Micropatterned arrays of porous silicon: toward sensory biointerfaces

We describe the fabrication of arrays of porous silicon spots by means of photolithography where a positive photoresist serves as a mask during the anodization process. In particular, photoluminescent arrays and porous silicon spots suitable for further chemical modification and the attachment of human cells were created. The produced arrays of porous silicon were chemically modified by means of a thermal hydrosilylation reaction that facilitated immobilization of the fluorescent dye lissamine, and alternatively, the cell adhesion peptide arginine-glycine-aspartic acid-serine. The latter modification enabled the selective attachment of human lens epithelial cells on the peptide functionalized regions of the patterns. This type of surface patterning, using etched porous silicon arrays functionalized with biological recognition elements, presents a new format of interfacing porous silicon with mammalian cells. Porous silicon arrays with photoluminescent properties produced by this patterning strategy also have potential applications as platforms for in situ monitoring of cell behavior.     

Dynamic internal gradients control and direct electric currents within nanostructured materials

Switchable nanomaterials--materials that can change their properties and/or function in response to external stimuli-have potential applications in electronics, sensing and catalysis. Previous efforts to develop such materials have predominately used molecular switches that can modulate their properties by means of conformational changes. Here, we show that electrical conductance through films of gold nanoparticles coated with a monolayer of charged ligands can be controlled by dynamic, long-range gradients of both mobile counterions surrounding the nanoparticles and conduction electrons on the nanoparticle cores. The internal gradients and the electric fields they create are easily reconfigurable, and can be set up in such a way that electric currents through the nanoparticles can be modulated, blocked or even deflected so that they only pass through select regions of the material. The nanoion/counterion hybrids combine the properties of electronic conductors with those of ionic gels/polymers, are easy to process by solution-casting and, by controlling the internal gradients, can be reconfigured into different electronic elements (current rectifiers, switches and diodes).     

Assembly of silica nanoparticles for two-dimensional nanomaterials

To realize the great potential of nanoparticles as new materials for biomedical applications, the nanoparticles will have to be assembled in such a way that the newly created assembly will have unique properties that conventional materials do not possess. This will enable nanomaterials to be used for many novel applications. We have attempted to assemble silica nanoparticles to create a two-dimensional nanomaterial, which might be useful for biosensor and biochip production. The silica nanoparticles are synthesized and assembled in a monolayer fashion through the use of halogenated silanes. Photolithography techniques are used to pattern the glass surface prior to nanoparticle attachment. The concentration of the silica nanoparticles in the solution controls the surface coverage of nanoparticles on the glass surface. Different patterned silica arrays can be made with controlled surface coverage. The nanoparticle-covered surface is successfully tested for surface-enhanced enzymatic reactivity for the detection of a neurotransmitter, glutamate. This report demonstrates the feasibility of assembling nanoparticles for biosensor development.     

Aligned two- and three-dimensional structures by directional freezing of polymers and nanoparticles

The preparation of materials with aligned porosity in the micrometre range is of technological importance for a wide range of applications in organic electronics, microfluidics, molecular filtration and biomaterials. Here, we demonstrate a generic method for the preparation of aligned materials using polymers, nanoparticles or mixtures of these components as building blocks. Directional freezing is used to align the structural elements, either in the form of three-dimensional porous structures or as two-dimensional oriented surface patterns. This simple technique can be used to generate a diverse array of complex structures such as polymer-inorganic nanocomposites, aligned gold microwires and microwire networks, porous composite microfibres and biaxially aligned composite networks. The process does not involve any chemical reaction, thus avoiding potential complications associated with by-products or purification procedures.     

Fabrication of oriented arrays of porous gold microsheaths using aligned silver nanowires as sacrificial template

A simple one-step process for preparation of oriented arrays of porous gold microsheaths has been developed by dissolution of sacrificial templates of aligned Ag nanowires in a mixture solution of HAuCl₄ and NaCl at room temperature. The morphology and crystal structure of the product were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Its composition was estimated by energy dispersive X-ray spectroscopy (EDX). The results indicated that the gold microsheaths had generally preserved the original orientation of Ag nanowires and their orientation was robust enough to survive the centrifugal process. The gold microsheaths consist of nanoparticles (ca. 100 nm) that form nanovoids (tens to hundreds of nanometers) between them, giving them a porous nature. Such arrays of well oriented gold microsheaths are expected to show interesting anisotropic optical and electronic properties, and their hollow porous structures might find broad potential applications in surface plasma resonance (SPR), catalysis and chemical sensing.     

