Tetracycline (TC) as one kind of characteristic antibiotic has caused serious environment problems. In this study, a Mo(VI)-cluster containing iron-based metal-organic framework (MOF), [Fe(Mo4O13)(TPT)(2)] (FeMo-TPT, TPT = 2,4,6-tri(4-pyridyl)-1,3,5-triazine), was synthesized and applied in the photocatalytic degradation of TC. The existence of Fe(II) cations and Mo(VI)-clusters could enhance the visible light harvesting through reducing the band gap energy. The synergistic effect in the structure enhances the photodegradation of TC. Photochemical characterizations proved FeMo-TPT has strong ability of photoinduced electron and hole separation. In the confined space, the ordered electrons transport occurred between each component. Consequently, FeMo-TPT exists a 98.01 % degradation rate with oxygen as an oxidant under mild condition. A possible degradation way of TC was investigated by mass spectrometry. And the reactive oxygen species (ROS) capture tests and EPR results show that O-1(2) and O-2(center dot-) play the important role in TC degradation process. This work provides an efficient photocatalyst for water environment treatment under mild condition.

A photoactive metal-organic framework (MOF), [K(H2O)][Cu(DPNDI)][Cu(DPNDI)(CH3CN)(H2O)] [Cu1.5(DPNDI)1.5H1.5P2W18O62]·2H2O (Cu(Ι)W-DPNDI), was prepared by combining a functional photosensitizer N, N'-bis(4-pyridylmethyl)naphthalene diimide (DPNDI), copper(I) ions, and an oxidation catalyst [P2W18O62]6- into a single framework via a hydrothermal process. Cu(Ι)W-DPNDI exhibited a stable structure, strong light absorption capacity, a suitable band gap, and photoelectric properties, which provided favorable conditions for photocatalysis. In the confined space, the well-aligned Cu(I) ions and POM polyanions played a synergetic effect in the electron-transfer process and reactive oxygen species generation. By coupling photocatalysis and heterogeneous Fenton-like catalysis, Cu(Ι)W-DPNDI displayed high efficiency for the selective oxidation of aromatic alcohols, with up to >99% selectivity and 75% yield.

Realizing photo-promoted saturated C-H functionalization is a significant challenge. [CuI3(H2O)6(TPT)2][H2BW12O40]·28H2O was assembled by combining electron reservoir [BW12O40]5- with photosensitizer TPT. The continuous coordination bonds and π-π stacking interactions facilitate hole-electron separation and electron transfer, and allow it to exhibit high photocatalytic activity toward ethylbenzene oxidation with O2/H2O as oxidants.

A photoactive polyoxometalate-based metal−organic framework (POMOF), NiW-DPNDI, was synthesized by combination of Ni(II) ions, [ZnW12O40]6‒ anions, and N,N'-bis(4-pyridylmethyl)naphthalene diimide (DPNDI) molecules into one single framework. NiW-DPNDI displays a three-dimensional structure by the strong anion⋅⋅⋅π interactions between the trapped [ZnW12O40]6‒ anions and the electron-deficient naphthalenic ring centroids and the π−π stacking interactions between DPNDI moieties. NiW-DPNDI displayed a highly efficient hole-electron separation and ordered electron transfer under irradiation, thus ensuing its excellent photocatalysis in oxidation of styrene to produce benzaldehyde. In addition, it gave a high efficiency for styrene oxide under thermocatalytic conditions. Because the carbonic anhydrase (CA)-mimicking Ni sites and the negative electron-enriched [ZnW12O40]6‒ anions are well aligned in the pores, it can promote the cycloaddition of CO2 with epoxides under mild conditions.

Nanoclusters, with their ultrasmall sizes, have emerged as an indispensable tool in designing structural materials with a wide range of applications, but predicting the synthesis mechanism and structures remains challenging. This work delineates a synthesis mechanism of gold nanoclusters (AuNCs), which is realized by functionalizing a wool keratin (WK) and silk fibroin (SF) resilience network structure via self-assembly with controllable microstructure transformation. We synthesized such AuNCs by reducing the thiol groups of WK into WK@AuNCs and then entering the WF&SF resilience framework during the reconstruction, achieving WK@AuNCs/WK&SF with high fluorescence intensity for selective quenching of heavy metal Cu 2+ ions. Further investigation indicated that α-helix and β-crystallites resulted in a soft–hard molecular segment denoted as WK&SF resilience network, which held and separated the WK@AuNCs into the nanocages. Owing to the synergism of these features, WK@AuNCs/WK&SF displayed superior fluorescence performances compared with WK@AuNCs.

