Ion-beam sculpting at nanometre length scales.

Manipulating matter at the nanometre scale is important for many electronic, chemical and biological advances, but present solid-state fabrication methods do not reproducibly achieve dimensional control at the nanometre scale. Here we report a means of fashioning matter at these dimensions that uses low-energy ion beams and reveals surprising atomic transport phenomena that occur in a variety of materials and geometries. The method is implemented in a feedback-controlled sputtering system that provides fine control over ion beam exposure and sample temperature. We call the method "ion-beam sculpting", and apply it to the problem of fabricating a molecular-scale hole, or nanopore, in a thin insulating solid-state membrane. Such pores can serve to localize molecular-scale electrical junctions and switches and function as masks to create other small-scale structures. Nanopores also function as membrane channels in all living systems, where they serve as extremely sensitive electro-mechanical devices that regulate electric potential, ionic flow, and molecular transport across cellular membranes. We show that ion-beam sculpting can be used to fashion an analogous solid-state device: a robust electronic detector consisting of a single nanopore in a Si3N4 membrane, capable of registering single DNA molecules in aqueous solution.     

Photocontrolled reversible release of guest molecules from coumarin-modified mesoporous silica

Since the discovery of MCM-41 more than ten years ago, many investigations have explored the suitability of hexagonal mesoporous silicas for potential practical applications. These range from catalysis and optically active materials to polymerization science, separation technology and drug delivery, with recent successes in the fabrication of hybrid mesoporous organosilicas expected to open up further application possibilities. Because the pore voids of this class of materials exhibit relatively narrow pore size distributions in the range of 2-4 nm in diameter, mesoporous silicas can selectively include organic compounds and release them continuously at a later stage. The functionalization of MCM-41 pore voids with photoactive derivatives provides influence over the material's absorption behaviour, but full control over the release process remains difficult. Here we show that the uptake, storage and release of organic molecules in MCM-41 can be regulated through the photocontrolled and reversible intermolecular dimerization of coumarin derivatives attached to the pore outlets. Successful functionalization requires uncalcined MCM-41 still filled with the template molecules that directed the formation of its pores, to ensure that coumarin derivatives attach preferentially to the pore outlets, rather than their inside walls. We find that this feature and the one-dimensional, isolated nature of the individual pores allow for efficient and reversible photocontrol over guest access to the material's interior.     

Template-directed synthesis of a genetic polymer in a model protocell

Contemporary phospholipid-based cell membranes are formidable barriers to the uptake of polar and charged molecules ranging from metal ions to complex nutrients. Modern cells therefore require sophisticated protein channels and pumps to mediate the exchange of molecules with their environment. The strong barrier function of membranes has made it difficult to understand the origin of cellular life and has been thought to preclude a heterotrophic lifestyle for primitive cells. Although nucleotides can cross dimyristoyl phosphatidylcholine membranes through defects formed at the gel-to-liquid transition temperature, phospholipid membranes lack the dynamic properties required for membrane growth. Fatty acids and their corresponding alcohols and glycerol monoesters are attractive candidates for the components of protocell membranes because they are simple amphiphiles that form bilayer membrane vesicles that retain encapsulated oligonucleotides and are capable of growth and division. Here we show that such membranes allow the passage of charged molecules such as nucleotides, so that activated nucleotides added to the outside of a model protocell spontaneously cross the membrane and take part in efficient template copying in the protocell interior. The permeability properties of prebiotically plausible membranes suggest that primitive protocells could have acquired complex nutrients from their environment in the absence of any macromolecular transport machinery; that is, they could have been obligate heterotrophs.     

Cyclic GMP-sensitive conductance of retinal rods consists of aqueous pores

The surface membrane of retinal rod and cone outer segments contains a cation-selective conductance which is activated by 3',5'-cyclic guanosine monophosphate (cGMP). Reduction of this conductance by a light-induced decrease in the cytoplasmic concentration of cGMP appears to generate the electrical response to light, but little is known about the molecular nature of the conductance. The estimated unitary conductance is so small that ion transport might occur via either a carrier or a pore mechanism. Here we report recordings of cGMP-activated single-channel currents from excised rod outer segment patches bathed in solutions low in divalent cations. Two elementary conductances, of approximately 24 and 8 pS, were observed. These conductances are too large to be accounted for by carrier transport, indicating that the cGMP-activated conductance consists of aqueous pores. The dependence of the channel activation on the concentration of cGMP suggests that opening of the pore is triggered by cooperative binding of at least three cGMP molecules.     

