Synthesis of structurally diverse diarylketones through the diarylmethyl sp CH oxidation

Under open-flask conditions, an efficient method to assemble a series of diversely functionalized diarylketones in the presence of commercially available NBS has been developed. Yields of up to 99% have been achieved employing diarylmethanes as starting material. Based on ¹⁸O-labeled experiment, the addition of stoichiometric water eventually leads to excellent yields in all carbonylation cases.     

硫代多联吡啶铂(Ⅱ)配合物的合成、性质及在光催化制氢中的应用

合成了2个新配体4-(4-硫代乙酸)甲苯基-6-苯基-2,2’-联吡啶HC^N^N(PhCH2SCOCH3)(L3)和6-(4-硫代乙酸)甲苯基-2,2’-联吡啶HC^N^N(CH2SCOCH3)(L5)及其发光的铂(Ⅱ)配合物ClPtC^N^N(PhCH2SCOCH3)(C3)和ClPtC^N^N(CH2SCOCH3)(C5).通过1H NMR谱和质谱对它们的结构进行了表征,采用X射线单晶衍射分析确定了C3的晶体结构.利用紫外-可见吸收光谱、发射光谱及激发态寿命测定研究了它们的光物理性质和电化学性质,以及配合物作为光敏剂在光催化制氢中的应用.通过系列配合物产氢效率的比较,揭示了它们的产氢效率和激发态寿命的关系.     

利用无标记的分子信标及核酸染料SYBR Green Ⅰ检测乙肝病毒

本文以野生型的乙型肝炎病毒(HBV)核酸片段为研究对象,利用无标记的分子信标及核酸染料SYBR Green I,建立了一种高灵敏、高选择性的特定序列核酸检测方法.在优化条件下,目标DNA浓度为4×10-11~400×10-11 mol/L之间时,SYBR Green I的荧光强度(ΔI)与目标DNA的浓度(C)具有良好的线性关系,其拟合的回归方程为ΔI=1.9556 C+31.4659(R2=0.9956),方法检测限(3ζ)为2×10-11 mol/L.该方法操作简单、检测速度快、灵敏度高、重现性好、检出限低.利用该方法,结合不对称PCR技术,实现了对HBV的定量检测.     

近红外二区活体荧光成像在肿瘤诊疗中的应用

由于具备组织穿透深度深和时空分辨率高等优势, 近年来近红外二区(Near-infrared-Ⅱ, NIR-Ⅱ, 1000~1700 nm)荧光成像技术得到了快速发展, 其在肿瘤临床诊断和治疗的潜力更是引发了广泛关注. 本文首先阐释了NIR-Ⅱ窗口荧光成像的原理及其优势, 随后根据结构分类归纳总结了现有荧光团的特征, 重点介绍了荧光探针在性能优化上的进展以及在肿瘤早期检测、 术中导航和光疗中的应用, 最后讨论了现有NIR-Ⅱ 荧光探针的局限以及临床转化面临的挑战, 并对未来的发展方向进行了展望.     

2-氨甲基-1H-苯并咪唑钴(Ⅱ)和镍(Ⅱ)配合物的合成、晶体结构和抑菌活性(英文)

利用双齿配体2-氨甲基-1H-苯并咪唑(AMBI)和硫氰酸钾以及硝酸钴或硝酸镍在甲醇-水中反应制备了2个新的异质同晶配合物trans-[M(AMBI)2(NCS)2](1:M=Co2+,2:M=Ni2+)。X-射线衍射单晶结构表明:2个配合物属于单斜晶系,C2/c空间群,M(Ⅱ)与来自AMBI的4个氮原子和异硫氰酸根的2个氮原子配位,形成八面体结构。配合物中的N-H…S氢键和π-π相互作用将配合物连接成三维网络结构。用红外光谱、紫外-可见光谱对配合物1和配合物2进行了表征,并对配合物的热稳定性做了研究。选取金黄色葡萄球菌和大肠杆菌作为抑菌菌种,研究了配体AMBI和2个配合物的抑菌能力。     

基于三唑配体的金属锰(Ⅱ)、锌(Ⅱ)配合物的合成、晶体结构与性质研究(英文)