The ZnII MOF with proton-conductivity obtained an optimal conductivity of 1.38 × 10−3 S cm−1 (100 °C) under 2 M aquaammonia vapor.

A powerful and attractive route to develop novel photocatalysts for C-N bond formation involves the use of pyrrolidine as the substrate and cocatalyst simultaneously. Herein, a new polyoxometalate (POM)-based metal-organic framework, namely, [Ni6(OH)3(H2O)9(DPNDIH)(SiW9O34)]2·2H2O (SiW9Ni6-DPNDI) (DPNDI = N,N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide), was prepared by incorporating a Ni6 cluster-substituted POM anion and a photosensitizer (DPNDI) into a framework. The anion···π interactions and covalent bonds between SiW9Ni6 and DPNDI are beneficial for the consecutive electron separation and transfer. Under visible-light irradiation, DPNDI can be easily excited to generate radical species DPNDI* that could be further excited in the presence of the electron donor pyrrolidine for the inert O2 activation. SiW9Ni6-DPNDI showed a high efficiency in the photocatalysis of C-N bond formation under a mild condition by the synergy of DPNDI and SiW9Ni6. The results of the reaction were confirmed by gas chromatography and 1H NMR. In addition, SiW9Ni6-DPNDI exhibited a high sustainability without an obvious change in yields after five cycles.

The exploration of new highly efficient and durable for the oxidation of amines to imines has gained immense attention. In this work, a new polyoxometalate-based metal–organic framework (POMOF) {Cu4(C26H16N4O4)4(CH3CN)2[SiW12O40]}·4H2O (SiW-Cu-DPNDI) was constructed with a catalytic oxidant Keggin-type [SiW12O40]4− anion, a photosensitizer N,N'-bis(4-pyridylmethyl)naphthalene diimide (DPNDI) ligand, and a Cu(I) cation via self-assembling. Although single-crystal X-ray diffraction, power X-ray diffraction (PXRD), infrared (IR) spectroscopy, etc., were employed to confirm the hierarchical structure of SiW-Cu-DPNDI, critical analyses through, such as the magnetic susceptibility measurements, the Mott–Schottky measurements, and the electron spin resonance studies were successfully applied to elucidate the properties of POMOF. SiW-Cu-DPNDI was highly active in the heterogeneous photocatalysis of the oxidation of amines to imines under mild conditions. Additionally, this catalyst exhibited high stability and reusability without losing its activity during the photocatalysis. The possible mechanism of the oxidation coupling was extensively investigated under visible-light (Vis)-irradiation.

In this article, a new compound H-2[{Cu(HL)(H2O)}(2)(P2Mo5O23)]center dot 5H(2)O (1) (HL= 2-acetylpyrazine thiosemicarbazone) has been synthesized and structurally characterized by single-crystal X-ray diffraction of and other detection techniques. Interestingly, the structure of 1 is different from many reported copper-based complexes, in which the [P2Mo5O23](6-), two Cu2+ ions and two HL were directly connected by covalent bands. Biological studies demonstrated that 1 indicated moderate antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), and a better cytotoxicity against human hepatic cancer line (SMMC-7721) than Mitoxantrone (Mito), the current clinical anticancer drug. Besides, the antibacterial mechanisms of 1 have been studied by the membrane integrity disruption, the destructive reactive oxygen species generation (ROS), the glutathione (GSH) depletion and the depressed enzymatic activity of respiratory chain dehydrogenases (RCD). These results revealed that the combination of HL, Cu2+, [P2Mo5O23](6-) shows a higher antibacterial and cytotoxic activity.

