A tumor pH-responsive complex: carboxyl-modified hyperbranched polyether and cis-dichlorodiammineplatinum(II)

To realize the pH-targeting delivery of antitumor drug cis-dichlorodiammineplatinum(II) (cisplatin, CDDP), a tumor pH-responsive polymer-platinum(II) complex (Suc-HPMHO-CDDP) from carboxyl-modified hyperbranched polyether (Suc-HPMHO) and cisplatin was designed and prepared. Because of the existence of hydrophobic core and ionization of surface carboxylic acid, Suc-HPMHO showed reversible pH-response in aqueous solution, and its responding pH value could be readily adjusted by only changing the degree of carboxylation of Suc-HPMHO. With plenty of terminal carboxyl groups, Suc-HPMHO could form the complex with CDDP by substituting the chloride ions with carboxyls. Methyl tetrazolium (MTT) assay showed that Suc-HPMHO had low cytotoxicity, while Suc-HPMHO-CDDP complex presented a similar antitumor effect with the free CDDP. Under the tumor acidic pH (pH(e)), Suc-HPMHO-CDDP complex deposited around/in cells because of its pH-response. Therefore, the pH-targeting of Suc-HPMHO-CDDP complex to tumor tissue could be realized. All of these results show that the tumor pH-responsive Suc-HPMHO-CDDP complex is a potential pH-targeting drug delivery system in cancer therapy.     

基于两阶段解耦的可变功能机械模块划分研究

可变功能机械是一类多功能集成的机械产品, 较适合于采用模块化设计方法. 但是, 这类产品的每个功能都有相应的私有构件与之对应, 除此之外还有一定数量的共享构件, 造成各功能(相应地各客户需求)间存在不同程度的耦合性, 因此传统的单纯解决构件间耦合的模块划分方法存在困难. 为解决这一问题, 本文提出通过分阶段解耦的方法实现可变功能机械的模块划分, 其中第一阶段通过引入客户需求设计结构矩阵, 将与产品功能相关的客户需求先进行解耦, 以此解决单一解耦方式无法解决客户需求耦合的问题; 第二阶段通过引入需求结构关联矩阵与构件设计结构矩阵, 根据构件内部的关联关系进行结构解耦, 获得模块内部高耦合、模块之间低耦合的模块划分方案. 在此基础上, 通过引入模块化指数的评判标准, 解决产品模块聚合度和模块间耦合度相背离的问题, 实现了多种模块划分方案的选优. 最后通过一个多功能电钻案例来验证这一两阶段解耦模块划分方法的可行性.     

弧拟凸函数的性质

本文对文［１］中引入的弧拟凸函数的性质做了进一步研究，找出了弧拟凸性与严格弧拟凸性及下半连续性之间的联系。同时，还对拟线性函数的性质做了进一步研究。     

Morphology analysis of magnesium hydroxide prepared by magnesium oxide hydration within seawater

In order to investigate the microstructure of magnesium oxide hydration product within seawater, two reaction conditions (liquid‐solid and gas‐liquid‐solid) and two solutions (seawater and deionized water) were adopted for magnesium oxide hydration. The characterization of the hydration product using X‐Ray diffraction and scanning electron microscope was performed. Experimental results indicate that cations and anions in seawater promote the hydration. Most of the hydration products within seawater system display flower‐like morphology, but the agglomeration phenomenon is not obvious within deionized water system, especially for the supernatant layer products within deionized water system under gas‐liquid‐solid reaction condition. There was no stratification phenomenon occurred when MgO hydrated with seawater under three‐phase reaction condition.     

光透薄层光谱电化学法研究灿烂甲酚兰的电极过程

在铂网光透电极上,采用紫外-可见和电子顺磁共振(ESR)技术研究了灿烂甲酚兰(BCB)的电极过程。测定了BCB的标准式电极电位和电子转移数。结果表明,BCB在铂电极上进行可逆的单电子转移反应,并且氧化态和还原态均较强烈地吸附在铂电极上。ESR波谱的现场监测直接确证了单电子转移过程,并首次发现BCB的氧化态在正电位激发下呈三线态,还原态具有单电子自由基。另外对BCB的电极过程机理进行了初步探讨。     

