目的 制备新型金@铂纳米复合材料-铜金属有机骨架/玻碳电极(gold platinum nanocomposites-copper metal organic framework/glassy carbon electrode,Au@PtNPs-Cu-MOF/GCE)传感器,并对水果中的葡萄糖进行快速检测分析.方法 先制备二维Cu-MOF纳米材料,并在其表面负载核壳结构的Au@PtNPs,合成Au@PtNPs-Cu-MOF纳米复合材料,最终构建一种新型Au@PtNPs-Cu-MOF/GCE传感器,通过对电解质pH、计时安培电位的优化确定Au@PtNPs-Cu-MOF/GCE传感器的最佳工作条件,并应用于梨中葡萄糖的定量分析.结果 葡萄糖浓度与其峰电流分别在0.1～10.0和10.0～2600.0μmol/L范围内呈良好的线性关系,检出限为0.0872μmol/L,定量限为0.9632μmol/L,线性范围宽、检出限低,明显优于其他的葡萄糖无酶传感器.Au@PtNPs-Cu-MOF/GCE传感器的重复性和抗干扰能力较好,8次扫描的相对标准偏差为1.32％.对梨汁中的检测结果为1.7449 mmol/L,与高效液相色谱法一致且偏差仅为5.46％.结论 Au@PtNPs-Cu-MOF/GCE操作简便、快捷且成本低廉,可用于果蔬中葡萄糖的快速定量分析.

目的 制备氧化锌@金纳米复合材料/玻碳电极(zinc oxide@gold nanocomposites/glassy carbon electrode,ZnO@Au/GCE)电化学传感器对双酚A进行检测分析.方法 合成了氧化锌纳米花(zinc oxide nano flower,ZnO)并在ZnO 上面生长纳米金(gold nanocomposites,Au)制备了新型的ZnO@Au 纳米复合材料.以ZnO@Au 为修饰材料,采用玻碳电极(glassy carbon electrode,GCE)构建了ZnO@Au/GCE 传感器.通过对缓冲液、ZnO@Au 修饰量的优化,确定ZnO@Au/GCE 的最佳工作条件,对双酚A 进行检测分析.结果 ZnO@Au不仅导电性、稳定性好而且具有良好的催化性,可有效提高ZnO@Au/GCE 的灵敏度.双酚A 浓度与氧化峰电流分别在0.05～1.00 μmol/L 和1.0～240.0 μmol/L 范围内呈线性关系,检出限(S/N=3)为0.021 μmol/L,加标检测结果与高效液相色谱法一致,且该传感器重复性、稳定性较好,对常见干扰物有良好的抗干扰能力.结论 ZnO@Au/GCE操作简便、快捷且准确度高,可用于双酚A 的快速定量分析.

Abstract A stable 3-D metal–organic framework (MOF), [Cd(H2DTPA)(1.2-mbix)] n (1), has been constructed with aromatic 2,3-dihydroxy terephthalic acid (H4DTPA) and cadmium salt under solvothermal conditions. The structure shows that H2DTPA2+ concatenates two Cd(II) cations to form a 1-D folded chain; the flexible nitrogen-containing 1,2-mbix sections link two adjacent 1-D chains into a 3-D framework. Complex 1 exhibited strong ligand-derived photoluminescence and was sensitive to nitroaromatic explosives (2-nitrophenol, nitrobenzene, 4-nitrophenol, 4-nitrotoluene and 4-nitrochlorobenzene). Graphical abstract

Single-molecule magnets in cobalt clusters is much less well known than it is in manganese(II)/(III)/(IV) clusters. To explore new types of cobalt clusters and their potential applications, a new mixed valence coordination polymer ([Co(III)3Co(II)2(mba)6(Hdtba) (H2O)4]n, H2dtba=2,2'-dithiodibenzoic acid, H2mba=2-mercaptobenzoic acid) (1) is constructed by employing cobalt chloride hexahydrate and H2mba as starting reactants under hydrothermal conditions. Single-crystal XRD studies indicate that 1 consists of a trinuclear cobalt(III)-sulfur cluster moiety and two discrete cobalt(II) nodes, which result in the formation of a covalent three-dimensional complex network. Similarly, the cobalt(III) cluster moiety acts as a building unit in this infinite coordination polymer 1 instead of the discrete and tiara-like clusters previously reported in the literature. Magnetic studies show its slow magnetic relaxation in the absence of an applied dc field, which is characteristic behavior of single-ion magnets, caused by the individual Co(II) ions.

