固态光聚合反应研究进展

光引发的固态聚合反应一直是令人感兴趣的研究领域.本文综述了固态光聚合的研究进展.着重介绍了双炔类体系,二烯类体系以及(甲基)丙烯酸酯体系的固态光聚合的研究工作以及应用前景.     

Synthesis,structure and property of diorganotin N‐[(3‐methoxy‐2‐oxyphenyl)methylene]tyrosinates

Five new diorganotin N‐[(3‐methoxy‐2‐oxyphenyl)methylene] tyrosinates, R₂Sn[2‐O‐3‐MeOC₆H₃CH=NCH (CH₂C₆H₄OH‐4)COO] (R = Me, 1 ; Et, 2 ; Bu, 3 ; Cy, 4 ; Ph, 5 ), have been synthesized and characterized by elemental analysis, IR, NMR (¹H, ¹³C and ¹¹⁹Sn) spectra, and the X‐ray single crystal diffraction. In non‐coordinated solvent, complexes 1 – 5 have penta‐coordinated tin atom. In the solid state, 1 – 3 are centrosymmetric dimmers in which each tin atom is seven‐coordinated in a distorted pentagonal bipyramid, and 4 displays discrete molecular structure with distorted trigonal bipyramidal geometry, and the tin atom of 5 is hexa‐coordinated and possess the distorted octahedral geometry with a coordinational methanol molecule. The intermolecular O‐H???O hydrogen bonds in 1 – 4 link molecules into the different one‐dimensional supramolecular chain with R₂² (30) or R₂² (20) macrocycles, and the molecules of 5 are joined into a two‐dimensional supramolecular network containing R₄⁴ (24) and R₄⁴ (28) two macrocycles. Bioassay results against human tumour cell HeLa indicated that 3 ‐ 5 belonged to the efficient cytostatic agents and the activity decreased in the order 4 > 3 > 5 > 2 > 1. The fluorescence determinations show the complexes may be explored for potential luminescent materials.     

Synthesis,crystal structure and antifungal activity of a divalent cobalt(II) complex with uniconazole

Azole compounds have attracted commercial interest due to their high bactericidal and plant‐growth‐regulating activities. Uniconazole [or 1‐(4‐chlorophenyl)‐4,4‐dimethyl‐2‐(1H‐1,2,4‐triazol‐1‐yl)pent‐1‐en‐3‐ol] is a highly active 1,2,4‐triazole fungicide and plant‐growth regulator with low toxicity. The pharmacological and toxicological properties of many drugs are modified by the formation of their metal complexes. Therefore, there is much interest in exploiting the coordination chemistry of triazole pesticides and their potential application in agriculture. However, reports of complexes of uniconazole are rare. A new cobalt(II) complex of uniconazole, namely dichloridotetrakis[1‐(4‐chlorophenyl)‐4,4‐dimethyl‐2‐(1H‐1,2,4‐triazol‐1‐yl‐κN⁴)pent‐1‐en‐3‐ol]cobalt(II), [CoCl₂(C₁₅H₁₈ClN₃O)₄], was synthesized and structurally characterized by element analysis, IR spectrometry and X‐ray single‐crystal diffraction. The crystal structural analysis shows that the Co^II atom is located on the inversion centre and is coordinated by four uniconazole and two chloride ligands, forming a distorted octahedral geometry. The hydroxy groups of an uniconazole ligands of adjacent molecules form hydrogen bonds with the axial chloride ligands, resulting in one‐dimensional chains parallel to the a axis. The complex was analysed for its antifungal activity by the mycelial growth rate method. It was revealed that the antifungal effect of the title complex is more pronounced than the effect of fungicide uniconazole for Botryosphaeria ribis, Wheat gibberellic and Grape anthracnose.     

Cobalt‐based metal coordination polymers with 4,4′‐bipyridinyl groups: highly efficient catalysis for one‐pot synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones under solvent‐free conditions

