Syntheses,Structures, and Luminescent Properties of Two Zn~Ⅱ-organic Polymers Based on [Zn(ox)]_n Chains and Different Imidazole Linkers

Hydrothermal reactions of two imidazole derivatives(1,3,5-tib = 1,3,5-tris(1Himidazol-1-yl)benzene, 1,4-bimb = 1,4-bis(1H-imidazol-1-ylmethyl)benzene) and the ZnⅡ cations in the presence of oxalic acid(H2ox) afford two coordination polymers, namely, {[Zn(ox)(1,3,5-tib)]·2(H2O)}n(1) and [Zn1.5(ox)1.5(1,4-bimb)1.5]n(2). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction(PXRD) analyses. Both complexes 1 and 2 are based on the 1D zigzag [Zn(ox)]n chains, and their final structures are controlled by the two different imidazole linkers, which expanded the structure along different directions, finally giving a 3D dia net for 1 and a 2D sql layer for 2. Moreover, the luminescent properties of 1 and 2 have been investigated.     

Syntheses,Structures, and Properties of Three Coordination Polymers: [Cd_2(bpp)_(1.5)(Hbpp)(phen)_2]_n, [Mn_3(Htptc)_2(phen)_2(H_2O)_2]_n,and {[Cu(btc)_(0.5)(1,4-bib)]·2H_2O}_n

Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers: [Cd2(bpp)1.5(Hbpp)(phen)2]n(1), [Mn3(Htptc)2(phen)2(H2O)2]n(2), and {[Cu(btc)0.5(1,4- bib)]·2H2O}n(3)(H2bpp = 2,6-bis(4'-carboxyphenyl)-4-phenylpyridine, H4tptc = terphenyl-2,5,2',5'-tetracarboxylic acid, H4btc = biphenyl-2,2',4,4'-tetracarboxylic acid, phen = 1,10-phenanthroline, and 1,4-bib = 1,4-bis(1H-imidazol-1-yl)benzene). Their structures have been determined by singlecrystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction(PXRD) analyses. In compound 1, the CdII cations are linked by bpp2- to form one ladder structure, based on which a 3D network is constructed with the help of non-covalent interactions. The topology of 2 is a 3D(3,4,5)-connected framework with the Point Schl?fli symbol of(42.6)32(4.62.8)(45.64.8)2. Compound 3 shows an unprecedented 3D(4,4)-connected framework with the Point Schl?fli symbol of(64.82)2(65.8). Moreover, the luminescent property of 1 has been investigated.     

Syntheses and Crystal Structures of Homleptic Lanthanide Complexes [C_6H_5COCHC(CH_3)N-(p-ClC_6H_4)]_3Ln(THF)_n (Ln =Yb,Y,Nd)

Three homoleptic lanthanide complexes, [C6H5COCHC(CH3)N(p-ClC6H4)]3Ln(THF)n(n = 0, Ln = Yb(1); n = 0, Ln = Y(2); n = 1, Ln = Nd(3)), were synthesized by amine elimination reaction of Ln[N(SiMe3)2]3 with 1-phenyl-3-N-(p-chlorophenylimino)-1-butanone. These complexes crystallize in triclinic, space group P1 with a = 9.805(3), b = 14.831(6), c = 16.075(6) A, α = 111.996(9), β = 91.570(7), γ = 93.744(6)°, V = 2159.4(13) A3, Z = 2, D3 c = 1.515 g/cm, F(000) = 986, μ(MoKα) = 2.396 mm-1, R = 0.0360 and wR = 0.0850 for 9548 observed reflections with I 2σ(I) for complex 1; a = 9.861(5), b = 14.852(9), c = 16.111(9) A, α = 112.362(13), β = 91.949(11), γ = 93.678(14)°, V = 2173(2) A3, Z = 2, Dc = 1.377 g/cm3, F(000) = 924, μ(MoKα) = 1.570 mm-1, R = 0.0735 and wR = 0.1389 for 8015 observed reflections with I 2σ(I) for complex 2; and a = 9.308(3), b = 15.357(3), c = 17.419(4) A, α = 66.493(13), β = 88.61(2), γ = 86.664(19)°, V = 2279.4(9) A3, Z = 2, Dc = 1.499 g/cm3, F(000) = 1046, μ(MoKα) = 1.364 mm-1, R = 0.0843 and wR = 0.2280 for 8433 observed reflections with I 2σ(I) for complex 3. Each central metal in complexes 1 and 2 is six-coordinated by three nitrogen and three oxygen atoms from three β-ketoiminate ligands to give a distorted octahedral geometry, while the central metal in 3 is seven-coordinated by three nitrogen and three oxygen atoms from three β-ketoiminate ligands and one oxygen atom from the solvated THF molecule to complete a distorted monocapped trigonal prism.     