Four coordination polymers (CPs), [Cd(2,7‐dpfo) 2 (NO 3 ) 2 (CH 3 OH)] n (1) , [Zn(2,7‐dpfo)(NO 3 )(CH 3 COO)] n (2) , [Co(2,7‐dpfo) 2 (H 2 L)] n (3) , and [Ni(2,7‐dpfo) 2 (H 2 L)] n (4) (where 2,7‐dpfo is 2,7‐di(pyridin‐4‐yl)‐9 H ‐fluoren‐9‐one and H 4 L is 1,1′:4′,1′′‐terphenyl‐4,2′,5′,4′′‐tetracarboxylic acid), were synthesized and structurally characterized. Compounds 1 – 4 were determined by elemental analyses, single crystal X‐ray diffraction analyses, powder X‐ray diffraction, infrared spectroscopy, and thermogravimetric analyses. Compound 1 displays a one‐dimensional (1D) zigzag chain structure, while compound 2 possesses a 1D ladder chain structure. Compounds 3 and 4 are isostructural and consist of 1D chains. The solid‐state luminescent properties of 1 and 2 and the magnetic properties of 3 and 4 were also investigated.

合成了一个铜单核配合物Cu(HL1)2(H2L1=2-羟基-3-(羟基亚氨基)甲基苯甲酸甲酯),利用红外光谱和X射线单晶衍射对这个配合物的结构和性质进行了表征.结果表明:该配合物属单斜晶系,C2/c空间群,晶胞参数为:a=16.939(2)nm,b=4.633(5)nm,c=23.245(3)nm,α=γ=90°,β=105.428(1)°,V=1758.3(3)nm3,Z=4,Dc=1.707 g·cm-3,μ=1.296 mm-1,F(000)=924,R1=0.0354,wR2=0.0802.配合物的结构是一个铜原子处于两个配体中间的平行四边形结构.在铜原子参与的情况下,合成的有机配体与甲醇发生了酯化反应,生成了新的配体H2 L1.

合成了一例四核化合物{[CuLPr(NO3)2(H2 O)]2}n(I),并通过IR、元素分析、UV-vis光谱、热重分析和单晶X射线衍射进行了表征.该化合物属于P21/n空间群,单斜晶系.晶胞参数:a=1.2169(3),b=1.2481(4),c=1.5071(4)nm,β=82.337(2)°,V=2.288(1)nm3,Z=4,C17 H17 CuN4 O11 Pr,M=657.80,ρc=1.909 g/cm3,μ(MoKα)=3.098 mm-1,F(000)=1292,GOOF=1.050,R1=0.0652,wR2=0.1913,I>2σ(I).在化合物I中,双核片段利用酰胺氧原子得到了一个四核结构.通过硝酸根离子在轴向位置与铜离子配位,得到了一个二维网状化合物.

基础化学实验涵盖常见化学实验基本操作技术,是化学相关学科发展的坚实物质基础.河南大学基础化学实验分中心承担学校七个学院二十多个专业基础化学实验教学任务,在开放实验室进一步优化建设中,探索运用"同质异形"教学法,强化基本实验操作技能训练,强调结合不同学科专业实际创新应用.

Two Cd(II) coordination polymers constructed from tris(p-carboxylphenyl)phosphine oxide (H3TPO), [Cd(HTPO)(1,4-bix)3H(2)O](n) (1) and [Cd-2(HTPO)(HBPO)(H2O)(2)](n) (2) (1,4-bix=1,4-bis(imidazol-1-ylmethyl)benzene, H3BPO=bis(4-carboxylphenyl)phosphinic acid), were synthesized and identified by IR, elemental analysis, and single-crystal X-ray diffraction analysis. The 1,4-bix ligand leads to 1 as a ladder-like 1D chain structure. In 2, adjacent Cd-2 units are bridged by HBPO2- and HTPO2- ligands to form a 3D structure. The H3BPO ligand is formed from the in situ reaction of H3TPO. It is the first example from hydrated Cd(II) salt promoting partial hydrolysis of a phosphine oxide ligand. The thermal behavior and solid-state photoluminescence properties correlated with the corresponding structural features were investigated.

