选择性传输的仿生水通道的研究进展

水通道蛋白是对水分子具有高选择性和渗透性的跨膜蛋白。仿生水通道是由各种无机或有机材料,如碳纳米材料、有机化合物以及肽等分别自组装而成,旨在模仿天然水通道蛋白的结构和功能。本文介绍了水通道蛋白的种类、结构及其特异性透水机理,在此基础上分别对以碳纳米材料、有机及肽孔的仿生水通道的研究进展进行了综述。重点阐述了三类仿生水通道的材料特性及其对仿生水通道结构和功能的影响。最后针对现有仿生水通道的不足,提出了开发新型仿生水通道面临的挑战,并展望了仿生水通道的发展前景。     

水分子通道蛋白的结构与功能

水分子穿越双磷脂生物膜的输运机理是生理学和细胞生物学中一个长期未能解决的重要问题.AQP1水通道蛋白的发现和鉴定使得人们确认出一个新的蛋白质家族--水通道蛋白家族.正是这一蛋白家族的存在,使得水分子可以进行快速的跨膜传输.由晶体学方法解出的哺乳动物AQP1水通道蛋白的原子结构,最终揭示了水通道蛋白只允许水分子快速传输而阻挡其他的小分子和离子(包括质子H+)的筛选输运机理.本文概述了水通道蛋白的发现和其对水分子的筛选传输机理.     

含AQP仿生膜在水处理中的应用

水通道蛋白(aquaporin, AQP)是一种对水分子具有高选择性和渗透性的跨膜蛋白。近几年来,含AQP的仿生膜有望克服传统膜材料通量与截留率之间的上限平衡问题,因此,它在海水淡化和水处理领域的应用吸引了越来越多研究者的关注。本文对含AQP仿生渗透膜的制备方法及性能进行了综述,分别介绍了含AQP双层膜结构仿生膜和封装含AQP囊泡的仿生膜这两大类膜结构所对应的不同制备方法。同时,对含AQP仿生膜中膜结构的组成方式、装载AQP蛋白的囊泡材料、制膜过程中的操作条件等因素对膜结构和性能的影响进行了探究讨论。综合文中所述不同膜的膜性能,得出现阶段含AQP仿生膜还存在着膜面积小、膜机械强度不够高、AQP装载量较低及易受外界因素影响的缺陷,并提出在克服膜缺陷的同时寻找其他仿生水通道及离子通道的思路,使未来仿生膜获得更宽阔的发展道路。     

纳米通道内酶组装及其催化反应研究进展

研究酶的组装和催化反应不仅有利于探索生命活动的本质,同时对开发酶在工业合成、分析检测、疾病治疗等领域的实际应用价值具有重要的指导意义. 研究发现,酶的有效固定和有序组装是保持酶活性、酶促反应的稳定性和对酶催化过程进行控制的重要途径,而在纳米通道内进行单酶或多酶的有序组装,利用纳米通道的限域效应可有效保持酶的构型进而提高酶催化反应的选择性和催化效率,增强酶级联反应的动力学进程. 本文概述了近年来基于纳米通道的酶反应器在生物传感领域的研究进展,着重描述纳米通道限域空腔内酶的组装方法、酶催化反应及其动力学机制,并展望了基于纳米通道的酶反应器的应用前景.     

黑磷夹层氧化钴纳米片构筑电催化水氧化的仿生通道

不论在自然光合作用系统中,还是在人工能量转换系统如电解水制氢、二氧化碳还原、电化学固氮和金属空气电池中,析氧反应(OER)均是一个非常重要的半反应.OER具有多电子、多质子的特性,反应过程复杂且动力学缓慢.在自然界水氧化过程中,光合系统Ⅱ中的氨基酸残基构筑了专门的质子转移通道和电子转移通道,通过质子耦合电子转移来高效输...     

