Template-synthesized nanotubes for chemical separations and analysis

We have developed a new class of synthetic membranes that consist of a porous polymeric support that contains an ensemble of gold nanotubes that span the thickness of the support membrane. The support is a commercially-available microporous polycarbonate filter with cylindrical nanoscopic pores. The gold nanotubes are prepared by electroless deposition of Au onto the pore walls, that is, the pores acts as templates for the nanotubes. We have shown that by controlling the Au deposition time, Au nanotubes that have effective inside diameters of molecular dimensions (<1 nm) can be prepared. These nanotube membranes can be used to cleanly separate small molecules on the basis of molecular size. Furthermore, use of these membranes as a novel electrochemical sensor is also discussed. This new sensing scheme involves applying a constant potential across the Au nanotube membrane and measuring the drop in the transmembrane current upon the addition of the analyte. This paper reviews our recent progress on size-based based transport selectivity and sensor applications in this new class of membranes.     

Molecular sieving and sensing with gold nanotube membranes

We have developed a new class of synthetic membranes that consist of a porous polymeric support that contains an ensemble of gold nanotubes that span the thickness of the support membrane. The support is a commercially available microporous polycarbonate filter with cylindrical nanoscopic pores. The gold nanotubes are prepared via electroless deposition of Au onto the pore walls; i.e., the pores act as templates for the nanotubes. We have shown that by controlling the Au deposition time, Au nanotubes that have effective inside diameters of molecular dimensions (<1 nm) can be prepared. These nanotube membranes can be used to cleanly separate small molecules on the basis of molecular size. Furthermore, use of these membranes as a novel electrochemical sensor is also discussed. This new sensing scheme involves applying a constant potential across the Au nanotube membrane and measuring the drop in the transmembrane current upon the addition of the analyte. This paper reviews our recent progress on size-based transport selectivity and sensor applications in this new class of membranes.     

Electromodulated molecular transport in gold-nanotube membranes

We have developed a new class of synthetic membranes that contain monodisperse Au nanotubes with inside diameters of molecular dimensions (<1 nm). The Au nanotubes span the complete thickness of the membrane and can act as conduits for molecule and ion transport between solutions placed on either side of the membrane. We have recently become interested in the concept of electromodulating neutral molecule transport across these membranes. This communication describes a novel approach for accomplishing this objective. This approach makes use of an anionic surfactant which, when a positive potential is applied to the Au nanotube membrane, partitions into the nanotubes to charge the solution side of the electrical double layer at the tube walls. Because of the hydrophobic tail of the surfactant, this renders the nanotube interior hydrophobic, and the membrane now preferentially extracts and transports neutral hydrophobic molecules. Because the anionic surfactant can be expelled from the nanotubes by applying a negative potential, this provides a route for reversibly electromodulating neutral molecule transport in these membranes.     

偶氮吡啶分子结的制备、表征及电学性质初步研究

具有特异电学性质的分子结的制备及电子输运特性研究是分子电子学领域中的主要内容,对构筑分子电子器件具有重要意义．但是,由于分子结的尺度通常在100nm以下,这使得分子结的低缺陷制备和准确有效的电学特性研究面临困难．目前,自组装方法已经成为降低分子结缺陷的主要手段,     

Layer-by-layer nanotube template synthesis

Electroless deposition of gold on the pore walls of polycarbonate templates is currently the best known method for controlling inside diameters of template-synthesized nanotubes. It would be very useful to have alternative template-based synthetic chemistries that yield nanotubes composed of other materials, but which still allow for precise control over the nanotube wall thickness and i.d. A film-formation process that is based on layer-by-layer deposition of the film-forming material along the pore walls of the template membrane provides this desired alternative synthetic chemistry. We describe here the use of Mallouk's alpha,omega-diorganophosphonate/Zr layer-by-layer film-forming method for preparing nanotubes within the pores of alumina template membranes. We have found that this method allows accurate, quantitative, and predictable control over the wall thickness, and thus i.d., of the layered nanotubes obtained.     