Asymmetric pores in a silicon membrane acting as massively parallel brownian ratchets

The brownian motion of mesoscopic particles is ubiquitous and usually random. But in systems with periodic asymmetric barriers to movement, directed or 'rectified' motion can arise and may even modulate some biological processes. In man-made devices, brownian ratchets and variants based on optical or quantum effects have been exploited to induce directed motion, and the dependence of the amplitude of motion on particle size has led to the size-dependent separation of biomolecules. Here we demonstrate that the one-dimensional pores of a macroporous silicon membrane, etched to exhibit a periodic asymmetric variation in pore diameter, can act as massively parallel and multiply stacked brownian ratchets that are potentially suitable for large-scale particle separations. We show that applying a periodic pressure profile with a mean value of zero to a basin separated by such a membrane induces a periodic flow of water and suspended particles through the pores, resulting in a net motion of the particles from one side of the membrane to the other without moving the liquid itself. We find that the experimentally observed pressure dependence of the particle transport, including an inversion of the transport direction, agrees with calculations of the transport properties in the type of ratchet devices used here.     

An equivalent 1D nanochannel model to describe ion transport in multilayered graphene membranes

Multilayered graphene-based membranes are promising for a variety of applications related to ion or molecule transport, such as energy storage and water treatment. However, the complex three-dimensional cascading nanoslit-like structure embedded in the membrane makes it difficult to interpret and rationalize experimental results, quantitatively compare with the traditional membrane systems, and quantitatively design new membrane structures. In this paper, systematic numerical simulations were performed to establish an equivalent onedimensional(1 D) nanochannel model to represent the structure of multilayered graphene membranes. We have established a quantitative relationship between effective diffusion length Leffand cross-section area Aeffof the1 D model and our recently developed two dimensional(2 D) representative microstructure for graphene membranes. We find that only in the cases of a relatively large lateral size L( ~100 nm) and a small slit size h( 2 nm), the effective diffusion length Leffand Aeffcan be calculated by an over-simplified but often used model. Otherwise, they show complex dependence on all three structural parameters of the 2 D structural model.Our equivalent 1 D nano-channel model can reproduce experimental results very well except for h 0.5 nm. The discrepancy could be attributed to the anomalous behaviour of molecules under nano-confinement that is not considered in our simulations. This model can also be extended to multilayered membranes assembled by other2 D materials.     

Determination of Mechanical Properties of Micromembranes with Compressive Residual Stress

A novel model of a load-deflection method to determine the mechanical properties of micromembranes with compressive residual stress is described. Since thin film structures are frequently used in micro devices, characterisation of mechanical properties of thin films is desired by the design and fabrication of micromachines. In this paper, the mechanical properties of thin micromembranes under compressive stress are characterised, which are fabricated by bulk micromachining. The relation between the center deflection and the load pressure on a square membrane is deduced by modelling the membrane as an elastic plate having large deflection with clamped boundaries. According to the model, whether the membrane has initial deflection or not has no effect on the measurement result. The Young's modulus and residual stress are simultaneously determined. The mechanical properties of siliconoxide, silicon nitride membranes and composite membranes of polysilicon with silicon nitride are measured.     

Structural determinants of water permeation through aquaporin-1

Human red cell AQP1 is the first functionally defined member of the aquaporin family of membrane water channels. Here we describe an atomic model of AQP1 at 3.8A resolution from electron crystallographic data. Multiple highly conserved amino-acid residues stabilize the novel fold of AQP1. The aqueous pathway is lined with conserved hydrophobic residues that permit rapid water transport, whereas the water selectivity is due to a constriction of the pore diameter to about 3 A over a span of one residue. The atomic model provides a possible molecular explanation to a longstanding puzzle in physiology-how membranes can be freely permeable to water but impermeable to protons.     

