孔蛋白-磷脂仿生膜的葡萄糖氧化酶电化学

采用孔蛋白（MspA）和双肉豆蔻磷脂酰胆碱（DMPC）在玻碳（GC）基底表面成功构建有仿生特性的纳米通道膜,同时将葡萄糖氧化酶（GOD）修饰于膜上. 使用循环伏安法研究GOD/MspA-DMPC/GC电极的GOD直接电化学过程以及其对氧气和葡萄糖的响应. 研究发现,MspA与DMPC形成的仿生纳米通道膜内,GOD在接近生物体系FAD/FADH标准电位处实现了自身两质子、两电子表面控制的电化学反应. MspA与DMPC的仿生纳米通道膜体系为GOD提供了理想活性环境.     

简易制备高整流比的异质纳米通道

生命体内的离子通道在各种生物功能调节过程及生命活动中具有重要的意义.模仿生物孔道的离子输运性质,构筑人工纳米通道,并研究人工纳米通道的离子输运性质是一项具有重大意义的研究课题.本文通过双面阳极氧化和原位扩孔结合的方法制备了对称结构的沙漏形氧化铝纳米通道.通过在对称结构的沙漏形氧化铝（AAO）纳米通道一侧粘贴一层透明胶带,经过热处理后,获得了一种具有高整流比的有机-无机异质纳米通道.基于非对称的结构和电荷分布,氧化铝纳米通道与有机纳米通道在复合区域形成异质结构.由于多孔AAO纳米通道和有机纳米通道的协同效应,异质纳米通道表现出独特的纳米流体二极管特性,即在比较宽的pH范围内具有单一的整流方向.在该体系中,氧化铝纳米通道内壁的羟基和有机纳米通道内壁的羧基在不同pH值下所带电荷性质不同,使异质结构纳米通道内壁表面电荷的性质和电荷密度发生改变,可以通过调节体系的pH来调控通道内的离子传输.     

仿生纳米通道的制备、修饰及生物分析应用

纳流控作为一种新兴技术,近年来得到了广泛关注.其产生和发展伴随着新流体现象的发现和新型器件的诞生.纳米流体中独特的物质传输性质和潜在的应用引起了广泛关注.迄今为止,纳米通道器件在DNA测序、单分子传感、能源储存与转换、离子门控等方面显示出了巨大的应用前景.本文总结了仿生纳米通道的设计与制备、纳米通道功能化修饰的策略及其在生物分析中的应用研究,并思考了仿生纳米通道的发展与面临的挑战.     

仿生制备多级化纳米通道及其离子电流行为研究

自然界中的多级化离子通道在生命活动中发挥着至关重要的作用.生物体内的多级化离子通道包括两种类型:胞间连接通道和多级复合离子通道.研究人员以生物体内的多级化离子通道结构为模型,在仿生制备多级化纳米通道方面做了大量的研究工作.本文综述了人工多级化纳米通道的离子电流行为及其在能量转换中的应用,并展望了仿生制备的多级化纳米通道在未来的应用前景.     

基于仿生膜的功能化单纳米通道在分析化学中的应用

灵感来源于蛋白质离子通道的仿生功能化单纳米通道,已逐渐成为一种成熟的单分子检测技术和离子整流器。功能化纳米通道包括两种:基因改造的蛋白质纳米通道和固体加工的纳米通道。常用的固体纳米通道有三种:在纳米氮化硅或石墨烯上用聚焦离子束(FIB)或电子束(FEB)轰击得到的纳米通道,化学腐蚀聚合物薄膜中的重金属离子轨迹得到的锥形纳米通道和拉制毛细管或激光刻蚀得到的玻璃纳米孔。相对于蛋白质纳米通道,固态的人工纳米通道具有更优越的机械稳定性,并可用于各种功能基团的修饰。经过近十年的发展,包括蛋白质纳米通道在内的各种仿生的纳米通道已广泛用于对小分子、蛋白质和聚合物等其他一些对象的定性和定量检测。本综述详细介绍了近年来国内外该领域的发展,并对未来的发展方向作了简要的展望。     