水溶液中碳酸铀酰化合物的电子结构

应用相对论密度泛函理论系统研究了水溶液中非水合化和水合化碳酸铀酰化合物Cn/m(其中n和m分别为结构中碳酸配体和水配体的个数)的结构.溶剂效应采用类导体屏蔽模型(COSMO),并采用零级规整近似(ZORA)方法考虑标量相对论效应和旋-轨耦合相对论效应.电子跃迁采用包含旋-轨耦合相对论效应的含时密度泛函理论并在相关交换势中采用轨道势能统计平均(SAOP)做近似计算.结果表明碳酸配体对配合物结构和电子跃迁有很大的影响.C3/0配合物的稳定性可归于5f轨道参与了高占据轨道的成键作用.增加碳酸盐配体导致最大波长的蓝移,并在近可见光区域出现高强度的吸收.     

光致增强TiO2超微粉在水相中的分散作用

通过对典型体系的湿润性、ζ电势、粘度和沉降性等界面特性的表征,系统地研究了有/无紫外光照射下TiO2超微粉在水相中的分散特性,发现紫外光对分散作用有明显的光致增强效应,可以改善TiO2超微粉在水相中的分散性能.机理研究表明,这一作用起源于TiO2光致亲水性增强效应.     

奇偶效应诱导的苯丙氨酸类水凝胶手性反转

为了模拟生物大分子(如DNA和蛋白质等)螺旋手性反转的现象,设计合成了4种酰胺基或脲基共价连接L-苯丙氨酸和苯环,外围为二甘醇胺与3-氨基-1,2-丙二醇的C2对称小分子凝胶因子,利用酰胺基(CONH)与脲基(NHCONH)之间的奇偶效应实现了超分子螺旋手性的反转.通过核磁共振波谱仪(1H-NMR和13C-NMR),高分辨质谱仪(HRMS)对凝胶因子结构和分子量进行了分析表征.并运用圆二色光谱(CD)、扫描电子显微镜(SEM)、紫外可见吸收光谱(UV-Vis)和红外光谱(FTIR)对其组装纤维结构和组装方式进行研究.实验结果表明酰胺基(CONH)与脲基(NHCONH)之间的奇偶效应改变凝胶因子的组装方式,调控了超分子手性特征,实现了超分子水凝胶螺旋手性的反转.     

聚甲基丙烯酸纳米水凝胶的水相合成及其磁性功能化

利用十二烷基硫酸钠/吐温20复配表面活性剂和原位生成的聚甲基丙烯酸甲酯(PMMA)种子乳胶,发展了一种可在全水相中"绿色"合成较高浓度的聚甲基丙烯酸(PMAA)纳米水凝胶的新方法.以PMAA纳米水凝胶为前驱体,采用原位氧化沉淀法制备了磁性PMAA纳米微球.利用动态光散射法、FTIR分析、TEM观察、振动样品磁强计测试(VSM)、热重分析(TG)等对纳米水凝胶和磁性微球进行了表征,并探讨了PMAA纳米水凝胶的形成机理.结果表明,吐温20与MAA和PMAA间的氢键作用,促成了交联PMAA/吐温20复合物层在PMMA种子乳胶表面的选择性生长,导致生成了具有核壳结构的PMAA纳米水凝胶.PMAA纳米水凝胶表现出良好的p H响应性,当介质的p H值由1增加至6时,其流体力学体积扩张了近50倍.磁性PMAA纳米微球具有超顺磁性,其饱和磁化强度高达50 A·m~2/kg.     

水杨酰苯胺衍生物分子内电荷/质子转移荧光

将苯甲酰苯胺(BA)类电荷转移(CT)反应基团耦合到具有激发态分子内质子转移(ESIPT)反应通道的水杨酸(SA)分子中,设计合成了苯胺对/间位取代的水杨酰苯胺及其羟基甲基化衍生物邻甲氧基苯甲酰苯胺,考察了环己烷、乙醚、乙腈和甲醇中两类水杨酰苯胺衍生物吸收光谱和荧光光谱的溶剂效应和取代基效应.结果表明,水杨酰苯胺的荧光为SA-型质子转移(PT)荧光,对取代基的依赖性较小;当电子给体苯胺基的给电子能力提高时,如N-甲基水杨酰苯胺分子,其荧光为BA-型CT荧光.而羟基甲基化后的衍生物邻甲氧基苯甲酰苯胺则表现出与BA类似的荧光光谱特性,具有明显的取代基效应.认为水杨酰苯胺衍生物的激发态存在着相互竞争的BA-型CT和SA-型PT通道,二者可经苯胺基上取代基的电子效应调控.     