Photochemical approach toward deposition of gold nanoparticles on functionalized carbon nanotubes

The development of new methods for the facile synthesis of hybrid nanomaterials is of great importance due to their importance in nanotechnology. In this work, we report a new method to deposit Au nanoparticles on the surface of single-walled carbon nanotubes (SWCNTs). Our approach consists of a one pot synthesis in which Au nanoparticles are generated in the presence of a photoreducing agent (Irgacure-2959) and carboxyl or polymer-functionalized SWCNTs (f-SWCNTs). We have observed that when carbon nanotubes are functionalized with polymers containing pendant amino groups, the latter can act as specific nucleation sites for well-dispersed deposition of Au nanoparticles. The surface coverage of the Au nanoparticles can be observed by transmission electron spectroscopy. These observations are compared to that of carboxyl functionalized SWCNTs, in which less surface coverage was observed. The f-SWCNT/Au nanocomposites were also characterized by UV-vis, infrared, and Raman spectroscopy and thermogravimetric analysis (TGA). This facile and effective route can be implemented to deposit gold nanoparticles on other surface-functionalized carbon nanotubes.     

Heterostructured magnetic nanotubes

Heterostructured magnetic tubes with submicrometer dimensions were assembled by the layer-by-layer deposition of polyelectrolytes and nanoparticles in the pores of track-etched polycarbonate membranes. Multilayers composed of poly(allylamine hydrochloride) and poly(styrene sulfonate) assembled at high pH (pH > 9.0) were first assembled into the pores of track-etched polycarbonate membranes, and then multilayers of magnetite (Fe3O4) nanoparticles and PAH were deposited. Transmission electron microscopy (TEM) confirmed the formation of multilayer nanotubes with an inner shell of magnetite nanoparticles. These tubes exhibited superparamagnetic characteristics at room temperature (300 K) as determined by a SQUID magnetometer. The surface of the magnetic nanotubes could be further functionalized by adsorbing poly(ethylene oxide)-b-poly(methacrylic acid) block copolymers. The separation and release behavior of low molecular weight anionic molecules (i.e., ibuprofen, rose bengal, and acid red 8) by/from the multilayer nanotubes were studied because these tubes could potentially be used as separation or targeted delivery vehicles. The magnetic tubes could be successfully used to separate (or remove) a high concentration of dye molecules (i.e., rose bengal) from solution by activating the nanotubes in acidic solution. The release of the anionic molecules in physiologically relevant buffer solution showed that whereas bulky molecules (e.g., rose bengal) release slowly, small molecules (i.e., ibuprofen) release rapidly from the multilayers. The combination of the template method and layer-by-layer deposition of polyelectrolytes and nanoparticles provides a versatile means to create functional nanotubes with heterostructures that can be used for separation as well as targeted delivery.     

Enhanced field emission from multiwall carbon nanotube films by secondary growth

We have studied nickel, gold, and ferritin coatings on catalytically grown multiwall carbon nanotubes as well as the generation of secondary nanotubes by resubmitting the decorated nanotubes to the chemical vapor deposition process. Nickel layers sputtered on nanotubes show a stronger interaction with the nanotube walls than gold coatings. At ambient temperature this results in a metal film that is more homogeneous for Ni than for Au. Surface mass transport at elevated temperatures leads to a transformation of the coating to nanoscale clusters on the nanotube surface. The resulting Au clusters are spherelike with a very small contact area with the nanotube whereas the Ni clusters are stretched along the tube axis and have a large contact area. Secondary nanotubes were established by growing nanotubes directly on the walls of primary nanotubes. Thin Ni layers or ferritin served as catalysts. We compared the field emission properties of samples with and without secondary nanotubes. The presence of secondary nanotubes enhances the field emission substantially.     

Conical-nanotube ion-current rectifiers: the role of surface charge

Ion channels are protein pores that span cell membranes and open and close in response to stimuli like changes in the transmembrane potential, binding of a ligand, or mechanical stress. When open, ions pass through the pore, and hence across the cell membrane, and when closed, ion-transport is precluded. Hence, these channels are nanodevices that have a current-rectification function. There is intense research effort aimed at understanding the molecular-level mechanism for this function. One approach for elucidating the mechanism is to construct a simple abiotic system that mimics this function and to use the mechanistic details of this mimic as a guide to understand the more complex biological channel. We describe here such an abiotic mimic: a synthetic membrane that contains a single conical gold nanotube. The advantage of this mimic is that the surface charge and chemistry of the nanotube wall can be varied, at will, by judicious choice of electrolyte or by thiol chemisorption. This has allowed us to make conical Au nanotubes that rectify the ion current and, just as importantly, to definitively elucidate the mechanism of this function.     

Synthesis of Various Metal/TiO2 Core/shell Nanorod Arrays

We present a general approach to fabricate metal/TiO₂ core/shell nanorod structures by two-step electrodeposition. Firstly, TiO₂ nanotubes with uniform wall thickness are prepared in anodic aluminum oxide (AAO) membranes by electrodeposition. The wall thickness of thenanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes' tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO₂ nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.     