聚合物基纳米通道的构筑、功能化及应用研究进展

纳米通道在生命过程中起着至关重要的作用。利用聚合物基纳米通道研究离子、分子等在通道内的输运、识别、响应及门控的仿生过程和性质,受到了科学家的广泛关注和研究。目前,构筑聚合物基纳米通道最常用方法是径迹刻蚀技术。刻蚀后的固态纳米通道具有可功能化的基团,科学家正在广泛开展探究纳米孔道功能化的方法研究。本文主要从几种聚合物的刻蚀方法及形状控制,来介绍纳米通道的构筑方法。同时,本文还总结了纳米通道功能化修饰的常用方法。最后,介绍了纳米通道在多方面的应用、未来的展望以及目前该领域存在的一些挑战。     

基于仿生智能纳米孔道的先进能源转换体系

自然界中的生命体系经过40多亿年的进化,实现了对能源的高效转换、存储和利用.特别是生物膜上的各类孔道结构在其中起着重要作用.基于仿生智能纳米通道的先进能源转换体系从生物离子通道中获取与能量转换相关的启示(例如,电鳗放电、ATP合成、视网膜、紫膜等),从原理和结构上模仿生命体系中高效能量转换的某一个侧面,通过产能材料的设计和转换器件的组装,实现机械能到电能、光能到电能、光能到化学能等不同能量形式之间的转换.我们综述了目前应用人工合成的纳米尺度孔道结构进行仿生能源转换的三个热点领域:纳米流体动能-电能转换,纳米流体反向电渗析系统和基于仿生智能纳米孔道的先进能源转换体系.基于智能纳米孔道的能源转换方法摆脱了传统发电设备所必需的机械转动装置的束缚,在可以预见的范围内,仿生产能器件的效能必将超越已有人工体系,为面向未来的能源技术的创新提供了新思路,新理论和新方法.     

基于贻贝仿生化学的分离功能材料

贻贝仿生的表面化学是近年来材料学、化学、生物医学等领域的交叉研究热点。多巴胺可以作为贻贝足丝蛋白(Mfp)超强黏附特性的模型分子,通过复杂的氧化-自聚和组装,形成多种功能的聚多巴胺(PDA)纳米涂层和纳米粒子,在分离膜、吸附材料、生物医用材料、生物黏结剂等领域有着广阔的应用前景。本研究小组近年来持续开展了基于贻贝仿生化学的分离功能材料制备与结构调控的研究工作,率先将多巴胺表面沉积方法应用于多孔分离膜表面的构建与功能化,提出了多巴胺的自聚-沉积过程模型,进而验证了PDA沉积层的纳滤分离特性,建立了一条简单方便的膜表面功能化与纳滤膜制备新途径。本文主要对基于贻贝仿生化学的分离功能材料,特别是分离膜的研究进展进行综述,并对将来的发展趋势进行展望。     

框架核酸辅助的仿生膜构建

仿生膜的构建有利于了解并掌握生物膜的功能及其机理, 同时对其在生命医学及疾病诊断等相关领域的应用具有重要意义. 以框架核酸为组装单元, 构建新型仿生膜材料是一种有效且具有发展前景的方法和研究方向. 本文综述了框架核酸的设计、 制备与表征, 总结了框架核酸修饰到脂质膜上的方式. 同时, 对框架核酸辅助的仿生膜的应用情况进行了阐述, 并探讨了框架核酸在仿生膜研究领域所面临的机遇与挑战.     

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。     

Construction and application of bioinspired nanochannels based on two-dimensional materials

With the development of nanotechnology and materials science, bioinspired nanochannels appeared by mimicking the intelligent functions of biological ion channels. They have attracted a great deal of attention in recent years due to their controllable structure and tunable chemical properties. Inspired by the layered microstructure of nacre, 2D layered materials as excellent matrix material of nanochannel come into our field of vision. Bionic nanochannels based on 2D materials have the advantages...     