Modelling carbon dioxide molecule interacting with aquaglyceroporin and aquaporin-1 channels

Aquaporin (AQP) is a family of membrane proteins that enable water and small individual molecules to permeate cell membranes. Examples of these protein channels are aquaglyceroporin and aquaporin-1 (AQP1). Here, we investigate the permeability of carbon dioxide $(\hbox {CO}_2)$ ( CO 2 ) through both aquglyceroporin and AQP1 channels and explain their selectivity mechanisms. We provide a mathematical model which determines the molecular interaction potential between carbon dioxide molecule and an AQP channel. We evaluate this interaction using two approaches, namely discrete-continuum and completed discrete approaches. Both calculations agree well and our results indicate the acceptance of $(\hbox {CO}_2)$ ( CO 2 ) molecule into these channels which is in good agreement with other recent studies.     

Synthetic K+ Channels Constructed by Rebuilding the Core Modules of Natural K+ Channels in an Artificial System

Different types of natural K⁺ channels share similar core modules and cation permeability characteristics. In this study, we have developed novel artificial K⁺ channels by rebuilding the core modules of natural K⁺ channels in artificial systems. All the channels displayed high selectivity for K⁺ over Na⁺ and exhibited a selectivity sequence of K⁺≈Rb⁺ during the transport process, which is highly consistent with the cation permeability characteristics of natural K⁺ channels. More importantly, these artificial channels could be efficiently inserted into cell membranes and mediate the transmembrane transport of K⁺, disrupting the cellular K⁺ homeostasis and eventually triggering the apoptosis of cells. These findings demonstrate that, by rebuilding the core modules of natural K⁺ channels in artificial systems, the structures, transport behaviors, and physiological functions of natural K⁺ channels can be mimicked in synthetic channels.     

Artificial K+ Channels Formed by Pillararene‐Cyclodextrin Hybrid Molecules: Tuning Cation Selectivity and Generating Membrane Potential

A class of artificial K⁺ channels formed by pillararene‐cyclodextrin hybrid molecules have been designed and synthesized. These channels efficiently inserted into lipid bilayers and displayed high selectivity for K⁺ over Na⁺ in fluorescence and electrophysiological experiments. The cation transport selectivity of the artificial channels is tunable by varying the length of the linkers between pillararene and cyclodexrin. The shortest channel showed specific transmembrane transport preference for K⁺ over all alkali metal ions (selective sequence: K⁺ > Cs⁺ > Rb⁺ > Na⁺ > Li⁺), and is rarely observed for artificial K⁺ channels. The high selectivity of this artificial channel for K⁺ over Na⁺ ensures specific transmembrane translocation of K⁺, and generated stable membrane potential across lipid bilayers.     

Light‐Induced Ion Rectification in Zigzag Nanochannels

Ion transport through nanoporous systems has attracted broad interest due to its crucial role in physiological processes in living organisms and artificial bionic devices. In this work, a nanochannel system with a zigzag inner surface was fabricated by using a two‐step anodizing technique. The rectification performance of the zigzag channels was observed by I–V measurement in KCl solution. Unlike channels with asymmetric geometry, the mechanism was analyzed based on the “point effect” of charge distribution and “shape effect” of the zigzag channel. The current rectification ratio decreases from nearly 3.0 to 1.0 when the KCl concentration increased from 0.1 mm to 100 mm . The fabrication of different nanopore systems and exploration of novel mechanisms will help to develop biomimetic membranes for practical applications.     