A new hexatungstate compound, [Ni-2(L)(3)](2)[W6O19]center dot 2H(2)O (1) (HL = 2-acetylpyrazine-N(4)-methyl thiosemicarbazone) has been synthesized and characterized by elemental analyses, infrared (IR) spectroscopy, thermal gravimetric analysis (TGA), powder X-ray diffraction (PXRD), single-crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and UV-Vis spectra. A 3D supramolecular structure of 1 is formed by hydrogen bonding, which exhibits a highly selective adsorption for methylene blue (MB), gentian violet (GV) and fuchsin basic (FB) organic dyes with the efficiencies of 99%, 94% and 94%, respectively. Additionally, the adsorption kinetics demonstrates that the MB removal corresponds to the pseudo-second-order model. The recyclability experiments illustrated that 1 could be reused at least five cycles, revealing a potential ability in the disposal to dye wastewater. (C) 2020 Elsevier B.V. All rights reserved.

Consecutive photoinduced electron transfer (ConPET) has advantages on overcoming the current energetic limitation of visible-light photoredox catalysis for utilizing the energies of two photons in one catalytic cycle. A heterogeneous approach for radical chain reduction of various aryl bromides and chlorides without adding any cocatalyst is introduced by incorporating polyoxometalates (POMs) and amine catalysts into a naphthalenediimide (NDI)-based polymer. CoW-DPNDI-PYI exhibits high activity in the photocatalytic reduction of aryl halides by the synergistic effects of ConPET and hydrogen-atom-transfer (HAT) processes and an enzyme-mimicking CO2 cycloaddition reaction. The ConPET process with N,N'-bis(4-pyridylmethyl)naphthalenediimide (DPNDI) facilitates effective solar energy conversion. POMs and amine catalysts, as efficient HAT catalysts and electron donors, improve the generation of the ConPET process. The success of this work demonstrates the great application of the synergistic effects of ConPET and HAT processes in heterogeneous photocatalysis C-H arylation.

It is a challenge to develop new photocatalysts for high selective oxidation of primary carbon-hydrogen (C-H) bonds with O-2 under mild condition. Herein, a novel hybrid K-6(H2O)(8)H-24(C26H16N4O4)(8) [P6W48Fe6O180]center dot 6H(2)O (FeW-DPNDI) was firstly synthesized by incorporating a rare Fe-substituted trimeric Dawson derivative and photosensitizer N,N'-bis(4-pyridylmethyl)naphthalene diimide (DPNDI) via solvothermal method. In FeW-DPNDI, [P6W48Fe6O180](30)- and DPNDI are orderly arranged in the three-dimensional framework by the anion center dot center dot center dot p interaction and C-H center dot center dot center dot O hydrogen bonds, that is beneficial to promote the electron transfer among components. FeW-DPNDI is a typical n-type semiconductor with the calculated energy level at 2.22 V vs. NHE of the highest occupied molecular orbital (HOMO) and -0.57 vs. NHE of the lowest unoccupied molecular orbital (LUMO), which is theoretically feasible for the reduction O-2 to O-2(center dot-) because of the more negative potential of CB than the standard redox potential (E(O-2(center dot-)/O-2) = - 0.33 V vs. NHE). The proton conductivity of FeW-DPNDI is 2.0 x 10(-4) S cm(-1) at 98% relative humidity and 358 K. FeW-DPNDI exhibits special selectivity for generating benzaldehyde in the photocatalytic oxidation of stubborn C-H bond of toluene under mild condition. Moreover, FeW-DPNDI can be easily isolated from the products and reused. FeW-DPNDI is the first example of the trimmer of Fe-substituted Dawson derivative, but also the first hybrid POM explored in the activating C-H bond of toluene under white light irradiation. (C) 2020 Elsevier Inc. All rights reserved.

Two inorganic-organic hybrid materials, [Co(L)(2)](2)Na-2[beta-Mo8O26]center dot 9H(2)O (1) and [Fe(L)(2)](2)Na-2[beta-Mo8O26]center dot 9H(2)O (2) (HL = 2-acetylpyrazine N-4-methyl thiosemicarbazone) have been synthesized and characterized by elemental analyses, infrared (IR) spectroscopy, thermal gravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The hybrids 1 and 2 were explored in the oximation of aldehydes and ketones with in situ generated hydroxylamine by a one-pot procedure. In the crystal structures of 1 and 2, N-containing thiosemicarbazide ligands, Lewis acid, and oxidation catalyst octamolybdate coexist within a confined space providing a promising synergistic catalytic way. Hybrids 1 and 2 displayed high catalytic activity and selectivity for the oximation of aldehydes and ketones.