The Combination of 2D Layered Graphene Oxide and 3D Porous Cellulose Heterogeneous Membranes for Nanofluidic Osmotic Power Generation

Salinity gradient energy, as a type of blue energy, is a promising sustainable energy source. Its energy conversion efficiency is significantly determined by the selective membranes. Recently, nanofluidic membrane made by two-dimensional (2D) nanomaterials (e.g., graphene) with densely packed nanochannels has been considered as a high-efficient membrane in the osmotic power generation research field. Herein, the graphene oxide-cellulose acetate (GO–CA) heterogeneous membrane was assembled by combining a porous CA membrane and a layered GO membrane; the combination of 2D nanochannels and 3D porous structures make it show high surface-charge-governed property and excellent ion transport stability, resulting in an efficient osmotic power harvesting. A power density of about 0.13 W/m² is achieved for the sea–river mimicking system and up to 0.55 W/m² at a 500-fold salinity gradient. With different functions, the CA and GO membranes served as ion storage layer and ion selection layer, respectively. The GO–CA heterogeneous membrane open a promising avenue for fabrication of porous and layered platform for wide potential applications, such as sustainable power generation, water purification, and seawater desalination.     

Building bio-inspired artificial functional nanochannels: from symmetric to asymmetric modification

Over millions of years, complex processes of intelligent control have evolved in nature. Learning from nature is a continuing theme in the development of smart materials and intelligent systems. For example, biological nanochannels, which are typically ion channels, play a very important role in basic biochemical processes in cells. Inspired by ion channels, in which the components are asymmetrically distributed between the membrane surfaces, the generation of biomimetic smart nanochannels is a broad and varied scientific research field. The design and development of new biomimetic channels includes the use of different shapes of channels, different stimuli-responsive molecules, and different symmetric/asymmetric modification methods. In this Minireview, we summarize recent developments in building functional nanochannels by applying various symmetric and asymmetric modifications.     

Ion Selectivity of Water Molecules in Subnanoporous Liquid-Crystalline Water-Treatment Membranes: A Structural Study of Hydrogen Bonding

We demonstrate hydrogen-bonded structures of water in self-organized subnanoporous water treatment membranes obtained using synchrotron-based high-resolution soft X-ray emission spectroscopy. The ion selectivity of these water treatment membranes is usually understood by the size compatibility of nanochannels in the membrane with the Stokes radius of hydrated ions, or by electrostatic interaction between charges inside the nanochannels and such ions. However, based on a comparison between the hydrogen-bonded structures of water molecules in the nanochannels of the water treatment membrane and those surrounding the ions, we propose a definite contribution of structural consistency among the associated hydrogen-bonded water molecules to the ion selectivity. Our observation delivers a novel concept to the design of water treatment membranes where water molecules in the nanochannel can be regarded as a part of the material that controls the ion selectivity.     

Biomimetic stimuli‐responsive nanochannels and their applications

Biomimetic smart nanochannels have been studied extensively to achieve the precise ionic transport compared to biological ion channels. Similar to ion channels in living organisms, biomimetic smart nanochannels can respond to various stimuli, which allows for promising applications in many fields. In this review, we mainly summarize the recent advances in the design of biomimetic stimuli‐responsive nanochannels and their potential applications including biosensors and drug delivery. Finally, an outlook on the challenges and opportunities for biomimetic stimuli‐responsive nanochannels is provided.     

Heterogeneous ion-exchange membranes

The field of heterogeneous ion exchange membranes is reviewed briefly. Specific advantages and disadvantages of heterogeneous ion exchange membranes are discussed compared with those of homogeneous ion exchange membranes. p]The development of heterogeneous ion exchange membranes is presented in historical perspective. The electrochemistry of ion-selective membranes began with Ostwald in 1890. After the classical work of Michaelis (1925) with collodion membranes, the first fully synthetic ion exchange membranes were prepared by Zhukov (1933) and Wassenegger (1940), based on sulfonated phenol—formaldehyde resins. These initial membranes, which were of the homogeneous type found no practical uses. The era of commercially useful ion exchange membranes began with the work of Wyllie (1948), Juda (1950), Bodamer (1953) and their collaborators who prepared heterogeneous ion exchange membranes by embedding ion exchange particles into polymer matrices. p]Methods for making heterogeneous ion exchange membranes include compression-molding of polymer powders, compounding on hot rolls, latex or solvent blending in situ generation of either the matrix or the ion exchange material. Microheterogeneous ion exchange membranes can be made from block and graft copolymers, interpolymers snake-cage resins, similar techniques and materials. p]Even though the first commercial ion exchange membranes were heterogeneous, the interest in this type of membranes subsided later. As polymer science progressed, speciality monomers and polymers were being made which opened the way to the preparation of quite sophisticated homogeneous ion exchange membranes of satisfactory mechanical strength. However, the possibilities of heterogeneous ion exchange membranes are by no means exhausted and this field may warrant further exploration, applying modern methods and materials and thus progressing beyond the relatively crude heterogeneous ion exchange membranes of the pioneer times.     

