Investigation into a hydrothermal reaction system with transition‐metal (TM) ions, 1,4‐bis(1,2,4‐triazol‐1‐lmethyl)benzene (BBTZ) and various charge‐tunable Keggin‐type polyoxometalates (POMs) led to the preparation of four new entangled coordination networks, [CoII(HBBTZ)(BBTZ)2.5][PMo12O40] ( 1 ), [CuI(BBTZ)]5[BW12O40] ? H2O ( 2 ), [CuII(BBTZ)]3[AsWV3WVI9O40] ? 10 H2O ( 3 ), and [CuII5(BBTZ)7(H2O)6][P2W22Cu2O77(OH)2] ? 6 H2O ( 4 ). All compounds were characterized by using elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The mixed valence of W centers in compound 3 was further confirmed by using XPS spectroscopy and bond‐valence sum calculations. In the structural analysis, the entangled networks of 1 – 4 demonstrate zipper‐closing packing, 3D polythreading, 3D polycatenation, and 3D self‐penetration, respectively. Moreover, with the enhancement of POM negative charges and the use of different TM types, the number of nodes in the coordination networks of 1 – 4 increased and the basic metal–organic building motifs changed from a 1D zipper‐type chain (in 1 ) to a 2D pseudorotaxane layer (in 2 ) to a 3D diamond‐like framework (in 3 ) and finally to a 3D self‐penetrating framework (in 4 ). The photocatalytic properties of compounds 1 – 4 for the degradation of methylene blue under UV light were also investigated; all compounds showed good catalytic activity and the photocatalytic activity order of Keggin‐type species was initially found to be {XMo12O40}>{XW12O40}>{XW12?nTMnO40}. 相似文献
A highly sensitive method for the determination of manganese (VII), chromium (VI) and nickel (II) in medicinal herb samples is proposed. The method is based on analytes reacted with ammonium pyrrolidinedithiocarbamate (APDC) to give hydrophobic chelates (M–APDC), which were separated and enriched by cloud-point extraction (CPE) with non-ionic surfactant Tergitol TMN-6 as extractant. The surfactant-rich phase containing the chelates is determined with a high-performance liquid chromatography system. To achieve the best CPE method, the Box–Behnken design was used to study the concentration of Tergitol TMN-6, equilibrium temperature, equilibrium time as well as their interaction. What followed was the individual research for the pH of the sample solutions and the concentration of APDC. What is more, in the given optimized experimental conditions, calibration plots were found to be linear in the range of 0.0200–0.500 mg/L for Mn (VII) and Cr (VI), meanwhile 0.0500–1.00 mg/L for Ni (II), the linear correlation coefficients were between 0.996 and 0.999, the recoveries ranged from 91.8 to 97.8 % and the relative standard deviations were between 1.09 and 2.30 % (n = 3). The limits of detection were 0.164 μg/L for Mn (VII), 0.562 μg/L for Cr (VI) and 5.12 μg/L for Ni (II), respectively. The proposed method was applied to determine manganese (VII), chromium (VI) and nickel (II) in medicinal herb samples with satisfactory results. 相似文献
The title compounds, bis{μ‐N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine‐κ2N1:P}disilver bis(perchlorate) acetonitrile monosolvate, [Ag2(C18H17N2P)2](ClO4)2·CH3CN, (1), and bis{μ‐N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine‐κ2N1:P}bis[(nitrato‐κ2O,O)silver], [Ag2(C18H17N2P)2(NO3)2], (2), each contain disilver macrocyclic [Ag2(C18H17N2P)2]2+ cations lying about inversion centres. The cations are constructed by two N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine (DPP) ligands linking two Ag+ cations in a head‐to‐tail fashion. In (1), the unique Ag+ cation has a near‐linear coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands. Two ClO4− anions doubly bridge two metallomacrocycles through Ag...O and N—H...O weak interactions to form a chain extending in the c direction. The half‐occupancy acetonitrile molecule lies with its methyl C atom on a twofold axis and makes a weak N...Ag contact. In (2), there are two independent [Ag(C18H17N2P)]+ cations. The nitrate anions weakly chelate to each Ag+ cation, leading to each Ag+ cation having a distorted tetrahedral coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands, and two chelating nitrate O atoms. Each dinuclear [Ag2(C18H17N2P)2(NO3)2] molecule acts as a four‐node to bridge four adjacent equivalent molecules through N—H...O interactions, forming a two‐dimensional sheet parallel to the bc plane. Each sheet contains dinuclear molecules involving just Ag1 or Ag2 and these two types of sheet are stacked in an alternating fashion. The sheets containing Ag1 all lie near x = , , etc, while those containing Ag2 all lie near x = 0, 1, 2 etc. Thus, the two independent sheets are arranged in an alternating sequence at x = 0, , 1, etc. These two different supramolecular structures result from the different geometric conformations of the templating anions which direct the self‐assembly of the cations and anions. 相似文献
A hypercrosslinked conjugated microporous polymer (HCMP‐1) with a robustly efficient absorption and highly specific sensitivity to mercury ions (Hg2+) is synthesized in a one‐step Friedel–Crafts alkylation of cost‐effective 2,4,6‐trichloro‐1,3,5‐triazine and dibenzofuran in 1,2‐dichloroethane. HCMP‐1 has a moderate Brunauer–Emmett–Teller specific surface (432 m2 g−1), but it displays a high adsorption affinity (604 mg g−1) and excellent trace efficiency for Hg2+. The π–π* electronic transition among the aromatic heterocyclic rings endows HCMP‐1 a strong fluorescent property and the fluorescence is obviously weakened after Hg2+ uptake, which makes the hypercrosslinked conjugated microporous polymer a promising fluorescent probe for Hg2+ detection, owning a super‐high sensitivity (detection limit 5 × 10−8 mol L−1).
