两个含1-苄基咪唑的Zn(Ⅱ)和Cu(Ⅱ)新配合物:合成和结构研究(英文)

1-苄基咪唑(L)与对苯二甲酸和Zn(NO_3)_2·6H_2O反应生成一维聚合链[ZnL_2(TP)]_n(1),在这个配合物中通过链间的C-H…π相互作用形成了二维超分子层。1-苄基咪唑(L)和CuCl_2·2H_2O反应生成四核配合物[Cu_4(μ_4-O)Cl_6L_4](2),在这个配合物中通过C-H…Cl氢键形成了一维超分子链。测定了L,1和2的荧光发射光谱。     

On the chaotic character of the stochastic heat equation, II

Consider the stochastic heat equation ${\partial_t u = (\varkappa/2)\Delta u+\sigma(u)\dot{F}}$ , where the solution u := u _t (x) is indexed by ${(t, x) \in (0, \infty) \times {\bf R}^d}$ , and ${\dot{F}}$ is a centered Gaussian noise that is white in time and has spatially-correlated coordinates. We analyze the large- ${\|x\|}$ fixed-t behavior of the solution u in different regimes, thereby study the effect of noise on the solution in various cases. Among other things, we show that if the spatial correlation function f of the noise is of Riesz type, that is ${f(x)\propto \|x\|^{-\alpha}}$ , then the “fluctuation exponents” of the solution are ${\psi}$ for the spatial variable and ${2\psi-1}$ for the time variable, where ${\psi:=2/(4-\alpha)}$ . Moreover, these exponent relations hold as long as ${\alpha \in (0, d \wedge 2)}$ ; that is precisely when Dalang’s theory [Dalang, Electron J Probab 4:(Paper no. 6):29, 1999] implies the existence of a solution to our stochastic PDE. These findings bolster earlier physical predictions [Kardar et al., Phys Rev Lett 58(20):889–892, 1985; Kardar and Zhang, Phys Rev Lett 58(20):2087–2090, 1987].     

氨基化修饰介孔Fe3O4@SiO2@mSiO2磁性核壳复合微球的可控制备及吸附性能

以水热法制备的高磁饱和强度Fe₃O₄纳米颗粒为核,正硅酸乙酯（TEOS）为前驱体,采用改进的Stöber法,制备介孔SiO₂包覆Fe₃O₄磁性核壳复合微球。利用XRD、SEM、TEM、N₂吸-脱附、FTIR和VSM对制备样品的物相结构、形貌和磁性能进行了测试表征。研究结果表明,制备的复合材料呈球形,粒径分布均一,材料的比表面积和磁饱和强度分别为413 m²·g^-1和68.93 emu·g^-1。研究了TEOS的添加量对复合微球形貌的影响,随着TEOS添加量的增加,SiO₂壳层增厚,复合粒子形貌均匀,饱和磁化强度有所下降,仍具有良好的超顺磁性。在此基础上,通过接枝法在复合微球的表面接枝-NH₂,制备了一种新型磁性纳米吸附剂（Fe₃O₄@SiO₂@mSiO₂-NH₂）,进而研究了其对水中重金属离子Cr（Ⅳ）的吸附性能。通过动力学拟合,Fe₃O₄@SiO₂@mSiO₂-NH₂对Cr（Ⅳ）的吸附过程是准二级动力学模型占主导地位。探究了该材料对Cr（Ⅳ）的吸附过程和吸附机理。结果表明,其吸附机理及吸附容量与Cr（Ⅳ）的离子形态及-NH₂有关,并通过吸附剂与吸附质之间的电子共用或静电吸附实现。     

Mixed-Valence CuI/CuIII Metal–Organic Frameworks with Non-innocent Ligand for Multielectron Transfer

We report two novel three-dimensional copper-benzoquinoid metal–organic frameworks (MOFs), [Cu₄L₃]_n and [Cu₄L₃ ⋅ Cu(iq)₃]_n (LH₄=1,4-dicyano-2,3,5,6-tetrahydroxybenzene, iq=isoquinoline). Spectroscopic techniques and computational studies reveal the unprecedented mixed valency in MOFs, formal Cu(I)/Cu(III). This is the first time that formally Cu(III) species are witnessed in metal–organic extended solids. The coordination between the mixed-valence metal and redox-non-innocent ligand L, which promotes through-bond charge transfer between Cu metal sites, allows better metal-ligand orbital overlap of the d-π conjugation, leading to strong long-range delocalization and semiconducting behavior. Our findings highlight the significance of the unique mixed valency between formal Cu(I) and highly-covalent Cu(III), non-innocent ligand, and pore environments of these bench stable Cu(III)-containing frameworks on multielectron transfer and electrochemical properties.