Structured spheres generated by an in-fibre fluid instability

From drug delivery to chemical and biological catalysis and cosmetics, the need for efficient fabrication pathways for particles over a wide range of sizes, from a variety of materials, and in many different structures has been well established. Here we harness the inherent scalability of fibre production and an in-fibre Plateau-Rayleigh capillary instability for the fabrication of uniformly sized, structured spherical particles spanning an exceptionally wide range of sizes: from 2?mm down to 20?nm. Thermal processing of a multimaterial fibre controllably induces the instability, resulting in a well-ordered, oriented emulsion in three dimensions. The fibre core and cladding correspond to the dispersed and continuous phases, respectively, and are both frozen in situ on cooling, after which the particles are released when needed. By arranging a variety of structures and materials in a macroscopic scaled-up model of the fibre, we produce composite, structured, spherical particles, such as core-shell particles, two-compartment 'Janus' particles, and multi-sectioned 'beach ball' particles. Moreover, producing fibres with a high density of cores allows for an unprecedented level of parallelization. In principle, 10(8) 50-nm cores may be embedded in metres-long, 1-mm-diameter fibre, which can be induced to break up simultaneously throughout its length, into uniformly sized, structured spheres.     

湿化学法制备多通道ZrO2超滤膜

采用孔径为200 nm的多通道ZrO2膜为底膜,利用湿化学法制备小孔径ZrO2超滤膜。结合N2吸附-脱附法和X线衍射分析,考察烧结温度对膜结构的影响,确定合适的烧结温度。通过扫描电镜(SEM)表征膜形貌,采用错流过滤考察膜的渗透和分离性能。结果表明:烧结温度为600℃时可以制备完整无缺陷的ZrO2超滤膜,所制备的超滤膜具有高纯水通量,截留相对分子质量(MWCO)为20 000,对相对分子质量为43 000卵清蛋白的截留率达到95%。     

Influence of pore size optimization in catalyst layer on the mechanism of oxygen transport resistance in PEMFCs

In PEMFC, the oxygen transport resistance severely hinders the cell from achieving high performance. In this paper, pore-forming agent was used to optimize the pore size distribution of the catalyst layer (CL), and to study its effect on the mechanism of oxygen transport resistance, including molecular diffusion resistance, Knudsen diffusion resistance, and local O₂ resistance in CL. The results showed that with the pore formation the cell performance had a significant improvement at high current density, mainly due to its better oxygen transport properties, especially under low platinum conditions. The addition of pore-forming agent moved the pore diameter toward a larger pore diameter with a range from 70 to 100 nm, and also obtaining a higher cumulative pore volume. It was found that the increase of the cumulative pore volume and larger pore size were conducive to the diffusion of oxygen molecules in CL, and the resistance caused by which was the dominant part in total transport resistance. Further tests indicated that the improvement of molecular diffusion resistance was much larger than that of Knudsen diffusion resistance in the catalyst layer after pore formed. In addition, the optimized pore structure will also get a higher number of effective pores, which resulted in an increased effective area of the ionomer on the Pt surface. The higher effective area of the ionomer was particularly beneficial for the reduction of local O₂ resistance with low Pt loading.     

Cell membranes impermeable to NH3

Classically, there is a direct correlation between the lipophilic nature of a molecule and its rate of permeation across a biological membrane, so cell membranes should be more permeable to small, neutral molecules than they are to charged molecular species of similar size. Consequently, the distribution of NH+4 in biological systems is generally believed to be due to the rapid diffusion and equilibration of lipophilic NH3 across cell membranes and the accumulation of NH+4 to be governed by pH differences between compartments. Here we report that renal tubule cells from the medullary thick ascending limb of Henle have an apical membrane which is not only virtually impermeable to NH3, but is also highly permeable to NH+4. These remarkable properties have been incorporated into a model which explains how this renal epithelium can mediate vectorial movement of NH+4 between compartments of equal pH.     