Gradients in polymeric materials

In this paper we consider the structure and properties of polymeric materials possessing spatial gradients as well as potential applications of such materials.These gradients may be generated by varying the chemical nature of the monomers, the molecular constitution of the polymers and the supramolecular structure or morphology of the polymers. Gradients in each of these categories are possible for single-phase as well as heterophase systems. Such gradients are associated with gradients in properties.The properties considered are chemical, mechanical, biomedical and transport properties. Structural gradients in the polymeric system may lead to a desired gradient in a single property, or to a combination of more than one property which may assume optimum values in different regions of the material. In the latter case, one of the properties is frequently related to mechanical integrity.Possible applications of gradient polymeric systems include platic gasoline tanks, biomedical implants, and damping materials for a wide frequency range.     

Preparation of functional nanostructured particles by spray drying

When particle dimensions are reduced to the order of several nanometers, their physical and chemical properties deviate significantly from the bulk properties of such materials. Because of this, there is abundant potential for their use in future technologies including electronic and optoelectronic, mechanical, chemical, cosmetic, medical, drug, and food technologies. However, due to their extremely small sizes, the particles suffer from many problems related to their surface and thermal stability, shape preservation, handling, assembly in devices, etc. It is therefore an important challenge to solve these problems by developing slightly larger particles (e. g. on the submicrometer scale) in which the properties generated by the nanoscale material are preserved. One approach to this is to trap nanoparticles in a micrometer-sized inert matrix. This approach allows the nanoscale properties to be retained, since nanoparticles are separated from each other in the inert matrix. The inert matrix also serves as a coating medium that inhibits any chemical changes to the surface of the nanoparticles. Their larger size allows easy handling or assembly in devices. A promising method for designing and fabricating these composite structures is a spray method, in which spherical particles can be produced. In this paper, we review the nanostructural processing (synthesis) of submicrometersized particles by a spray method, which provides a restricted reaction environment (such as pores or cages) in the matrix for their synthesis and handling. The characterization and potential applications of these composites are also discussed.     

Introducing porosity into polyimide nanoparticles

Novel porous polyimides (PIs) having diameters of several hundred nanometers have been fabricated successfully from precursor poly(amic acid) (PAA) derivatives with poly(acrylic acid) (PAS) as the porogen, using a reprecipitation method and subsequent imidization. The superficial high porosity with deep pores was introduced when using a more compatible combination of PAA and the porogen, i.e., PI (BPDA-PDA) and PAS rather than PI (10FEDA-4FMPD and PAS); the pore sizes ranged from 20 to 100 nm. The resulting porous PI nanoparticles had thermally stabilities (determined from their 5% weight loss temperatures at 400 degrees C) similar to those of corresponding PI nanoparticles lacking porous structures. Microphase separation within the PAA nanoparticles after reprecipitation induced the porous surface structure, the properties of which were influenced by the molecular weight of PAS and the chemical structure of PAA. These unique porous PI nanoparticles have great potential for application as low-k materials in next-generation technologies.     

Mass Measurements Reveal Preferential Sorption of Mixed Solvent Components in Porous Nanoparticles

The interplay of physical and chemical properties at the nanometer scale provides porous nanoparticles with unique sorption and interaction capabilities. These properties have aroused great interest toward this class of materials for application ranging from chemical and biological sensing to separation and drug delivery. However, so far the preferential uptake of different components of mixed solvents by porous nanoparticles is not measured due to a lack of methods capable of detecting the resulting change in physical properties. Here, a new method, nanomechanical mass correlation spectroscopy, is used to reveal an unexpected dependence of the effective mass density of porous metal–organic framework (MOF) nanoparticles on the chemistry of the solvent system and on the chemical functionalization of the MOF's internal surface. Interestingly, the pore size of the nanoparticles is much too large for the exclusion of small solvent molecules by steric hindrance. The variation of effective density of the nanoparticles with the solvent composition indicates that a complex solvent environment can form within or around the nanoparticles, which may substantially differ from the solvent composition.     

Elastic membranes of close-packed nanoparticle arrays

Nanoparticle superlattices are hybrid materials composed of close-packed inorganic particles separated by short organic spacers. Most work so far has concentrated on the unique electronic, optical and magnetic behaviour of these systems. Here, we demonstrate that they also possess remarkable mechanical properties. We focus on two-dimensional arrays of close-packed nanoparticles and show that they can be stretched across micrometre-size holes. The resulting free-standing monolayer membranes extend over hundreds of particle diameters without crosslinking of the ligands or further embedding in polymer. To characterize the membranes we measured elastic properties with force microscopy and determined the array structure using transmission electron microscopy. For dodecanethiol-ligated 6-nm-diameter gold nanocrystal monolayers, we find a Young's modulus of the order of several GPa. This remarkable strength is coupled with high flexibility, enabling the membranes to bend easily while draping over edges. The arrays remain intact and able to withstand tensile stresses up to temperatures around 370 K. The purely elastic response of these ultrathin membranes, coupled with exceptional robustness and resilience at high temperatures should make them excellent candidates for a wide range of sensor applications.     