Stabilizing gold adatoms by thiophenyl derivatives: a possible route toward metal redispersion

Tris(phenylthio)benzene molecules have been synthesized in order to explore their ability to trap single Au adatoms on an Au(111) surface. The resulting metal-organic complexes have been characterized with low-temperature scanning tunneling microscopy and infrared reflection absorption spectroscopy; possible structure models have been derived from density functional calculations. Upon room temperature deposition, the thiophenyl derivatives form dimer structures, comprising two molecules and six Au adatoms. Below 100 K, isolated molecules are found as well that have trapped up to six Au atoms. On the basis of the experimental results and calculated formation energies of the complexes, we discuss potential applications of the thioethers for the redispersion of metals on a catalyst surface. First experiments performed on Au particle ensembles prepared on alumina thin films suggest that the molecular ligands are indeed able to change the distribution of gold on the oxide surface.     

Preparation and electrocatalytic properties of gold nanoparticles loaded carbon nanotubes

Here, we report a new method of preparation of gold nanoparticles loaded carbon nanotubes (Au/CNTs) and the eleltrocatalystic properties of the obtained Au/CNTs as composite catalyst. This method shows advantages as it is easy to wash sodium citrate and the particle size of Au nanoparticles could by controlled by pH.     

Raman spectroscopy probing of self-assembled monolayers inside the pores of gold nanotube membranes

Electroless deposition was used to coat porous alumina membranes with gold. This process reduced the pore diameters and provided a platform suitable for surface modifications with self assembled monolayers (SAMs). The surface enhanced Raman scattering (SERS) effect was employed in order to confirm and characterise the formation of SAMs of 3-mercaptobenzoic acid (mMBA) inside the pores of gold nanotube membranes prepared using porous alumina (PA) templates. The investigation of the coverage and reproducibility of SAMs within porous matrices is of utmost importance in the design of filtration membranes and sensing platforms. Raman spectroscopy is capable of spatially resolved techniques such as mapping which was used to characterise the distribution of mMBA assembly within the pores. Due to the highly ordered structure of porous alumina and well controlled electroless gold deposition, these gold coated membranes have the potential to develop into SERS active substrates for ultrasensitive sensing technologies.     

Template synthesis of polyaniline and poly(2-methoxyaniline) nanotubes: comparison of the formation mechanisms

The process of polyaniline (PANI), poly(2-methoxyaniline) (POMA) nanotubes formation was investigated. Polyaniline and poly(2-methoxyaniline) nanotubes were prepared by chemical in situ deposition within the pores of polycarbonate membranes. It was found that the formation of polyaniline and poly(2-methoxyaniline) proceeds by two substantially different mechanisms. In the case of PANI, the polymer is first formed in the polymerization solution (the solution containing the monomer and oxidant, where the polycarbonate substrate is placed), and then it precipitates on/into the membrane. In the case of POMA, the oxidized 2-methoxyaniline molecules are first adsorbed on polycarbonate surface, and then, as a consequence of their accumulation, they recombine to form the polymer.     

Synthesis and optical properties of nanorattles and multiple-walled nanoshells/nanotubes made of metal alloys

The galvanic replacement reaction between silver and chloroauric acid has been exploited as a powerful means for preparing metal nanostructures with hollow interiors. Here, the utility of this approach is further extended to produce complex core/shell nanostructures made of metals by combining the replacement reaction with electroless deposition of silver. We have fabricated nanorattles consisting of Au/Ag alloy cores and Au/Ag alloy shells by starting with Au/Ag alloy colloids as the initial template. We have also prepared multiple-walled nanoshells/nanotubes (or nanoscale Matrioshka) with a variety of shapes, compositions, and structures by controlling the morphology of the template and the precursor salt used in each step of the replacement reaction. There are a number of interesting optical features associated with these new core/shell metal nanostructures. For example, nanorattles made of Au/Ag alloys displayed two well-separated extinction peaks, a feature similar to that of gold or silver nanorods. The peak at approximately 510 nm could be attributed to the Au/Ag alloy cores, while the other peak was associated with the Au/Ag alloy shells and could be continuously tuned in the spectral range from red to near-infrared.     