Ultrathin compound semiconductor on insulator layers for high-performance nanoscale transistors

Over the past several years, the inherent scaling limitations of silicon (Si) electron devices have fuelled the exploration of alternative semiconductors, with high carrier mobility, to further enhance device performance. In particular, compound semiconductors heterogeneously integrated on Si substrates have been actively studied: such devices combine the high mobility of III-V semiconductors and the well established, low-cost processing of Si technology. This integration, however, presents significant challenges. Conventionally, heteroepitaxial growth of complex multilayers on Si has been explored-but besides complexity, high defect densities and junction leakage currents present limitations in this approach. Motivated by this challenge, here we use an epitaxial transfer method for the integration of ultrathin layers of single-crystal InAs on Si/SiO(2) substrates. As a parallel with silicon-on-insulator (SOI) technology, we use 'XOI' to represent our compound semiconductor-on-insulator platform. Through experiments and simulation, the electrical properties of InAs XOI transistors are explored, elucidating the critical role of quantum confinement in the transport properties of ultrathin XOI layers. Importantly, a high-quality InAs/dielectric interface is obtained by the use of a novel thermally grown interfacial InAsO(x) layer (~1?nm thick). The fabricated field-effect transistors exhibit a peak transconductance of ~1.6?mS?μm(-1) at a drain-source voltage of 0.5?V, with an on/off current ratio of greater than 10,000.     

电泳沉积法制备氧化铝陶瓷膜的研究

以工业级陶瓷片为支撑体,氧化铝溶胶为电泳液,采用电泳沉积的方法制备了氧化铝陶瓷膜。当在30 V的电压条件下电泳3 min,经沉积-干燥-烧结工艺,反复进行3次后,即可得到氧化铝纳滤膜。采用SEM和液-液排除法等手段对纳滤膜进行表征,结果表明,膜厚在50 μm左右,孔隙率为31.51%,平均孔径为3.1 nm,孔径分布为2.88～5.76 nm。性能测试表明,氧化铝纳滤膜对无机污染物和有机污染物均有强的截留作用,且性能较稳定。     

Nanoscopic channel lattices with controlled anisotropic wetting

Engineered microscopic surface structures allow local control of physical surface properties such as adhesion, friction and wettability. These properties are related both to molecular interactions and the surface topology--for example, selective adsorption and molecular recognition capabilities require controlled anisotropy in the surface properties. Chemistry with extremely small amounts of material has become possible using liquid-guiding channels of sub-micrometre dimensions. Laterally structured surfaces with differing wettabilities may be produced using various techniques, such as microcontact printing, micromachining, photolithography and vapour deposition. Another strategy for introducing anisotropic texture is based on the use of the intrinsic material properties of stretched ultrathin polymer coatings. Here we present a fast and simple method to generate extended patterned surfaces with controlled wetting properties on the nanometre scale, without any lithographic processes. The technique utilizes wetting instabilities that occur when monomolecular layers are transferred onto a solid substrate. The modified surfaces can be used as templates for patterning a wide variety of molecules and nanoclusters into approximately parallel channels, with a spatial density of up to 20,000 cm(-1). We demonstrate the transport properties of these channels for attolitre quantities of liquid.     

Self-assembled monolayer organic field-effect transistors

The use of individual molecules as functional electronic devices was proposed in 1974 (ref. 1). Since then, advances in the field of nanotechnology have led to the fabrication of various molecule devices and devices based on monolayer arrays of molecules. Single molecule devices are expected to have interesting electronic properties, but devices based on an array of molecules are easier to fabricate and could potentially be more reliable. However, most of the previous work on array-based devices focused on two-terminal structures: demonstrating, for example, negative differential resistance, rectifiers, and re-configurable switching. It has also been proposed that diode switches containing only a few two-terminal molecules could be used to implement simple molecular electronic computer logic circuits. However, three-terminal devices, that is, transistors, could offer several advantages for logic operations compared to two-terminal switches, the most important of which is 'gain'-the ability to modulate the conductance. Here, we demonstrate gain for electronic transport perpendicular to a single molecular layer ( approximately 10-20 A) by using a third gate electrode. Our experiments with field-effect transistors based on self-assembled monolayers demonstrate conductance modulation of more than five orders of magnitude. In addition, inverter circuits have been prepared that show a gain as high as six. The fabrication of monolayer transistors and inverters might represent an important step towards molecular-scale electronics.     