Funktionelle Schichten auf der Basis von Hybridpolymeren

Functional layers on the base of hybrid polymers The present study describes the synthesis and application of functional nanoparticles based of silicon. Examples for technical interesting applications are antiadhesive layers, layers with adjustable hydrophobic/hydrophilic properties of the surface as well as porous layers for ink‐jet‐materials. By reaction of functional nanoparticles with maleic acid copolymers or polyepoxides hybrid polymers can be obtained which have good barrier properties depending from their structure and are useful as protective coatings for plastic container.     

基于纳米材料的气凝胶制备及应用

气凝胶是一种三维多孔材料,具有孔隙率高、比表面积大、密度低等特性。以纳米材料构筑气凝胶可进一步调控孔隙结构、改善机械强度,同时还能赋予气凝胶高导电性、低热导率、高吸附性和隔音吸声等特性,在储能、保温隔热、吸附材料等领域有重要的应用。重点对近年以纳米颗粒、纳米纤维素、碳纳米纤维、碳纳米管、石墨烯等不同形态纳米材料构筑的气凝胶的制备、结构、性能和应用进行了综述,同时展望了气凝胶的发展前景与方向。     

Tetrazoles: Unique Capping Ligands and Precursors for Nanostructured Materials

Capping agents play an important role in the colloidal synthesis of nanomaterials because they control the nucleation and growth of particles, as well as their chemical and colloidal stability. During recent years tetrazole derivatives have proven to be advanced capping ligands for the stabilization of semiconductor and metal nanoparticles. Tetrazole‐capped nanoparticles can be prepared by solution‐phase or solventless single precursor approaches using metal derivatives of tetrazoles. The solventless thermolysis of metal tetrazolates can produce both individual semiconductor nanocrystals and nanostructured metal monolithic foams displaying low densities and high surface areas. Alternatively, highly porous nanoparticle 3D assemblies are achieved through the controllable aggregation of tetrazole‐capped particles in solutions. This approach allows for the preparation of non‐ordered hybrid structures consisting of different building blocks, such as mixed semiconductor and metal nanoparticle‐based (aero)gels with tunable compositions. Another unique property of tetrazoles is their complete thermal decomposition, forming only gaseous products, which is employed in the fabrication of organic‐free semiconductor films from tetrazole‐capped nanoparticles. After deposition and subsequent thermal treatment these films exhibit significantly improved electrical transport. The synthetic availability and advances in the functionalization of tetrazoles necessitate further design and study of tetrazole‐capped nanoparticles for various applications.     

Realization of thermally durable close-packed 2D gold nanoparticle arrays using self-assembly and plasma etching

Realization of thermally and chemically durable, ordered gold nanostructures using bottom-up self-assembly techniques are essential for applications in a wide range of areas including catalysis, energy generation, and sensing. Herein, we describe a modular process for realizing uniform arrays of gold nanoparticles, with interparticle spacings of 2?nm and above, by using RF plasma etching to remove ligands from self-assembled arrays of ligand-coated gold nanoparticles. Both nanoscale imaging and macroscale spectroscopic characterization techniques were used to determine the optimal conditions for plasma etching, namely RF power, operating pressure, duration of treatment, and type of gas. We then studied the effect of nanoparticle size, interparticle spacing, and type of substrate on the thermal durability of plasma-treated and untreated nanoparticle arrays. Plasma-treated arrays showed enhanced chemical and thermal durability, on account of the removal of ligands. To illustrate the application potential of the developed process, robust SERS (surface-enhanced Raman scattering) substrates were formed using plasma-treated arrays of silver-coated gold nanoparticles that had a silicon wafer or photopaper as the underlying support. The measured value of the average SERS enhancement factor (2?×?10(5)) was quantitatively reproducible on both silicon and paper substrates. The silicon substrates gave quantitatively reproducible results even after thermal annealing. The paper-based SERS substrate was also used to swab and detect probe molecules deposited on a solid surface.     