Facile preparation of electrode modified materials with low-cost nanocomposites is an important step to develop highly active electrochemical sensors for mass-market applications. Here we fabricated Au nanoparticles (AuNPs)-loaded ZnS nanocomposites for the sensitive determination of rutin due to the cooperative amplification of the conductivity and catalytic activity of AuNPs on ZnS spheres resulting from the high loading ratio of AuNPs on ZnS spheres. Under the optimal conditions, the developed sensor based on AuNPs-loaded ZnS nanocomposites exhibited excellent electrocatalytic activity towards rutin in a linear range from 1 × 10-7 mol/L to 2 × 10-5 mol/L with a limit of detection of 15.3 nM at a signal-to-noise ratio of 3. Furthermore, the proposed method gave satisfactory results for rutin determination in pharmaceutical tablets, which offer promising potential for rutin electrochemical analysis in serum monitoring or Chinese medical analysis owing to its simplicity, low cost, high sensitivity and good stability.

Two metal-organic coordination polymers constructed from tris(p-carboxylphenyl) phosphine oxide (TPOH3), namely, [Zn(TPOH)(2,2'-bipy)(H2O) center dot H2O center dot DMF](n) (1) and [Zn-2 (TPOH)(2) (1,4-bix)(2) center dot 5H(2)O](n) (2) (2,2'-bipy = 2,2'-bip-ydine, 1,4-bix = 1,4-bis(imidazol-1-ylmethyl) benzene), were synthesized and identified by IR, elemental analysis and single-crystal X-ray diffraction analysis. Both of the 2,2'-bipy and 1,4-bix ligands tailor the complexes 1 and 2 into chain structures. The thermal behavior and solid state photoluminescence properties correlated with the corresponding structural features were investigated.

Three Ag(I) coordination complexes, namely [Ag3(2-stp)(2-apy)2·3H2O]n (1), [Ag3(2-stp)(2-apy)2]n (2) and [Ag3(2-stp)(3-apy)(H2O)]n (3) (2-NaH2stp = 2-sulfoterephthalic acid monosodium salt, 2-apy = 2-aminopyridine and 3-apy = 3-aminopyridine), have been synthesized and structurally characterized. They all show two-dimensional network structures. In complex 1, the Ag3 units are linked by stp ligands to form a 1D chain. Consequently, the 2-apy ligands link the adjacent 1D chain into 2D polymeric sheets. In 2, Ag1 and Ag2 atoms are bridged by stp ligands to form a 2D infinite sheet. In 3, the stp anion adopts a μ7-(η1,η2):(η1,η1,η0):(η1,η1) coordination mode to Ag3 units to 2D layer sheet and the network is consolidated by 3-apy ligands. The thermogravimetric analyses and photoluminescence of the complexes were also investigated.

Five Ag(I) coordination complexes, namely, [Ag6(2-stp)2(3-methyl-2-apy)3·H2O]n (1), [Ag3(2-stp)(4-methyl-2-apy)3]n (2), [Na2Ag18(2-stp)4(2-Hstp)4(5-methyl-2-apy)16 (H2O)4·11H2O]n (3), Ag3(2-stp)(6-methy-2-apy)4·H2O (4), and [Ag6(2-stp)2(6-methyl-2-apy)8(H2O)2·H2O]n (5) (2-NaH2stp = 2-sulfoterephthalic acid monosodium salt, 3-methyl-2-apy = 3-methyl-2-aminopyridine, 4-methyl-2-apy = 4-methyl-2-aminopyridine, 5-methyl-2-apy = 5-methyl-2-aminopyridine, 6-methyl-2-apy = 6-methyl-2-aminopyridine), have been synthesized and structurally characterized. Complexes 1 and 2 show two-dimensional network. In complex 3, the adjacent Ag10 units are bridged by 5-methyl-2-apy ligands to form a 2D infinite undulated sheet. Adjacent 2D sheets are linked by coordinative bonds between carboxylic oxygen atoms and Na(I) ions to form a 3D coordination polymer. Complex 4 is a 0-D discrete trinuclear molecule, and the self-complementary the OH⋯O and NH⋯O hydrogen bonds incorporating hydrogen bond motifs extend these molecules into a 2D supramolecular framework. Compound 5 exhibits 1D-chain structure. However, complex 5 shows 3D supramolecular structure results from the linkage of neighboring layers through a rich hydrogen-bonding between uncoordinated sulfonates, amino groups and coordinated carboxylates. The thermogravimetric analyses and photoluminescence of the complexes were also investigated.