Construction and application of photoresponsive smart nanochannels

In living organisms, many biological processes are inextricably linked with light, such as the photosynthesis systems and rhodopsin. Hence, construction of light-sensitive biomimetic-nanochannels, which can realize the functions of cells and other membrane structures with high degree of spatial and temporal control, is particularly attractive and challenging. As a cornerstone of light-sensitive nanochannels, the photoresponsive materials are a big family and at their mature stage after several decades of development, which can provide different strategies to construct biomimetic photoresponsive nanochannels. In this review, we mainly summarize the construction and applications of photoresponsive nanochannels on the basis of various photoresponsive materials. The construction of photoresponsive nanochannels can be classified into four categories: photoresponsive inorganic nanochannels based on inorganic-compound-based photonic sensitive materials; photoresponsive organic nanochannels based on organic-compound-based photonic sensitive materials; photoresponsive polymers nanochannel based on photoresponsive polymers materials and potential photoresponsive nanochannels based on other photoresponsive materials. After introducing the construction of photoresponsive nanochannels, the review highlights some of the most recent applications of photoresponsive nanochannels in separation, energy conversion and storage, drug delivery and so on.     

仿生光响应智能纳米孔道的构筑及应用

在生命体中,很多生物过程都和光息息相关,例如光合作用过程和视觉感受系统等,而这些过程大都由生命体中对光敏感的蛋白质离子通道主导。近年来,受这些蛋白质离子通道的启发,具有光响应性的仿生智能固态纳米孔道广受关注。光响应纳米孔道具有灵活的空间和时间可控性,除了和生命过程息息相关,还在能源存储与转化、药物可控释放和分离等方面显示了巨大的应用前景。本综述主要从材料属性出发阐述光响应仿生智能纳米孔道的构筑和分类,并对其应用进行总结和展望。     

Biomimetic Ion Nanochannels as a Highly Selective Sequential Sensor for Zinc Ions Followed by Phosphate Anions

A novel biomimetic ion‐responsive multi‐nanochannel system is constructed by covalently immobilizing a metal‐chelating ligand, 2,2′‐dipicolylamine (DPA), in polyporous nanochannels prepared in a polymeric membrane. The DPA‐modified multi‐nanochannels show specific recognition of zinc ions over other common metal ions, and the zinc‐ion‐chelated nanochannels can be used as secondary sensors for HPO₄^2? anions. The immobilized DPA molecules act as specific‐receptor binding sites for zinc ions, which leads to the highly selective zinc‐ion response through monitoring of ionic current signatures. The chelated zinc ions can be used as secondary recognition elements for the capture of HPO₄^2? anions, thereby fabricating a sensing nanodevice for HPO₄^2? anions. The success of the DPA immobilization and ion‐responsive events is confirmed by measurement of the X‐ray photoelectron spectroscopy (XPS), contact angle (CA), and current–voltage (I–V) characteristics of the systems. The proposed nanochannel sensing devices display remarkable specificity, high sensitivity, and wide dynamic range. In addition, control experiments performed in complex matrices suggest that this sensing system has great potential applications in chemical sensing, biotechnology, and many other fields.     

Construction of biomimetic smart nanochannels with polymer membranes and application in energy conversion systems

Learning from nature has inspired the creation of intelligent devices to meet the increasing needs of the advanced community and also to better understand how to imitate biology. As one of biomimetic nanodevices, nanochannels or nanopores aroused particular interest because of their potential applications in nanofluidic devices, biosensing, filtration, and energy conversions. In this review we have summarized some recent results mainly focused on the design, construction and application in energy conversion systems. Like biological nanochannels, the prepared smart artificial nanochannels fabricated by ion track-etched polymer membranes and smart molecules show a great potential in the field of bioengineering and biotechnology. And these applications can not only help people to know and understand the living processes in nature, but can also inspire scientists to study and develop novel nanodevices with better performance for the mankind.