Arrays of Hollow Silica Half‐Nanospheres Via the Breath Figure Approach

Breath figures (BFs) are patterns of liquid droplets that usually form upon condensation on a cold surface. Earlier work has shown that BFs can be used to produce continuous films of porous honeycomb‐structured patterns on various types of materials, paving the path to a number of important applications such as the manufacturing of highly ordered nano‐ and micron‐sized templates, micro lenses, and superhydrophobic coatings. It is worth noting, however, that few new findings have been reported in this area in recent years, limiting pursuits of novel architectures and key applications. In this report, an alternative method is described by which arrays of hollow silica half‐nanospheres can be produced via BF templates. In the present method, a chemical vapor deposition (CVD) protocol performed while the BF is formed on a glass substrate yields a nanostructured pattern of silica half‐spheres, which size (100–700 nm) and density across the glass surface vary with substrate modification and with the relative rates of water condensation and hydrolysis from silica precursors (a process carried out at room temperature). This method of forming arrays of hollow half‐nanospheres via the BF approach may be applicable to various other oxides and a broad range of substrates including large‐area flexible plastics.     

Aerosol route to functional nanostructured inorganic and hybrid porous materials

The major advances in the field of the designed construction of hierarchically structured porous inorganic or hybrid materials wherein multiscale texturation is obtained via the combination of aerosol or spray processing with sol-gel chemistry, self-assembly and multiple templating are the topic of this review. The available materials span a very large set of structures and chemical compositions (silicates, aluminates, transition metal oxides, nanocomposites including metallic or chalcogenides nanoparticles, hybrid organic-inorganic, biohybrids). The resulting materials are manifested as powders or smart coatings via aerosol-directed writing combine the intrinsic physical and chemical properties of the inorganic or hybrid matrices with defined multiscale porous networks having a tunable pore size and connectivity, high surface area and accessibility. Indeed the combination of soft chemical routes and spray processing provides "a wind of change" in the field of "advanced materials". These strategies give birth to a promising family of innovative materials with many actual and future potential applications in various domains such as catalysis, sensing, photonic and microelectronic devices, nano-ionics and energy, functional coatings, biomaterials, multifunctional therapeutic carriers, and microfluidics, among others.     

纳米碳管的孔结构、相关物性和应用

评述了纳米碳管（CNT）的纳米孔隙结构及其决定的特殊物化性质,以及潜在的应用。CNT孔径体系由多层次的孔隙组合而成,开口的一维中空管腔是最基本的孔隙结构,其纳米级的尺度和物理形态决定了它的超常吸附性质和其它物化特性,使CNT成为极具潜力的纳米级能量载体;提供了进行一维物理化学过程的极限反应空间,是真正意义上的纳米反应器;CNT的比表面积和孔径结构及其决定的吸附性质还决定或者影响着许多其它物化性质（如电磁性质）。发展纳米碳管中的物理化学研究,制备基于大表面积、可控孔结构CNT的纳米器件,是CNT领域的重要研究方向。     

Unveiling the formation pathway of single crystalline porous silicon nanowires

Porous silicon nanowire is emerging as an interesting material system due to its unique combination of structural, chemical, electronic, and optical properties. To fully understand their formation mechanism is of great importance for controlling the fundamental physical properties and enabling potential applications. Here we present a systematic study to elucidate the mechanism responsible for the formation of porous silicon nanowires in a two-step silver-assisted electroless chemical etching method. It is shown that silicon nanowire arrays with various porosities can be prepared by varying multiple experimental parameters such as the resistivity of the starting silicon wafer, the concentration of oxidant (H(2)O(2)) and the amount of silver catalyst. Our study shows a consistent trend that the porosity increases with the increasing wafer conductivity (dopant concentration) and oxidant (H(2)O(2)) concentration. We further demonstrate that silver ions, formed by the oxidation of silver, can diffuse upwards and renucleate on the sidewalls of nanowires to initiate new etching pathways to produce a porous structure. The elucidation of this fundamental formation mechanism opens a rational pathway to the production of wafer-scale single crystalline porous silicon nanowires with tunable surface areas ranging from 370 to 30 m(2) g(-1) and can enable exciting opportunities in catalysis, energy harvesting, conversion, storage, as well as biomedical imaging and therapy.     

粉状纳米材料的表面研究进展与展望

粉状纳米材料表面是决定其性能的关键性因素之一。用热物理法,化学法和机械制造法都可制得纳米粉,但其表面却有所不同。热物理法能得到表面比较纯净的纳米粉。纳米粉表面与其成分、结构和形态有关,它对纳米粉的化学和物理性能有着决定性的影响。因此,粉状纳粉材料应用前景也决取于其表面研究的进展。