在不同反应条件下,采用三唑衍生物作为配体与乙酸锰和硝酸锌反应,合成了2个具有三维结构的配位化合物{Mn(pytyba)(H2O)3]·2H2O}n(1)和{[Zn(pytyba)(H2O)3]·4H2O}n(2),并通过元素分析、热重分析、荧光性、X射线单晶衍射对化合物进行分析。结构分析表明1和2有许多共同特征:两个聚合物的晶体均属于单斜晶系,C2/c空间群,Mn2+和Zn2+均为六配位畸变八面体配位结构,具有相似的热稳定性、荧光性以及相近的孔隙率。配体中的氧原子与金属离子配位形成一维链状结构,然后又通过O-H…N、O-H…O氢键作用和π…π芳香堆积形成超分子结构。此外,通过测定化合物抗氧化活性(SOD)的经典方法-Marklund法对配合物1和2的抗氧化活性进行了研究。     

A Dinuclear Cu(Ⅱ)-based Coordination Framework with Two-fold Interpenetrated 3D pcu Topology Displaying Catalytic Activity

A new Cu(Ⅱ) coordination polymer, [Cu2(mip)2(bmix)]n(bmix = 1,4-bis(2-methylimidazole-1-ylmethyl)benzene, H2 mip = 5-methylisophthalic acid), has been hydrothermally synthesized and characterized by elemental analyses, IR, TGA and single-crystal X-ray diffraction. The title compound belongs to the triclinic system, space group P1 with a = 9.435(5), b = 12.241(6), c = 13.666(6), β = 94.396(8)o, V = 1565.5(13) 3, Z = 2, C34H30Cu2N4O8, Mr = 749.70, Dc = 1.590 g/cm3, μ = 1.419 mm-1 and F(000) = 768. The title metal-organic coordination polymer exhibits the first two-fold interpenetrated pcu topological structure assembled by two types of dinuclear copper(Ⅱ) clusters and a flexible bis(imidazole)-based ligand. In addition, the fluorescence and catalytic performances of the complex for the degradation of Congo red azo dye in Fenton-like process were presented.     

Syntheses,Crystal Structures,and Properties of a New Lead(Ⅱ) Complex Involving Holo-and Hemidirected Coordination Spheres with 3,5,6-Tris(2-pyridyl)-1,2,4-triazine Ligand

[Pb(TPT)(μ-I)2PbI2(μ-I)2Pb(TPT)] 1(TPT is the abbreviation of 3,5,6-tris(2-pyridyl)-1,2,4-triazine ligand) has been synthesized and characterized by elemental analysis, IR, 1HNMR spectroscopy and studied by thermal and electrochemical properties as well as X-ray crystallography. The single-crystal X-ray data show two different kinds of Pb2+ ions in 1 with coordination numbers of six, Pb1 = PbI6, and five, Pb2 = PbN3I2, with holodirected and hemidirected coordination spheres, respectively. The supramolecular features in 1 are negotiated through the weak but directional Pb···I, C–H···N and C–H···I interactions and aromatic π-π stacking interactions.     

Synthesis and Characterization of a Two-dimensional Cadmium(Ⅱ) Metal Organic Framework with Fes Topology

A new Cd(Ⅱ) coordination polymer, {[Cd(Hnbta)(L)]·H2O}n(L = 1,4-bis(5,6-dimethylbenzimidazol-1-yl)butane), H3nbta= 5-nitrobenzene-1,2,3-tricarboxylic acid), has been hydro-thermally synthesized and characterized by elemental analyses, IR, XRPD, and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/n with a = 17.3056(13), b = 11.0114(9), c = 17.7484(14) A, β = 117.3640(10)o, V = 3003.7(4) A3, Z = 4, C31H31CdN5O9, Mr = 730.01, Dc = 1.614 g/cm3, μ = 0.792 mm-1 and F(000) = 1488. The cadmium(Ⅱ) ions are bridged by Hnbta2- to generate a two-dimensional metal organic framework with fes topology. In addition, the thermal stability and fluorescence properties of the complex were also studied.