Biomimetic Transmembrane Channels with High Stability and Transporting Efficiency from Helically Folded Macromolecules

Membrane channels span the cellular lipid bilayers to transport ions and molecules into cells with sophisticated properties including high efficiency and selectivity. It is of particular biological importance in developing biomimetic transmembrane channels with unique functions by means of chemically synthetic strategies. An artificial unimolecular transmembrane channel using pore‐containing helical macromolecules is reported. The self‐folding, shape‐persistent, pore‐containing helical macromolecules are able to span the lipid bilayer, and thus result in extraordinary channel stability and high transporting efficiency for protons and cations. The lifetime of this artificial unimolecular channel in the lipid bilayer membrane is impressively long, rivaling those of natural protein channels. Natural channel mimics designed by helically folded polymeric scaffolds will display robust and versatile transport‐related properties at single‐molecule level.     

Highly active artificial potassium channels having record-high K+/Na+ selectivity of 20.1

Replicating extraordinarily high membrane transport selectivity of protein channels in artificial channel is a challenging task. In this work, we demonstrate that a strategic application of steric code-based social self-sorting offers a novel means to enhance ion transport selectivities of artificial ion channels, alongside with boosted ion transport activities. More specifically, two types of mutually compatible sterically bulky groups (benzo-crown ether and tert-butyl group) were appended onto a monopeptide-based scaffold, which can order the bulky groups onto the same side of a one-dimensionally aligned H-bonded structure. Strong steric repulsions among the same type of bulky groups (either benzo-crown ethers or tert-butyl groups), which are forced into proximity by H-bonds, favor the formation of hetero-oligomeric ensembles that carry an alternative arrangement of sterically compatible benzo-crown ethers and tert-butyl groups, rather than homo-oligomeric ensembles containing a single type of either benzo-crown ethers or tert-butyl groups. Coupled with side chain tuning, this social self-sorting strategy delivers highly active hetero-oligomeric K⁺-selective ion channel (5F12‧BF12)_n, displaying the highest K⁺/Na⁺ selectivity of 20.1 among artificial potassium channels and an excellent EC₅₀ value of 0.50 μmol/L (0.62 mol% relative to lipids) in terms of single channel concentration     

Na-nitroprusside and HgCl2 modify the water permeability and volume of human erythrocytes

The passage of water through the aquaporin-1 (AQP1) transmembrane channel protein of the human erythrocyte is known to be inhibited by organic mercurials such as p-chloromercuribenzoate (pCMB), which react with the free SH-group of the critical cysteine (Cys189) located near the constriction of the AQP1 water-specific channel. Sodium nitroprusside (SNP), which is known as a nitric oxide (NO) donor in interactions with SH-containing molecules, is shown here to suppress the diffusional water permeability (P(d)) of the erythrocyte membrane, presumably as a result of reaction with the Cys189 of the human erythrocyte AQP1 water channels. Further, treatment of erythrocytes with HgCl(2) is found to result in a cell volume decrease that can be related to activation of membrane K(+)-selective Gárdos channels and subsequent loss of intracellular K(+) and cell shrinkage. The variations in P(d) and volume of the erythrocyte were deduced from induced variations in the measured proton ((1)H) nuclear magnetic resonance (NMR) transverse (T(2)) relaxation functions of water exchanging between diamagnetic intracellular and paramagnetic extracellular compartments of the 20-25% hematocrit samples. The extracellular solvent contained 10 mM membrane-impermeable paramagnetic Mn(2+) ions. The (1)H-T(2) NMR technique allows determination of the time constant tau(exch) (for exchange of the erythrocyte intracellular water) that is inversely proportional to the permeability coefficient P(d) when the intracellular water volume is left unmodified, as in the case of SNP-treated erythrocytes. However, for HgCl(2)-treated erythrocytes, this technique showed simultaneous variation of both tau(exch) and the volume ratio V(in)/V(out) of intracellular and extracellular water in proportions suggesting that P(d) was left unmodified. The HgCl(2) effect has been found to be partly reversible by the reducing activity of added mercaptoethanol.