Ester Hydrolysis by a Cyclodextrin Dimer Catalyst with a Tridentate N,N′,N′′‐Zinc Linking Group

A new β‐cyclodextrin dimer, 2,6‐dimethylpyridine‐bridged‐bis(6‐monoammonio‐β‐cyclodextrin) (pyridyl BisCD, L), is synthesized. Its zinc complex (ZnL) is prepared, characterized, and applied as a catalyst for diester hydrolysis. The formation constant (log K_ML=7.31±0.04) of the complex and deprotonation constant (pK_a1=8.14±0.03, pK_a2=9.24±0.01) of the coordinated water molecule were determined by a potentiometric pH titration at (25±0.1)°C, indicating a tridentate N,N′,N′′‐zinc coordination. Hydrolysis kinetics of carboxylic acid esters were determined with bis(4‐nitrophenyl)carbonate (BNPC) and 4‐nitrophenyl acetate (NA) as the substrates. The resulting hydrolysis rate constants show that ZnL has a very high rate of catalysis for BNPC hydrolysis, yielding an 8.98×10³‐fold rate enhancement over uncatalyzed hydrolysis at pH 7.00, compared to only a 71.76‐fold rate enhancement for NA hydrolysis. Hydrolysis kinetics of phosphate esters catalyzed by ZnL are also investigated using bis(4‐nitrophenyl)phosphate (BNPP) and disodium 4‐nitrophenyl phosphate (NPP) as the substrates. The initial first‐order rate constant of catalytic hydrolysis for BNPP was 1.29×10^?7 s^?1 at pH 8.5, 35 °C and 0.1 mM catalyst concentration, about 1600‐fold acceleration over uncatalyzed hydrolysis. The pH dependence of the BNPP cleavage in aqueous buffer was shown as a sigmoidal curve with an inflection point around pH 8.25, which is nearly identical to the pK_a value of the catalyst from the potentiometric titration. The k_BNPP of BNPP hydrolysis promoted by ZnL is found to be 1.68×10^?3 M ^?1 s^?1, higher than that of NPP, and comparatively higher than those promoted by its other tridentate N,N′,N′′‐zinc analogues.     

一种基于单元型红外光谱辐射计的成像光谱数据获取系统设计

依据单元非成像型光谱辐射计的特点,提出了一种单元非成像型红外光谱辐射计的成像光谱数据获取系统.该系统采用在光谱辐射计前端加装扣描装置.结合同步控制器,实现光谱辐射计的空间扫描.利用光谱辐射计提供的接口,完成了采集获得的成像光谱数据的批量定标.该系统可达到500×500像素的空间分解能力,光谱范围667～5 000 cm-1,光谱分辨率为1 cm-1,空间视场角为150°,瞬时视场角为0.3°.将该系统应用于实际的场景光谱数据获取,通过对得到的实验数据分析和比较,说明本文给出的基于非成像光谱辐射计的成像数据获取系统,能够实现实际场景的成像光谱数据获取,能够满足实时性要求不太高的成像光谱数据获取.     

一类非线性相对转动动力系统的平衡稳定性及组合谐波近似解

建立一类含广义非线性弹性力的两质量相对转动系统的非线性动力学方程. 应用变量梯度法构造李雅普诺夫函数,研究相对转动非线性自治系统的稳定性. 应用摄动法求得相对转动非线性非自治系统在两种不同频率谐波共同激励下的组合谐波响应的近似解. 关键词： 相对转动 非线性动力系统 稳定性 组合谐波响应     

A novel two‐dimensional cobalt(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene

In the crystal structure of the title complex, poly­[[di­azidocobalt(II)]‐di‐μ‐1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene‐κ⁴N⁴:N^4′], [Co(N₃)₂(bbtz)₂]_n, where bbtz is 1,4‐bis(1,2,4‐triazol‐1‐yl­methyl)­benzene (C₁₂H₁₂N₆), the Co^II atom, which lies on an inversion centre, is six‐coordinated by four N atoms from four bbtz ligands and by two N atoms from two azide ligands, in a distorted octahedral coordination environment. The Co^II atoms are bridged by four bbtz ligands to form a two‐dimensional [4,4]‐network.     

Properties on solutions of some q-difference equations

We consider the properties on solutions of some q-difference equations of the form ∑ n j=0 aj（z）f（qj z）=an＋1（z）, where a0（z）,..., an＋1（z） are meromorphic functions, a0（z）an（z） ≠ 0 and q ∈ C such that 0 〈 ｜q｜ ≤ 1. We give estimates on the upper bound for the length of the gap in the power series of entire solutions of （＊） when the coefficients a0（z）,..., an＋1（z） are polynomials and 0 〈 ｜q｜ 〈 1. For some special cases, we give estimates of growth of f（z）. And we also show that the case 0 〈 ｜q｜ 〈 1 is different from the case ｜q｜=1.     

填料填充型聚合物基导热材料的研究进展

大多数聚合物由于导热性差等缺点,限制了其在许多领域的应用,因此需要添加导热填料增强聚合物的导热性能,提高材料的使用价值.但是导热填料难以均匀分散到聚合物中,极大地制约了其在高性能热界面材料中的应用,所以需要对填料进行表面功能化,提高其分散性和降低填料与基体之间的界面热阻.无论表面功能化的类型如何,不可避免地都会减弱填料...     

Calderón——Zygmund 型算子及其交换子的有界性

本文得到了Calderón--Zygmund型算子及其与BMO函数或Lipschitz函数生成的交换子在Herz 型 Hardy空间上的一些有界性结果.     

Best Simultaneous Approximation in LΦ(I,X)

Let X be a Banach space and Φ be an Orlicz function.Denote by LΦ(I,X)the space of X-valued Φ-integrable functions on the unit interval I equipped with the Luxemburg norm.For f1,f2,...,fm ∈ LΦ(I,X),a distance formula disΦ(f1,f2,...,fm,LΦ(I,G))is presented,where G is a close subspace of X.Moreover,some existence and characterization results concerning the best simultaneous approximation of LΦ(I,G)in LΦ(I,X)are given.     

α‐Chymotrypsin–catalyzed direct C (Sp3)–H functionalization reactions for synthesis of azaarene derivatives in water

α‐Chymotrypsin from the bovine pancreas has been shown for the first time to display catalytic nonnatural catalytic ability toward the C (sp³)–H functionalization reaction of 2‐methylquinoline and aromatic aldehydes in water. α‐Chymotrypsin exhibited favorable catalytic activity with good adaptability to different substrates. The activity of the enzyme could be improved by adjusting the solvent, temperature, molar ratio of substrates, and protein loading. The products were obtained in moderate to excellent yields (51%‐93%) in 24 samples. This process afforded a potential biocatalytic approach as an alternative to chemical synthesis for azaarene derivatives.     

NA序列完全矩收敛精确渐近性的一般结果

本文利用NA序列的弱收敛定理及概率不等式,证明了其完全矩收敛精确渐近性的一般结果,改进并推广了已有的结果.