Hydrophilic anchors for transmembrane anion–π slides

The concept of hydrophilic anchoring is introduced to activate rigid oligonaphthalenediimide (O-NDI) rods as anion–π slides for multi-ion hopping across lipid bilayers. We report that short peptide solubilizers suffice to reach the rare combination of high activity and high selectivity that is needed for anion pumping in vesicles.     

Effect of sodium deoxycholate and sodium cholate on DPPC vesicles: A fluorescence anisotropy study with diphenylhexatriene

Effects of two bile salts, namely sodium deoxycholate (NaDC) and sodium cholate (NaC), on DPPC small unilamellar vesicles have been investigated using the steady-state fluorescence anisotropy (r _ss ) of diphenylhexatriene (DPH) as a tool. It was found that the variation of r _ss is sensitive enough to monitor different stages of interaction of bile salts with DPPC vesicles. NaDC induced significant changes in the membrane well below its CMC (6 mM). Even at 4 mM, which is still lower than the CMC, the phospholipids were completely solubilised by the NaDC micelles. The effect of NaC on DPPC vesicles, however, was much less significant, especially in the sub-micellar concentration regime. Being more hydrophilic NaC does not interact with the membrane efficiently. Complete solubilisation of phospholipids took place only when the concentration of NaC was above its CMC (16 mM). The experiments also showed that the bile salt-induced changes of vesicle structure were strongly dependent on the concentration of the bile salt and not on the molar ratio of lipid and bile salt.     

变温拉曼光谱和DSC探讨人参皂苷Rb1分子与DPPC双层膜的作用

研究人参皂苷分子与生物膜的作用对于深入了解中药人参的药理活性及其生物学功效至关重要。DPPC作为具有双分子层结构的脂质分子,常被许多国内外学者作为模拟膜的模型来研究药物分子与细胞膜的作用;Rb1作为中药人参中的重要皂苷成分,具有显著的药理学功效和生物性能。拉曼光谱是探讨分子间作用的有力工具,差示扫描量热技术（differential scanning calorimetry, DSC）是研究脂双层分子单体及其与药物分子作用的常用技术,而将两者结合研究药物分子对细胞膜作用的研究的报道较少。本文采用变温拉曼光谱和DSC探讨了在温度变化条件下人参皂苷Rb1单体分子与DPPC双层膜的作用。通过拉曼光谱测试,在Rb1作用前后,DPPC分子极性头部O—C—C—N+和C—C伸缩振动区域以及烷基链部分C—H键的伸缩振动区域的变化表明,随着温度的增加,含有一定浓度Rb1的DPPC磷脂极性头部旁氏构象没有发生变化,脂酰链的无序性构象增多,侧向排列的无序性增强,DPPC脂双层的流动性增加。由DSC实验得到的几个热力学常数[相变温度（T_m）、半峰宽（ΔT_1/2）及相转变焓值（ΔH）]的变化表明,DSC进一步验证了变温拉曼实验结果,随着Rb1浓度的增大,DPPC双层膜的相变温度显著下降,流动性增强,说明Rb1对DPPC双层膜的影响较大。     

新型三唑桥联杂化复式环糊精手性固定相的构筑及性能研究

运用Cu(I)催化的1,3-偶极环加成反应(点击化学), 以乙酸酐修饰单叠氮环糊精为底层, 炔基衍生的天然环糊精为顶层, 在硅胶表面通过自下而上的方式构建了一种新型“天然-乙酰基衍生化”三唑桥联杂化复式环糊精手性固定相材料(ANCDCSP), 并通过红外光谱、热重和元素分析等测试手段对其结构进行了表征. 该固定相材料可提供包合作用、氢键给体、氢键受体、偶极-偶极作用等多重识别位点以及底层和顶层环糊精间的协同效应. 在HPLC反相分离模式下, 该固定相材料对10种丹磺酰氨基酸类(Dns amino acids)、10种小分子芳香酸(phenyl carboxylic acids)、5种异噁唑啉类(isoxazolines)以及多种其它手性对映体具有良好的手性拆分效果. 其中Dns-Phe、DL-3PhLacA以及Bendroflumethiazide的分离度分别达到5.3、4.1和4.1, 且多数手性对映体的分离度优于课题组先前制备的复式天然环糊精手性固定相(DCDCSP).     

大豆分离蛋白与壳聚糖复合材料的制备

蛋白质与多糖的静电作用是生物体内一个基本医学-化学现象,是实现自组装的主要驱动力,可利用这种非共价作用设计和构筑理想的微结构。 以大豆分离蛋白(Soybean Protein Isolates,SPI)和壳聚糖(Chitosan,CS)为原料,采用浊度法考察了配比、溶液pH值、离子强度和温度对SPI与CS在溶液中相互作用的影响。 结果显示,由于pH值影响静电作用强度,从而成为影响SPI与CS相互作用的主要因素,其中,当pH值为5.5~6.6时,SPI与CS可以实现有效结合。在较低的离子强度下,有利于形成具有紧凑结构的CS/SPI聚集体,较高离子强度下聚集体发生解离。 蛋白质受热发生变性,多肽链上的疏水氨基酸残基暴露在溶液中,导致与壳聚糖链的疏水作用增强。 DLS结果显示,CS与SPI自组装形成了分布均一的纳米粒子,变性后的SPI与CS形成的纳米粒子粒径有所增大,分布均一;经戊二醛交联,粒径有所减小。 SEM显示,壳聚糖单层膜表面存在龟裂现象,与SPI形成双层膜后龟裂消失;同时,单层膜厚度约为300 nm,双层膜厚度约为500 nm。     