Solid acids as fuel cell electrolytes

Fuel cells are attractive alternatives to combustion engines for electrical power generation because of their very high efficiencies and low pollution levels. Polymer electrolyte membrane fuel cells are generally considered to be the most viable approach for mobile applications. However, these membranes require humid operating conditions, which limit the temperature of operation to less than 100 degrees C; they are also permeable to methanol and hydrogen, which lowers fuel efficiency. Solid, inorganic, acid compounds (or simply, solid acids) such as CsHSO4 and Rb3H(SeO4)2 have been widely studied because of their high proton conductivities and phase-transition behaviour. For fuel-cell applications they offer the advantages of anhydrous proton transport and high-temperature stability (up to 250 degrees C). Until now, however, solid acids have not been considered viable fuel-cell electrolyte alternatives owing to their solubility in water and extreme ductility at raised temperatures (above approximately 125 degrees C). Here we show that a cell made of a CsHSO4 electrolyte membrane (about 1.5 mm thick) operating at 150-160 degrees C in a H2/O2 configuration exhibits promising electrochemical performances: open circuit voltages of 1.11 V and current densities of 44 mA cm-2 at short circuit. Moreover, the solid-acid properties were not affected by exposure to humid atmospheres. Although these initial results show promise for applications, the use of solid acids in fuel cells will require the development of fabrication techniques to reduce electrolyte thickness, and an assessment of possible sulphur reduction following prolonged exposure to hydrogen.     

一种求得纳滤膜截留分子量的方法

利用回归方法,建立表征纳滤膜分离性能常用的有机分子的Stokes半径(rs)与分子量(Ms)之间定量关系方程.根据提出的纳滤膜截留分子量(Mp)所对应的分子Stokes半径与膜的等效细孔半径(rp)相等的假设,得到Mp与rp之间的关系方程,即只要知道纳滤膜细孔半径就能求得Mp.通过NF270纳滤膜对葡萄糖和蔗糖的透过实验,采用细孔模型(SHP模型)和S-K模型对NF270纳滤膜的rp进行了估算,进而计算出NF270膜的截留分子量为540左右,与供应商提供的截留分子量基本相符.利用文献数据计算了几种纳滤膜的Mp,与文献报道的结果基本一致.因此,为膜截留分子量的估算提供了一种更加方便、实用的新方法.     

页岩储层纳米孔气体传输耦合模型新研究

页岩气在纳米孔隙的传输过程中受多种因素影响,包括孔隙尺寸和压力、孔隙壁面粗糙度、孔隙力学反应、吸附诱导膨胀反应以及权重因子等。因此需要综合考虑以上因素以及吸附气分子在孔隙中所占空间对气体流动影响的条件下,厘清页岩气的不同运移机制（表面扩散、滑脱流、Knudsen扩散和黏性流动）在不同孔隙尺寸和压力下对纳米孔中总气体流量的贡献率。首先,对页岩气的不同运移方式进行了物理描述及数学表征,然后,在考虑孔隙壁面粗糙度、孔隙力学反应、吸附诱导膨胀反应和权重因子等因素的条件下,建立页岩气在储层纳米孔中的气体传输耦合数学模型,模型可靠性通过格子Boltzmann方法计算结果验证。研究结果表明,当孔径小于10 nm时,纳米孔的总流量主要由表面扩散流量组成,孔径越小,表面扩散流量越大;当孔径为40~250 nm和低压条件下,滑脱流和Knudsen扩散对气体传输影响较大;当孔径大于10 μm时,纳米孔的总流量主要为黏性流量。     

Silicon nanowires as efficient thermoelectric materials

Thermoelectric materials interconvert thermal gradients and electric fields for power generation or for refrigeration. Thermoelectrics currently find only niche applications because of their limited efficiency, which is measured by the dimensionless parameter ZT-a function of the Seebeck coefficient or thermoelectric power, and of the electrical and thermal conductivities. Maximizing ZT is challenging because optimizing one physical parameter often adversely affects another. Several groups have achieved significant improvements in ZT through multi-component nanostructured thermoelectrics, such as Bi(2)Te(3)/Sb(2)Te(3) thin-film superlattices, or embedded PbSeTe quantum dot superlattices. Here we report efficient thermoelectric performance from the single-component system of silicon nanowires for cross-sectional areas of 10 nm x 20 nm and 20 nm x 20 nm. By varying the nanowire size and impurity doping levels, ZT values representing an approximately 100-fold improvement over bulk Si are achieved over a broad temperature range, including ZT approximately 1 at 200 K. Independent measurements of the Seebeck coefficient, the electrical conductivity and the thermal conductivity, combined with theory, indicate that the improved efficiency originates from phonon effects. These results are expected to apply to other classes of semiconductor nanomaterials.