On the Function and Structure of Synthetically Modified Porins

The attachment of modulators to a trimeric porin ion channel was investigated (see picture of the trimer with a crown ether modulator (orange)). The interplay of modulator and protein is essential for the conformational heterogeneity of the hybrid channel. Single‐site attachment in large pores is not sufficient to change the electrophysiological characteristics of the pores—such change requires additional noncovalent interactions or second‐site attachments.

     

Cover Picture: Direct C?H Metalation with Chromium(II) and Iron(II): Transition‐Metal Host / Benzenediide Guest Magnetic Inverse‐Crown Complexes (Angew. Chem. Int. Ed. 18/2009)

Chromation and ferration are the latest additions to the concept of alkali‐metal‐mediated metalation, as described by J. Klett, R. E. Mulvey, and co‐workers in their Communication on page 3317 ff. While the more electropositive sodium is essential for the reaction, it is the less electropositive chromium or iron that actually performs deprotonation of benzene. This novel reactivity can be likened to a game of chess in which the queen (Na) holds the king in check, while the knight (Cr, Fe) scores checkm(etal)ate.

     

Sulfonated poly(ether ether ketone) as an alternative charged material to poly(vinyl chloride) in the design of ion-selective electrodes

To date, poly(vinyl chloride) (PVC) is the most used polymer in the design of ion selective electrode (ISE) membranes. This paper is focused on the use of sulfonated poly(ether ether ketone) (SPEEK) as an alternative material to PVC for the design of ISEs. SPEEK of the desired degree of sulfonation is synthesized from poly(ether ether ketone) (PEEK). An NH₄⁺-ISE has been chosen as a model electrode to study the efficiency of SPEEK as polymer matrix of the membrane. The material was evaluated in ionophore free ion exchanger membranes as well as in ion-selective electrodes membranes containing nonactine as ionophore. Analytical performance parameters of the prepared electrodes were evaluated. The electrodes show a slope between 50 and 60 mV dec⁻¹ depending on both the calibration medium and the membrane composition. A linear range of response between 10⁻⁴ and 1.0 M and a lifetime of 1-2 months were obtained. The interferences of cations such us Ca²⁺, Na⁺, Li⁺ and K⁺ over the prepared ISEs are studied as well. Although the plasticizer in the SPEEK based membrane matrix is not necessary, its presence improves the sensibility. This makes SPEEK a good potential choice over alternative membrane matrices reported in the literature and a promising platform for the establishment of membrane components.     

Design and synthesis of simple macrocycles active against vancomycin-resistant enterococci (VRE)

16-membered meta,para-cyclophanes mimicking the vancomycin binding pocket (D-O-E ring) were designed and synthesized. The structural key features of these biaryl ether containing macrocycles are (1) the presence of beta-amino-alpha-hydroxy acid or alpha,beta-diamino acid as the C-terminal component of the cyclopeptide and (2) the presence of a hydrophobic chain or lipidated aminoglucose at the appropriate position. Cycloetherification by an intramolecular nucleophilic aromatic substitution reaction (S(N)Ar) is used as the key step for the construction of the macrocycle. The atropselectivity of this ring-closure reaction is found to be sensitive to the peptide backbone and chemoselective cyclization (phenol versus primary amine) is achievable. Glycosylation of phenol was realized with freshly prepared 3,4,6-tri-O-acetyl-2-N-lauroyl-2-amino-2-deoxy-alpha-D-glucopyranosyl bromide under phase-transfer conditions. Minimum inhibitory concentrations for all of the derivatives are measured by using a standard microdilution assay, and potent bioactivities against both sensitive and resistant strains are found for some of these compounds (MIC (minimum inhibitory concentration) = 4 microg mL(-1) against VRE). From these preliminary SAR studies, it was anticipated that both the presence of a hydrophobic substituent and an appropriate structure of the macrocycle were required for this series of compounds to be active against VRE.     