Nine coordination polymers (CPs) [Mn(H3L)(H2L)0.5(phen)]n (1), [Ni2L(phen)2(μ2-H2O)]n (2), {[Mn2L(phen)2]·(DMA)(H2O)}n (3), {[Co2L(μ2-H2O)(μ2-DMA)]·DMF}n (4), [CoL0.5(H2O)(phen)]n (5), {[Ni2L(μ2-H2O)(μ2-DMA)]·DMA}n (6), {[Co2L(μ2-H2O)(μ2-DMA)]·DMA}n (7), {[Ni2L(μ2-H2O)(H2O)2(DMF)2]·(H2O)2(DMF)}n (8), and {[Ni4L2(μ2-H2O)4(H2O)2]·(H2O)2(NMP)}n (9) (H4L = 1,1':4',1''-terphenyl-2',4,4'',5'-tetracarboxylic acid, DMA = N,N-dimethylacetamine, DMF = N,N-dimethylformamide, NMP = N-methyl-2-pyrrolidone, phen = 1,10-phenanthroline) have been synthesized and structurally characterized. Crystal structural analyses reveal that 1 features the uninodal 2D (4,4) network with the dinuclear Mn2(COO)2 units as 4-connected nodes. 3 and 5 possess the binodal 2D (4,4) network with dinuclear Mn2(COO)4/Co2O2 units and L4- ligands as 4-connected nodes, respectively. In 2 and 8, each dinuclear Ni2(COO)2(μ2-H2O) unit links to four L4- ligands and each L4- ligand bridges four dinuclear Ni2(COO)2(μ2-H2O) units to generate the 3D framework, which can also be rationalized as a binodal 4,4-connected (42·84)(42·84) topological network by considering the dinuclear Ni2(COO)2(μ2-H2O) units as non-planar 4-connected nodes and L4- ligands as planar 4-connected nodes, respectively. In 4, 6-7 and 9, there exist a series of parallel-aligned metal-carboxylate chains, which are linked along two directions by para-terphenyl moieties of L4- ligands to generate the 3D frameworks. Moreover, direct current magnetic susceptibility measurements were carried out to study their magnetic properties. In complexes 2 and 9, weak ferromagnetic interactions between the magnetic centers were observed. In addition, the other compounds show weak antiferromagnetic exchange interactions between the adjacent metal ions.

A dinuclear complex Ni2 H3 LHL1 ·CH3 OH (Ⅰ) was sythesized and characterized by IR, elemental analysis, UV-vis and fluorescence spectra, thermal gravimetric analysis and single crystal X-ray diffraction. Complex Ⅰ crystallizes in the triclinic system, space group Pī, with a = 1.2295(1) nm, b = 1.2368(1) nm, c = 1.6429(2) nm, α = 69.083(2)°, β = 82.337(2)°, γ = 86.421 (2)°, V = 2.312(4) nm3, Z = 2, C45H52NiN8O13, M = 1030.37,ρc= 1.480 g/cm3,μ(MoKα) =0.888 mm-1, F(000) = 1076, GOOF = 0.908, Z = 2, the final R1= 0.0583 and wR2= 0.1007 for I > 2σ( I) . The structure of complexⅠconsists of dinuclear units. The complex exhibits a tetranu-clear hydrogen bonding framework through intermolecular O-H…O and N-H…O interactions.