Ion Pair Catalyst - Pentanidinium

In this account, we further describe our already developed N-sp² hybrid guanidinium as an efficient phase-transfer catalyst and ion pair catalysis based on N-sp² hybrid pentanidinium and its application in some new reactions. The sp³ hybrid quaternary ammonium salt has a tetrahedral structure, which means that three sides of it can be effectively steric, allowing the remaining side to be close to the substrate. However, the sp² hybrid ammonium salt allows the substrate to form ion pairs from both directions respectively, so it is a greater challenge to control the stereoselectivity of the reaction. Van der Waals forces, such as hydrogen bonds and interactions, have been used to make electrophiles approach from a certain direction, leading to a higher enantioselectivity. Based on the above idea, we designed an N-sp² hybrid phase-transfer catalyst, pentanidinium. Pentanidinium has five conjugated nitrogen atoms, one of which has a formal positive charge, which is necessary for it to become an ion pair catalyst. We have confirmed that pentanidinium can catalyze α-hydroxylation of 3-substituted-2-oxindoles, Michael addition of 3-alkyloxindoles with vinyl sulfone, and alkylation reactions of sulfenate anions and dihydrocoumarins, desymmetrization of pro-chiral sulfinate to afford enantioenriched sulfinate esters. Pentanidinium with side chain structure changes can also be catalyzed efficiently with enantioconvergent halogenophilic nucleophilic substitution, including azidation and thioesterification. In the reaction catalyzed by pentanidinium, it always attracts us with the advantages of low catalytic load and good enantioselectivity.     

Spectral heat content on a class of fractal sets for subordinate killed Brownian motions

We study the spectral heat content for a class of open sets with fractal boundaries determined by similitudes in ${\mathbb{R}}^d$, $d\ge 1$, with respect to subordinate killed Brownian motions via $\alpha /2$-stable subordinators and establish the asymptotic behavior of the spectral heat content as $t\to 0$ for the full range of $\alpha \in (0,2)$. Our main theorems show that these asymptotic behaviors depend on whether the sequence of logarithms of the coefficients of the similitudes is arithmetic when $\alpha \in [d-\mathfrak{b},2)$, where $\mathfrak{b}$ is the interior Minkowski dimension of the boundary of the open set. The main tools for proving the theorems are the previous results on the spectral heat content for Brownian motions and the renewal theorem.     

Superconductivity in an Orbital-Reoriented SnAs Square Lattice: A Case Study of Li0.6Sn2As2 and NaSnAs

Searching for functional square lattices in layered superconductor systems offers an explicit clue to modify the electron behavior and find exotic properties. The trigonal SnAs₃ structural units in SnAs-based systems are relatively conformable to distortion, which provides the possibility to achieve structurally topological transformation and higher superconducting transition temperatures. In the present work, the functional As square lattice was realized and activated in Li_0.6Sn₂As₂ and NaSnAs through a topotactic structural transformation of trigonal SnAs₃ to square SnAs₄ under pressure, resulting in a record-high T_c among all synthesized SnAs-based compounds. Meanwhile, the conductive channel transfers from the out-of-plane p_z orbital to the in-plane p_x+p_y orbitals, facilitating electron hopping within the square 2D lattice and boosting the superconductivity. The reorientation of p-orbital following a directed local structure transformation provides an effective strategy to modify layered superconducting systems.     

Synthesis of rare-earth metal-containing polymers and their fluorescence properties

Four kinds of polymeric β-diketone compounds, including poly(vinylbenzyldibenzoylmethane)(1), poly(vinylbenzylacetoacetone)(2), poly(vinylbenzyl-2-thenoyltrifluoroacetone)(3) and poly(p-benzoylacetylstyrene)(4) were synthesized. And then polymeric β-diketone-europium(III), -terbium(III), -samarium(III), -dysprosium(III), -europium(III)-gadolinium(III), -terbium(III)-gadolinium(III), and -europium(III)-terbium(III) chelates were also synthesized. The chelate structures were confirmed. The influence of the structure on the fluorescence properties was investigated. The fluorescence intensity of polymeric rare-earth metal complexes is closely related to the ligand and metal content. Polymeric complexes possess a higher fluorescence stability than that of corresponding low-molecular-weight complexes.