Polymer network gel method combines the advantages of solid-phase method and liquid phase method, triggering acrylamide (AM) radical polymerization in aqueous solution and N, N′- methylene bis acrylamide (MBAM) active double bond cross-linking reaction, forming polymer chains to form a three-dimensional network. The polymer network space formed by the gel is bound and evenly distributed to the ions in the solution, thereby reducing the contact and aggregation of molecules and achieving the purpose of uniform particle size and small particle size. The principle diagram of network gel is shown in Figure. Using cubic zinc acetate and ammonium molybdate tetrahydrate as raw materials, cubic ZnMoO4 negative electrode materials were prepared with polymer network gel method. The polymer network gel method has various effects on the structure, morphology and electrochemical properties of materials. Besides, the calcination temperature and calcination time were also the key factors to the electrochemical properties of the materials. In this paper, the effects of the ratio of monomer and crosslinker, calcination temperature and calcination time on ZnMoO4 materials were studied by single variable method, the preparation process was optimized, and its characterization and electrochemical tests were carried out. After 100 cycles, the optimized ZnMoO4 electrode has a discharge capacity of 374.0 mAh· g?1, 332.5, 263.5 and 177.1 mAh · g?1 at current densities of 0.1, 0.5, 1.0 and 2.0 A g?1, respectively. The electrochemical results show that the optimized ZnMoO4 has high capacity, large rate capability and excellent cycle stability. 相似文献
Journal of Radioanalytical and Nuclear Chemistry - In this study, the imidazole-based poly(ionic liquid)s (PILs) synthesized by one step method has been applied for the enrichment and recovery of... 相似文献
Stereocomplex (SC) crystallization has been an effective way to improve the physical performances of stereoregular polymers. However, the competition between homo and SC crystallizations can lead to more complicated crystallization kinetics and polymorphic crystalline structure in stereocomplexable polymers, which influences the physical properties of obtained materials. Herein, we select the medium-molecular-weight (MMW) poly(L-lactic acid)/poly(D-lactic acid) (PLLA/PDLA) asymmetric blends with different PDLA fractions (fD=0.01–0.5) as the model system and investigate the effects of fD and crystallization temperature (Tc) on the crystallization kinetics and polymorphic crystalline structure. We observe the fractionated (i.e., multistep) crystallization kinetics and the formation of peculiar β-form homocrystals (HCs) in the asymmetric blends under quiescent conditions, which are strongly influenced by both fD and Tc. Precisely, crystallization of β-form HCs is favorable in the MMW PLLA/PDLA blends with high fD (≥0.2) at a low Tc (80–100 °C). It is proposed that the formation of metastable β-form HCs is attributed to the conformational matching between β-form HCs and SCs, and the stronger constrain effects of precedingly-formed SCs in the early stage of crystallization. Such effects can also cause the multistep crystallization kinetics of MMW PLLA/PDLA asymmetric blends in the heating process.
Quaternary ammonium compounds (QACs) have outstanding antimicrobial effect, but covalent immobilization of plentiful QAC onto cotton fiber surface to realize a durable function remains a challenge. Herein, a quaternary ammonium monomer, [2-(methacryloyloxy) ethyl] trimethylammonium chloride (DMC) was co-polymerized with methyl acrylate (MA) to prepare an antibacterial copolymer, poly(DMC-co-MA). To graft the copolymer with an improved grafting efficiency, cotton fabric was treated using carboxymethyl chitosan (CMC) to establish an amino-functionalized fiber surface first. This treatment allows the amidation reactions between the amino groups and the pendant ester groups in the poly(DMC-co-MA) to take place, achieving a durable anionic polymer coating onto the fiber surfaces with remarkably antibacterial effect. Characterization results indicated that when DMC/MA monomer ratio was 100:1, the resulting copolymer endows the modified cotton fabric with antibacterial capability that inactivates all Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Even after 50 laundering cycles, more than 98.0% of the antibacterial rate could still be retained. Moreover, the wearing comfort properties such as softness, water absorption and air permeability of the finishing cotton fabrics have been insignificantly changed by comparing to the untreated cotton fabric.