Au/Al2O3催化剂的制备及其在CH4/CO2重整反应中的催化活性

采用浸渍法和沉积－沉淀法制备了四种不同的Au/Al2O3催化剂，测定了它们在氢气还原前后及催化反应后的金含量及比表面积，结果表明，制备方法明显影响催化剂的金含量，应用X－光粉末衍射技术研究了这些催化剂经还原处理及反应后的物相变化，金以Au^0物相存在，没有发现氧化态的金物相，考察了该催化剂在CH4／CO2重整反应中的催化活性，发现金催化剂的活性取决于金粒子的大小，浸渍法制备的金催化剂具有较大的金晶粒尺寸，催化活性低，沉积－沉淀法制备的金催化剂金晶粒尺寸较小，催化活性较高，以尿素为沉淀剂制备的催化剂给出1073K时的CH4和CO2转化率分别为8．1％和17．6％，高温反应不仅导致金晶粒的聚集，而且存在明显的金流失现象。     

Template synthesized molecularly imprinted polymer nanotube membranes for chemical separations

In this report, we describe the synthesis of a molecularly imprinted polymer (MIP) nanotube membrane, using a porous anodic alumina oxide (AAO) membrane by surface-initiated atom transfer radical polymerization (ATRP). The use of a MIP nanotube membrane in chemical separations gives the advantage of high affinity and selectivity. Furthermore, because the molecular imprinting technique can be applied to different kinds of target molecules, ranging from small organic molecules to peptides and proteins, such MIP nanotube membranes will considerably broaden the application of nanotube membranes in chemical separations and sensors. This report also shows that the ATRP route is an efficient procedure for the preparation of molecularly imprinted polymers. Furthermore, the ATRP route works well in its formation of MIP nanotubes within a porous AAO membrane. The controllable nature of ATRP allows the growth of a MIP nanotube with uniform pores and adjustable thickness. Thus, using the same route, it is possible to tailor the synthesis of MIP nanotube membranes with either thicker MIP nanotubes for capacity improvement or thinner nanotubes for efficiency improvement.     

Coaxially gated in-wire thin-film transistors made by template assembly

Nanowire field effect transistors were prepared by a wet chemical template replication method using anodic aluminum oxide membranes. The membrane pores were first lined with a thin SiO2 layer by the surface sol-gel method. Au, CdS (or CdSe), and Au wire segments were then sequentially electrodeposited within the pores, and the resulting nanowires were released by dissolution of the membrane. Electrofluidic alignment of these nanowires between source and drain leads and evaporation of gold over the central CdS (CdSe) stripe affords a "wrap-around gate" structure. At VDS = -2 V, the Au/CdS/Au devices had an ON/OFF current ratio of 103, a threshold voltage of 2.4 V, and a subthreshold slope of 2.2 V/decade. A 3-fold decrease in the subthreshold slope relative to that of planar nanocrystalline CdSe devices can be attributed to coaxial gating. The control of dimensions afforded by template synthesis should make it possible to reduce the gate dielectric thickness, channel length, and diameter of the semiconductor segment to sublithographic dimensions while retaining the simplicity of the wet chemical synthetic method.     

Transport and separation of small organic molecules through nanotubules.

An electroless plating method was applied to deposit Au onto the surfaces and the walls of pores of polycarbonate membranes to prepare gold nanotubules. The nanotubules were modified with cysteine (Cys) or with carbamidine thiocyante (Gua). The effects of modifiers and of the fine structure of organic molecules on the transport properties of those molecules through the gold nanotubules were investigated. Studies show that the hydrophilicity of modifiers and the planar structure of permeating molecules clearly affect the transport of small organic molecules in gold nanotubules. Tryptophan (Try) and vitamin B(2) (VB(2)) was cleanly separated at pH 6.8.     

羊抗人IgG在金纳米通道中的迁移

以聚碳酸酯超滤膜为基板,用化学镀的方法在超滤膜上沉积金,制得直径在45nm左右的金纳米通道阵列,利用制得的金纳米通道阵列搭建离子电流测量平台,可实现对羊抗人IgG分子的浓度检测.当羊抗人IgG分子通过直径45nm的金纳米通道时,由于物理占位及表面电荷的影响,会引起离子电流发生变化;在KCl浓度为0.15mol/L(pH7.48)溶液中,IgG分子的物理占位对离子电流有阻塞作用,会导致电流减小,IgG浓度在1.8～18ng/mL范围内,减小量与浓度成线性关系;实现了对IgG的定量检测.KCl浓度降低到0.025mol/L时,由于IgG分子扩散层内反离子对通道内离子浓度的贡献占主导地位,从而造成离子电流随着IgG浓度增大而增大.