Royal crown-shaped electride Li3-N3-Be containing two superatoms: new knowledge on aromaticity

The structure and aromaticity of a royal crown-shaped molecule Li(3)-N(3)-Be are studied at the CCSD(T)/aug-cc-pVDZ level. This molecule is a charge-separated system and can be denoted as Li(3) (2+)N(3) (3-)Be(+). It is found that the Li(3) (2+) ring exhibits aromaticity mainly because the Li(3) (2+) ring can share the pi-electron with the N(3) (-3) ring. The 4n+2 electron counter rule can be satisfied for the Li(3) (2+) subunit if the shared pi valence electron of N(3) (3-) subunit is also taken into account. This new knowledge on aromaticity of a ring from the interactions between subunits is revealed first time in this paper. Li(3)-N(3)-Be can be also regarded as a molecule containing two superatoms (Li(3) and N(3)), which may be named as a "superomolecule." Li(3)-N(3)-Be is a new metal-nonmetal-metal type sandwich complex. The N(3) (3-) trianion in the middle repulses the electron clouds of the two metal subunits (mainly to the Li(3) superatom) to generate an excess electron, and thus Li(3)-N(3)-Be is also an electride. This phenomenon of the repulsion results in: (a) the HOMO energy level increased, (b) the electron cloud in HOMO distended, (c) the area of the negative NICS value extended, and (d) the VIE value lowered. So the superomolecule Li(3)-N(3)-Be is not only a new metal-nonmetal-metal type sandwich complex but also a new type electride, which comes from the interaction between the alkali superatom (Li(3)) and the nonmetal superatom (N(3)).     

一种新型微乳液体系的制备及在含油污泥原油回收中的应用

双十二烷基二苯醚双磺酸钠在低浓度时有正辛醇、正庚烷、盐存在的情况下能形成中相微乳液.采用正交试验确定了中相微乳液的最佳组成:m(自制表面活性剂)为0.253g,m(正辛醇)为0.411g,m(NaCl)为0.232g,蒸馏水(水相)5mL,正庚烷(油相)5mL.考察了中相微乳液制备过程中的电导率变化和温度对中相微乳液稳定性的影响.探讨了脱油温度、脱油时间以及含油污泥处理量对含油污泥中原油脱除率的影响.实验结果表明:随温度的升高和时间的延长,处理油泥质量的减小,脱油率都有一定的增加,最佳条件下含油污泥中原油脱除率可达98.9%,并探讨脱油机理.     

二甲醚精制分离序列的动态规划

针对合成气一步法合成二甲醚的精馏精制过程,研究分离二甲醚-二氧化碳-甲醇-水混合物的顺序问题.根据精馏分离过程特点,将二甲醚混合物精馏精制分离过程分成多阶段的决策过程,建立相应的分离工艺方案动态规划模型.在模型求解过程中,提出年操作费用最小准则,并利用动态规划算法计算出不同阶段、不同决策下的目标函数最优解,得到最优的分离序列.结合研究体系的特点,将动态规划结果加以改进,给出二甲醚精馏精制最优分离方案.     

一种新型多官能度乙烯基醚树脂的制备及在光刻负胶中的应用

以苯乙烯,2-异氰酸甲基丙烯酸酯(IEMA),以及乙二醇单乙烯基醚(EGME)等为原料,分两步合成了一种主链为聚苯乙烯结构的多乙烯基醚(VEs)树脂(PSIM-VE).通过测定该树脂的红外光谱、核磁氢谱及核磁碳谱,确定了其分子结构式.测定了该树脂的紫外透光性,并且研究了基于该树脂的紫外光刻负胶以甲苯及四氢呋喃为溶剂时的成膜性及紫外光固化性能.通过接触式光刻工艺,在光刻胶膜层上得到了4μm周期的光栅结构.     

纳米SiO2/苄基缩水甘油醚丙烯酸酯活性稀释剂的制备与表征

以苄基缩水甘油醚丙烯酸酯( BGEA)、纳米二氧化硅与γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)合成了一种纳米SiO2改性的活性稀释剂SiO2-BGEA.利用SEM观察固化薄膜的断裂截面与表面.后将SiO2-BGEA作为稀释剂加入到环氧丙烯酸树脂中配制成光固化涂料,利用TG、紫外—可见分光光度计等表征手段对其光固化膜的热性能、透明度等性能进行研究.     

活性稀释剂苄基缩水甘油醚丙烯酸酯的合成及性能表征

本文以苄基缩水甘油醚和丙烯酸为原料合成活性稀释剂苄基缩水甘油醚丙烯酸酯(BGEA),研究了反应温度、催化剂和阻聚剂用量对反应的影响.结果表明最佳的反应条件为:反应温度110℃左右,催化剂N,N’-二甲基苄胺质量分数为0.9%,阻聚剂对甲氧基苯酚质量分数为0.2%.后将BGEA作为稀释剂加入到双酚A型环氧丙烯酸树脂中配制成光固化涂料,利用TG、AFM等表征手段对光固化膜的热性能、表面形貌及物理机械性能进行研究.