4]arene-Based Two-Dimensional Zn(II) Supramolecular Isomers Synthesized via a Structure-Directing Strategy for Knoevenagel Condensation.

Herein, in the presence of three structure-directing agents (SDAs), a family of imidazole-functionalized resorcin[4]arene-based coordination polymers (CPs), [Zn(TIC4R)(HCOO)]·HCOO·0.5DMF·1.5H2O (1), [Zn(TIC4R)(CN)]·HCOO·DMF·2.5H2O (2), and [Zn(TIC4R)(H2O)]·2HCOO·2H2O (3), were assembled under solvothermal conditions [TIC4R = tetra(imidazole) resorcin[4]arene]. 1 exhibits a double-layer structure with rectangle windows, and 2 and 3 display monolayer structures. The layers of CPs 2 and 3 are slides with different offsets along the a-axis. In addition, three CPs were used as catalysts to catalyze Knoevenagel condensations. Strikingly, all CPs exhibit remarkable catalytic performance for several substrates. To the best of our knowledge, this is the first time that a small organic acid as SDA was used in the syntheses of resorcin[4]arene-based supramolecular isomers.

A copper(ii)-based porous metal-organic framework for the efficient and rapid capture of toxic oxo-anion pollutants from water.

The efficient and selective capture of toxic oxo-anions is highly desirable for environmental retrieval and hazardous waste disposal. This has remained an important task and gained considerable scientific attention due to their harmful effects on the ecosystem and human health. Herein, a porous cationic metal-organic framework (MOF), namely, [Cu3Cl(L)(H2O)2]·Cl·4DMA·8H2O (1), was synthesized (H4L = 1,4,8,11-tetrazacyclotetradecane-N,N',N'',N'''-tetramethylenecinnamic acid and DMA = N,N'-dimethylacetamide). 1 shows high stability in aqueous solution and represents an extraordinary example that is capable of efficiently capturing environmentally toxic Cr2O72- and MnO4- anions. Moreover, the removal of Cr2O72- and MnO4- anions from water was also explored in the presence of other competing anions.

Polyoxometalate-Templated Cobalt-Resorcin[4]arene Frameworks: Tunable Structure and Lithium-Ion Battery Performance.

By employing a bowl-like tetra(benzimidazole)resorcin[4]arene (TBR4A) ligand, two new polyoxometalate-templated metal-organic frameworks (POMOFs), [Co8Cl14(TBR4A)6]·3[H3.3SiW12O40]·10DMF·11EtOH·20H2O (1) and [Co3Cl2(TBR4A)2(DMF)4]·[SiW12O40]·2EtOH·3H2O (2), have been prepared under solvothermal conditions (DMF = N,N'-dimethylformamide). 1 shows a 2D cationic layer, whereas 2 exhibits a 3D framework. Remarkably, the Keggin POMs in 1 and 2 were located in the cavities formed by two bowl-like resorcin[4]arenes in sandwich fashions. Their framework structures were highly dependent on the coordination modes of the TBR4A ligands. To increase the conductivity of POMOFs, the samples of 1 and 2 were loaded on the conductive polypyrrole-reduced graphene oxide (PPy-RGO) via ball milling (1@PG and 2@PG). Then, the obtained composites experienced calcination at a proper temperature to produce 1@PG-A and 2@PG-A. The resulting 1@PG-A and 2@PG-A composites, with improved conductivities, uniform sizes and micropores, exhibited promising electrochemical performance for lithium-ion batteries. We herein proposed a size-controlled route for the rational fabrication of functional POMOFs and their usage in energy fields.

Assembly of polyoxometalate-thiacalix[4]arene-based inorganic-organic hybrids as efficient catalytic oxidation desulfurization catalysts.

Self-assembly of polyoxometalates, Ni(ii)/Ag(i) cations and tetra-[5-(mercapto)-1-methyltetrazole]-thiacalix[4]arene (L) yielded three inorganic-organic hybrids, namely, [Ni3L2(CH3OH)6(H2O)4][PMo12O40]2·3CH3OH·2H2O (1), [Ni3L2(CH3OH)6(H2O)4][PW12O40]2·3CH3OH·2H2O (2) and [Ag3L(PMo12O40)] (3). In hybrids (1) and (2), Ni(ii) cations are linked by L ligands to produce layered frameworks, and H bonds among the [PMo12O40]3-/[PW12O40]3- anions and L ligands lengthen the structures to form 3D supramolecular architectures. Hybrid (3) exhibits a 3D architecture, of which Ag(i) cations not only coordinated with the N and O atoms of L ligands and [PMo12O40]3- anions simultaneously, but also connected each other by Ag-Ag interactions. It is worth mentioning that 1 and 3 as recyclable catalysts show excellent heterogeneous catalytic activity in oxidation desulfurization reactions.

A Nanosized Propeller-like Polyoxometalate-linked Copper(I)-Resorcin[4]arene for Efficient Catalysis.

The design and assembly of polyoxometalate-resorcin[4]arene-based metal-organic molecular materials are particularly attractive for their elegant structures and potential functions. By applying a newly designed resorcin[4]arene ligand (TPC4R-II), a copper(I)-coordinated polyoxometalate-based metal-organic molecular material, namely, [CuI6(Br)3(TPC4R-II)3(PMo12O40)]·8H2O (1), was rationally assembled. Three copper(I)-coordinated resorcin[4]arenes are held together by a central [PMo12O40]3- to yield a supramolecular propeller. 1 features efficient catalytic performances for oxidation desulfurization (ODS) and azide-alkyne cycloaddition (AAC) reactions. This work affords a feasible method for the nanosized polyoxometalate-based metal-resorcin[4]arene assemblies by well combinating two types of large composites as well as low coordination metal cations.