苏丹红猝灭吖啶染料荧光的动力学研究

在体积分数95%乙醇介质中,吖啶黄、吖啶橙的荧光发射波长与苏丹红染料的吸收波长十分接近。实验数据表明,随着苏丹红I~IV用量的增加,溶液中吖啶黄、吖啶橙荧光发射强度明显降低,其荧光猝灭程度与苏丹红用量成正比。动力学研究表明苏丹红I,II与吖啶黄或吖啶橙之间可形成非共价复合物,从而发生静态荧光猝灭;而苏丹红III,IV猝灭吖啶黄或吖啶橙则表现为一种复杂的动力学特点,可能同时存在静态荧光猝灭与动态猝灭。     

羟基磷灰石/聚乙烯醇/壳聚糖水凝胶在模拟体液中的力学性能

从仿生学角度出发,将自制的人工角膜支架材料羟基磷灰石/聚乙烯醇/壳聚糖(n-HA/PVA/CS)浸泡在模拟体液中,对材料的含水率及力学性能进行了测试,并利用扫描电镜、X射线衍射仪、电感耦合等离子体原子发射光谱仪及热重分析仪研究了材料在模拟体液中的形貌、晶体结构、元素组成及热稳定性.结果表明,在模拟体液中,n-HA/PVA/CS复合水凝胶的含水率为80%~86%,具有较高的拉伸强度,能承受正常眼压,且热稳定性较好.在浸泡后期,n-HA/CS/PVA复合材料对Ca2+的吸附和释放达到动态平衡;而其表面含有微量的纳米羟基磷灰石沉积,有利于纤维细胞的长入.     

分级纳米材料的结构、制备及其应用

纳米材料因其独特的表面效应、体积效应和量子效应等特点,在化工、生物工程、医学和能源等领域有着广阔的应用。 由简单的低维纳米结构作为主要的构建单元并按照特定的排列方式组装成规整有序的三维结构,即分级纳米结构,已经开展了许多的研究。 本文综述了分级纳米结构的制备方法和微观结构,及其在污水处理、超级电容器、太阳能电池以及光催化等领域的应用。     

Synthesis and Electronic Structure of Triazasubporphyrin with Peripherally Low Symmetric Push-pull Substitutions

Peripherally low symmetric substitution with electron-donating(EDG)and electron-withdrawing(EWG)substituents caused the rational modulation of geometric structure and even the electronic structure of triazasubporphyrin,the smallest 14πconjugated aza-porphyrinoids.Both structural characterization and spectroscopic investigation were discussed to provide an in-depth understanding of the relationship between peripheral push-pull substituents and SubPz core.     

Crystal Structure of Scheelite-type LiTb(WO_4)_2 and Multi-color Emitting Properties Doped by Eu~(3+)

Single crystal of lithium terbium tungstate LiTb(WO4)2 has been grown by the flux method. The crystal structure was refined from single-crystal X-ray data. It crystallizes in tetragonal system, space group I41/a with a = 5.1749(9), c = 11.1953(19) ?, V = 299.81(12) ?~3, Z = 2, Mr = 661.56, Dc = 7.328 g/cm^3, F(000) = 560, μ(MoKα) = 49.94 mm^-1, R(F^2 > 2σ(F^2)) = 0.026 and wR(F^2) = 0.070. It features a typical scheelite-type structure composed of two-direction packing of isolated WO4 tetrahedra. Li and Tb atoms in the structure occupy the same crystallographic site. Moreover, a series of solid solution phosphors LiTb(1-x)Eux(WO4)2(x = 0.004~0.1) were synthesized by high temperature solid-state reactions. The phosphors could be effectively excited by a wavelength range from 379 to 487 nm, which matches well with the UV and near-UV LED chip. The emission color of the phosphor can be tuned from green, through yellow to red by simply adjusting the relative Eu³⁺ and Tb³⁺ concentration due to the Tb³⁺ to Eu³⁺ energy transfer.     

双金属氮化物Co3W3N/CNTs纳米复合材料的制备及其室温常压氮还原性能

采用水热法并经氨气保护热处理制备了双过渡金属氮化物Co3W3N/CNTs复合材料,得到了价格低廉且拥有良好氮电化学还原性能(NRR)的催化剂。通过调节已经预氧化的CNTs与过渡金属氮化物前驱体CoWO4的比例以及氨气热处理温度,实现了Co3W3N在CNTs表面的均匀负载。扫描电子显微镜(SEM)及透射电子显微镜(TEM)测试结果显示该电化学活性纳米微粒均匀地分散于CNTs表面,表明经预氧化的CNTs由于表面富集了较多的活性基团,有利于双过渡金属氮化物的分散生长。热处理后CNTs表面的Co3W3N微粒尺寸约为20 nm,相较于无载体的Co3W3N尺寸(100 nm)有明显减小。室温条件下,在N2饱和的0.01 mol·L^-1 H2SO4溶液中测试了该纳米复合材料在不同过电位下的NRR,该材料在-0.3 V(vs RHE)时的产氨率及法拉第效率分别可达12.73μg·h^-1·cm-2和13.59%,对比同样条件下,纯相Co3W3N的产氨率及法拉第效率仅为1.08μg·h^-1·cm^-2和1.76%。结果表明,通过水热反应和氨气保护热处理的Co3W3N/CNTs纳米复合材料具有良好的NRR性能。     

磁单极与磁洛伦兹力

概述了磁单极概念的历史发展,从洛伦兹变换出发,利用电磁场张量和四维力的协变性以及电荷相对论不变,直接证明了运动磁单极受磁洛伦兹力,建议了一个磁洛伦兹力的验证方案,并用磁洛伦兹力公式导出狄拉克电荷量子化条件．证明了磁洛伦兹力公式具有与库仑定律相同的精确度．