含缺陷双层石墨烯的纳米压痕模拟研究

石墨烯具有独特的力学、电学性能,被誉为是具有战略意义的新材料,具有广泛的应用前景. 目前生产的石墨烯含有各种缺陷,相较于完美石墨烯,其仍有较大应用价值. 因此有必要研究和掌握缺陷对石墨烯性能的影响,以便在目前的生产技术下,推动其工业化应用. 采用Tersoffff 势来模拟C—C 共价键的相互作用,Lernnard-Jones 势来模拟非成键碳原子之间相互作用力,基于分子动力学模拟了金刚石压头压入含缺陷双层石墨烯的纳米压痕过程,讨论了Lernnard-Jones 势函数的截断半径最佳值以及得到了典型的载荷-位移曲线. 重点探讨了Stone-Thrower-Wales、空位(包括单空位和双空位缺陷) 以及圆孔缺陷当位置不同和数目不同时对石墨烯力学性能的影响. 得出结论:薄膜中心存在缺陷时,破坏强度下降幅度特别明显. 空位缺陷在压头半径范围内存在时,临界载荷与缺陷与薄膜中心的距离成线性关系;缺陷数目越多,其杨氏模量、破坏强度等就越低. 圆孔缺陷数目在压头范围外达到一定浓度后会使石墨烯的力学性质显著降低. 本文结论也说明石墨烯结构稳定,对小缺陷不敏感,缺陷石墨烯仍具有较好的性能和使用价值.      

Tuning the energy gap of bilayer α-graphyne by applying strain and electric field

Our density functional theory calculations show that the energy gap of bilayer α-graphyne can be modulated by a vertically applied electric field and interlayer strain. Like bilayer graphene, the bilayer α-graphyne has electronic properties that are hardly changed under purely mechanical strain, while an external electric field can open the gap up to 120 meV. It is of special interest that compressive strain can further enlarge the field induced gap up to 160 meV, while tensile strain reduces the gap. We attribute the gap variation to the novel interlayer charge redistribution between bilayer α-graphynes.These findings shed light on the modulation of Dirac cone structures and potential applications of graphyne in mechanicalelectric devices.     

Superfluidity of indirect excitons vs quantum Hall correlation in double Hall systems: Different types of physical mechanisms of correlation organization in Hall bilayers

Bilayer Hall systems can be divided into two groups—with and without tunneling of carriers across the barrier between layers. We demonstrate that these both classes differ in topology sense which leads to the distinct quantum Hall hierarchy. In the case of forbidden interlayer carrier tunneling we developed the Metropolis Monte Carlo simulation for an energy competition of the reentrant integer quantum Hall state against the superfluid Bose Einstein condensate of indirect excitons in double-layer 2D Hall systems, GaAs/GaAlAs/GaAs and b-graphene/hBN/b-graphene, with complementary layer filling, ${\nu }_{bot}+{\nu }_{top}=1$. The resulted phase diagrams for both systems have been determined in consistence with the experimental data.     

压电压磁双层板的锯齿形结构理论

压电压磁复合材料具有力、电、磁之间的多场耦合特性,在智能元器件上有广泛的应用前景,近年来得到了众多研究者的关注.以压电压磁双层板为例,基于锯齿形结构理论的思想,在每一层中单独假设位移、电势和磁势,通过满足界面处位移和剪应力连续及上下表面剪应力为零的条件,将独立变量或常数的个数降低为7个.进一步采用变分原理,建立了相应的控制方程和边界条件.针对四边简支的压电压磁双层板,给出了类似于经典纳维解的解析解,并进行了数值计算.结果表明,采用锯齿形板理论,可以保证剪应力在界面是连续的,这在电磁耦合特性依赖于界面传递的压电压磁复合材料结构的分析中十分重要.     

三维各向异性超常媒质交错结构的亚波长谐振特性研究

以填充各向异性超常媒质矩形波导中的电磁场解为基础,通过建立与求解填充各向异性超常媒质交错结构的矩形谐振腔的谐振方程,深入研究了三维各向异性超常媒质交错结构的亚波长谐振特性.结果发现,三维各向异性超常媒质交错结构的亚波长谐振条件具有更为多样性的物理解,在固定参数下,其物理解的个数往往超过一个,还针对谐振结构的横向尺寸对亚波长谐振条件的影响进行了讨论.结果表明,随着横向尺寸的减小亚波长谐振条件的物理解数量将逐渐增多直至趋于无穷.这意味着即使超常媒质的本构参数无法控制,仍然可以通过调节谐振结构的横向尺寸来得到亚波长谐振腔. 关键词： 各向异性 超常媒质 交错结构 亚波长谐振