Three new metal coordination complexes, namely [Co(BPY)₂(H₂O)₂](BPY)(BS)₂(H₂O)₄ ( 1 ), [Co(BPY)₂(H₂O)₄](ABS)₂(H₂O)₂ ( 2 ) and [Co(BPY)(H₂O)₄](MBS)₂ ( 3 ) (BPY = 4,4′‐bipyridine, BS = phenylsulfonic acid, ABS = p‐aminobenzenesulfonic acid, MBS = p‐methylbenzenesulfonic acid), were obtained under hydrothermal conditions. Complexes 1 , 2 , 3 were structurally characterized using single‐crystal X‐ray diffraction and infrared spectroscopy. All of them display low‐dimensional motifs: complex 1 displays a two‐dimensional structure; and complexes 2 and 3 exhibit a one‐dimensional tape structure. Through strong intermolecular hydrogen bonding interactions and weak packing interactions, all of them further stack to generate a three‐dimensional supramolecular architecture. Catalysts 1 , 2 , 3 were involved in the green synthesis of a variety of 3,4‐dihydropyrimidin‐2(1H)‐ones under solvent‐free conditions through Biginelli reactions. The corresponding catalytic product was obtained in quantitative yields (99%) under eco‐friendly synthesis conditions for the variety of reactions. Catalysts 1 , 2 , 3 exhibit excellent efficiency for the desired product, and their catalytic performance shows the following order: 2  >  1  ≈  3 , which can be ascribed to the hydrophobic interactions of different phenylsulfonate groups. The catalytic performance for the Biginelli reaction is not only dependent on the selected solvents, but also inversely proportional to the polarities of the solvents. Copyright © 2016 John Wiley & Sons, Ltd.     

Acetate anion-selective encapsulation in the ellipsoidal cavity of symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril

Four symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril-based compounds have been prepared and characterised by X-ray crystallography. Their crystal structures displayed the acetate anion-selective encapsulating capability of symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril. The host–guest interaction between the symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril and the acetate anion in aqueous solution has also been observed by variable temperature ¹H NMR spectroscopy.     

Electrochemical Aptasensor for Zearalenone Based on DNA Assembly and Exonuclease III as Amplification Strategy

A sensitively electrochemical aptasensor was developed to detect zearalenone, utilizing DNA assembly based on hybridization chain reaction to amplify the signal current and exonuclease III to reduce the background current. The linear range 5.0×10⁻⁵ ng/mL-50 ng/mL, and the limit of detection is 0.013 pg/mL. The fabricated aptasensor showed the high specificity toward aflatoxin B1 (AFB1), fumonisin B1 (FB1) and ochratoxin A (OTA), good repeatability and reproducibility. In addition, the average recoveries of spiked corn and beer samples were in the range of 89 % to 102 %. The established method is of great significance in the field of food safety detection.     

PtM/MxBy (M=Ni,Co, Fe) Heterostructured Nanobundles as Advanced Electrocatalyst for Hydrogen Evolution Reaction

Optimizing the electronic and synergistic effect of hybrid electrocatalysts based on Pt and Pt-based nanocatalysts is of tremendous importance towards a superior hydrogen evolution performance under both acidic and alkaline conditions. However, developing an ideal Pt-based hydrogen evolution reaction (HER) electrocatalyst with moderated electronic structure as well as strong synergistic effect is still a challenge. Herein, we fabricated boron (B)-doped PtNi nanobundles by a two-step method using NaBH₄ as the boron source to obtain PtNi/Ni₄B₃ heterostructures with well-defined nanointerfaces between PtNi and Ni₄B₃, achieving an enhanced catalytic HER performance. Especially, the PtNi/Ni₄B₃ nanobundles (PtNi/Ni₄B₃ NBs) can deliver a current density of 10 mA cm⁻² at the overpotential of 14.6 and 26.5 mV under alkaline and acidic media, respectively, as well as outstanding electrochemical stability over 40 h at the current density of 10 mA cm⁻². Remarkably, this approach is also universal for the syntheses of PtCo/Co₃B and PtFe/Fe₄₉B with outstanding electrocatalytic HER performance.     

Analytical layer-element solutions of Biot’s consolidation with anisotropic permeability and incompressible fluid and solid constituents

Based on the governing equations of 2D plane-strain Biot’s consolidation, the relationship between generalized displacements and stresses of a single soil layer with anisotropic permeability and incompressible fluid and solid constituents is described by an analytical layer-element, which is deduced in the Laplace–Fourier transform domain by using the eigenvalue approach. Taking the boundary conditions and the continuity of the soil layers into consideration, a global stiffness matrix is subsequently assembled and solved. As to the 3D case, the same derivation is employed after the application of a decoupling transformation. The actual solutions in the physical domain can further be acquired by inverting the Laplace–Fourier transform. Finally, numerical examples are carried out to verify the presented theory and discuss the influence of the anisotropic permeability on the consolidation behavior.