Currently, the efficient preparation of imines is still a great challenge under mild conditions. In this article, by incorporating 2-acetylpyridine thiosemicarbazone (HL), Co(NO3)2·6H2O and Na2MoO4·2H2O, a new compound [Co(L)2]2[Mo6O19] (1) was prepared and characterized by elemental analysis (EA), infrared (IR) spectra, ultraviolet–visible (UV–Vis) spectra, powder X-ray diffractometry (PXRD) spectra, X-ray photoelectron spectroscopy (XPS) and X-ray single-crystal diffraction. 1 could be used as a heterogeneous catalyst for oxidative coupling of amines in a comparatively mild condition. Furthermore, 1 exhibited remarkable catalytic performance for oxidation coupling of amines to imines with high yield in the presence of tert-butyl hydroperoxide (TBHP) (up to 92%). Kinetic measurements of the oxidation of benzylamine suggest that the rate law is r = k′[BnNH2][TBHP] (k′ = k[cat] = 0.2338 L mol−1 h−1). Additionally, 1 can be recycled at least three times without a distinct loss of activity. A new compound [Co(L)2]2[Mo6O19] (1) (HL = 2-acetylpyridine thiosemicarbazone) has been synthesized and characterized. Furthermore, 1 can efficiently catalyze the oxidative coupling of amines to imines with high activity and exhibited good recyclability and high stability.

The reaction of the lacunary polyoxotungstate [B-alpha-BiW9O33](9-) with Cu(Ac)(2)center dot H2O in the presence of diethylenetriamine under hydrothermal conditions generating a new 2-D layer-like organic-inorganic hybrid tungstobismuthate [cu(dien)(H2O)](2)[Cu-2(dien)(2)](2)H-2[Bi2W20O70] center dot 15H(2)O (1) (dien = diethylenetriamine). 1 has been carefully characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), X-ray single-crystal diffraction. 1 crystallizes in the orthorhombic Pbca space group with a= 21.077(2) angstrom, b = 21.788(2) angstrom, c= 22.821(2 ) angstrom, V= 10480.1(17) angstrom(3), Z=4, GOOF= 1.043, R-1= 0.0454, wR(2)= 0.0710. Structural analyses show that 1 exhibits an organic-inorganic hybrid 2-D layer-like architecture constructed by [Bi2W20O70](14-) polyanions by means of the [Cu-2(dien)(2)](4+) bridges. Notably, the dien ligand presents two kinds of coordination modes in 1, which has been rarely observed in previously reported polyoxometalates. The magnetic study of 1 demonstrates the existence of ferromagnetic coupling interactions between Cu2+ ions in dimeric [Cu-2(dien)(2)](4+) groups. (C) 2018 Elsevier B.V. All rights reserved.

Developing new photocatalysts for settling the tightest bottlenecks that lower efficiency, inferior selectivity and harsh conditions in organic oxidation reactions with air is very significant. Herein, ZnW-DPNDI-PYI was achieved by assembling a functional photosensitizer, an oxidation catalyst [BW(12)O40](5-), and an organocatalyst into one single framework. The anion center dot center dot center dot pi and N-H center dot center dot center dot O hydrogen bonds interactions facilitate the consecutive photo-induced electron transfer (conPET) process for the photocatalytic oxidation by stabilizing the radical-anion intermediate and catalyst-substrate interacted moiety. Besides, N,N'-bis(4-pyridylmethyl)naphthalene diimide (DPNDI) can be excited by visible light, the photogenerated electron and hole would further activate oxygen and substrates, respectively, to give the corresponding redox products. High conversion and selectivity of ZnW-DPNDI-PYI in photocatalytic coupling of primary amines and olefins epoxidation with air under visible-light have been demonstrated. (C) 2019 Elsevier Inc. All rights reserved.