A copper mononuclear complex Cu(HL )2 ,where H2 L denotes the (ethyl salicylate shrink hydrazine hydrate) shrink 2‐pyridyl formaldehyde ,has been synthesized and its struc‐ture and properties were determined by infrared spectra ,UV‐Vis spectra and X‐ray single crys‐tal diffraction .Results indicate that this compound belongs to orthorhombic system ,and the space group is Aba2 with lattice parameters a = 1 .292 0(2) nm ,b = 1 .806 0(3) nm ,c =1 .092 4(2) nm ,α = β = γ = 90° ,V = 2 .549 0(7) nm3 ,Z = 4 ,D c = 1 .418 g ?cm- 3 ,μ =0 .901 mm- 1 , F(000) = 1 116 , R1 = 0 .074 9 , wR2 = 0 .164 9 .The structure of complex is that a copper atom is sandwiched of two ligand molecules in crossing directions .

Two novel trinuclear oxamato-bridged thiosemicarbazone complexes, [Cu(obte)](2)Cd(DMF)(2) (2) and [Cu(obte)](2)Mn(DMF)(2) (3) (H(2)obte = N-(2-benzaldehyde) oxamic acid ethyl ester thiosemicarbazone (1); DMF = dimethylformamide), have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Complexes 2 and 3 are isostructural, displaying a trinuclear structure. The luminescence properties of complexes 2 and 3 were investigated in the solid state at room temperature. The ligand 1 and its complex 2 have been evaluated for their antitumor activities against K562 cells.

The synthesis and characterization of a family of heterometallic Ni4Ln2 complexes (Ln = Pr(1), Sm(2), Eu(3), Gd(4), Tb(5), Ho(6) and Er(7)) of the formula [Ni2LnL1L2(OH)(H2O)]2 are reported, where H4L1 is 3,3′-(1E,1′E)-(2,2′-(2-aminoethylazanediyl)bis(ethane-2,1-diyl)bis(azan-1-yl-1-ylidene))bis(methan-1-yl-1-ylidene)bis(2-hydroxybenzoic acid) and H2L2 is 3-formyl-2-hydroxybenzoic acid. The molecular structures of 1–7 were determined by single-crystal X-ray diffraction and reveal that they are isostructural. In all of these compounds, the six metal ions are held together to form a novel Ni4Ln2O10 core and exhibit a relatively rare dumbbell-type structure. In these compounds, the Ni ions are in slightly distorted square-pyramidal or octahedral environments. An all-oxygen coordination environment (8O) is present around the central lanthanide ion, which is present in a distorted square antiprismatic geometry. The Ln–Ln and Ln–Oavg bond distances in 1–7 show a gradual reduction proceeding from 1 to 7, in accordance with the lanthanide contraction. The luminescent properties of all the compounds have been studied. The magnetic susceptibility analysis demonstrate antiferromagnetic interactions within complex 4.

Two new dissymmetrical Schiff-base copper(II) complexes, [(Cu2L)2(H2O)4]·(CuL)2·4H2O (1) and [Cu2L(dca)]n (2) (H3L=1-(2-hydroxybenzamido)-2-(2-hydroxy-3-methoxybenzylideneamino)ethane), have been synthesized and characterized by IR, elemental analysis, X-ray crystal diffraction and magnetic properties. Single-crystal structural analysis shows that complex 1 contains a tetranuclear [Cu4L2(H2O)4]2+ cation, two [CuL]− anions and four uncoordinated water molecules. Complex 2 is an infinite two-dimensional network structure in which the tetranuclear [Cu4L2] cations are interlinked by dicyanamide (dca−) bridges in the end-to-end (μ1,5) fashion. The magnetic properties of two complexes have been determined in the temperature range of 2.7–300K.

A new tetranuclear copper(II) compound containing dissymmetrical oxamidate ligand was synthesized and structurally characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, and magnetic properties. The title compound 1 crystallizes in triclinic, space group Pi with a = 8.9547(9), b = 11.7018(9), c = 12.0288(10) angstrom, alpha = 110.1790(10), beta = 100.0700(10), gamma = 100.6780(10), V= 1122.97(17) angstrom(3), C34H48Cl2Cu4N10O16, M-r. = 1177.92, D-c = 1.742 g/cm(3), mu(MoK alpha) = 2.067 mm(-1), F(000) = 600, Z = 1, the final R = 0.0391 and wR = 0.1073 for 3904 observed reflections (I> 2 sigma(I)). In the structure, complex 1 consists of a tetranuclear unit and two perchlorate anions. Furthermore, its magnetic properties have also been investigated.