The magnetic adsorbent, Fe3O4@[Ni(HL)2]2H2[P2Mo5O23]·2H2O (Fe3O4@1), is synthesized by employing the nanoparticles Fe3O4 and polyoxometalate hybrid 1. Zero-field-cooled (ZFC) and field-cooled (FC) curves show that the blocking temperature of Fe3O4@1 was at 120 K. Studies of Fe3O4@1 removing cationic and anionic dyes from water have been explored. The characterization of Fe3O4@1, effects of critical factors such as dosage, the concentration of methylene blue (MB), pH, adsorption kinetics, isotherm, the removal selectivity of substrate and the reusability of Fe3O4@1 were assessed. The magnetic adsorbent displayed an outstanding removal activity for the cationic dye at a broad range of pH. The adsorption kinetics and isotherm models revealed that the adsorption process of Fe3O4@1 was mainly governed via chemisorption. The maximum capacity of Fe3O4@1 adsorbing substance was 41.91 mg g−1. Furthermore, Fe3O4@1 showed its high stability by remaining for seven runs of the adsorption-desorption process with an effective MB removal rate, and could also be developed as a valuable adsorbent for dyes elimination from aqueous system.

信息化时代,大量的数据处理、数据操作、数据再加工是生产、工作中必不可少的一项基本任务,提高大量数据处理的自动化程度,有助于提高社会生产力.在计算理论中,确定有限状态自动机(deterministic finite automation,DFA)是一个能实现状态转移的自动机,它能根据事先给定的转移函数自动转移到下一个状态,而笛卡尔集(Cartesian Set)定义了两个集合的操作集.文中基于确定有限状态自动机(DFA)理论和笛卡尔集构建了一种数据自动处理机器人模型,并以财政支付数据自动录入为切入点,设计和实现了财政支付数据录入机器人.通过这种机器人,2个员工一天的录入工作量,可以用1个小时来完成,极大提高了工作效率;同时,人工录入的准确率很难达到100％,而数据自动录入机器人可以达到无差错录入.

Developing efficient photocatalysts for direct oxidative coupling of alkenes and amines with O2 under mild conditions is very significant. Herein, ZnW-PYI is well-designed by assembling a [PZnW11O39(H2O)]5- photooxidation catalyst and chiral aminocatalyst pyrrolidine-2-ylimidazole (PYI) via a coordination model. ZnW-PYI efficiently catalyzed the synthesis of imines from alkenes and amines using O2 as the oxidant through nucleophilic catalysis by employing pyrrolidine as an organocatalyst. Combining a polyoxometalate and PYI within one single framework is an effective approach not only for stabilization and heterogenization of the redox-active catalyst and aminocatalyst but also for realization of compatibility between the reaction intermediates and synergy of multiple catalytic cycles.

In this work, two magnetic adsorbents Fe3O4@1 and Fe3O4@2 were prepared by combining Fe3O4 nanoparticles and polyoxometalate hybrids [Ni(HL)2]2H2[P2Mo5O23]·4H2O (1), [H2L]5H[P2Mo5O23]·12H2O (2) (HL = 2-acetylpyridine-thiosemicarbazone). The temperature-dependent zero-field-cooled (ZFC) and field-cooled (FC) measurements indicated the blocking temperature at 160 K and 180 K, respectively. The Brunauer–Emmett–Teller (BET) surface area of Fe3O4@1 and Fe3O4@2 is 8.106 m2/g and 1.787 m2/g, respectively. Cationic dye methylene blue (MB) and anionic dye methyl orange (MO) were investigated for selective dye adsorption on Fe3O4@1 and Fe3O4@2. The two adsorbents were beneficial for selective adsorption of cationic dyes. The adsorption efficiency of MB was 94.8% for Fe3O4@1, 97.67% for Fe3O4@2. Furthermore, the two adsorbents almost maintained the same adsorption efficiency after seven runs. The maximum MB adsorption capacity of Fe3O4@1 and Fe3O4@2 is 72.07 and 73.25 mg/g, respectively. The fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) spectra of the adsorbents collected after adsorption of MB are very similar to the initial as-synthesized Fe3O4@polyoxometalates indicating the high stability of the two adsorbents. The adsorption kinetics indicated that the MB removal followed the pseudo-second-order model. These results showed that the two adsorbents had a potential application in treating wastewater.