Adhesion and friction force coupling of gecko setal arrays: implications for structured adhesive surfaces

The extraordinary climbing ability of geckos is partially attributed to the fine structure of their toe pads, which contain arrays consisting of thousands of micrometer-sized stalks (setae) that are in turn terminated by millions of fingerlike pads (spatulae) having nanoscale dimensions. Using a surface forces apparatus (SFA), we have investigated the dynamic sliding characteristics of setal arrays subjected to various loading, unloading, and shearing conditions at different angles. Setal arrays were glued onto silica substrates and, once installed into the SFA, brought toward a polymeric substrate surface and then sheared. Lateral shearing of the arrays was initiated along both the "gripping" and "releasing" directions of the setae on the foot pads. We find that the anisotropic microstructure of the setal arrays gives rise to quite different adhesive and tribological properties when sliding along these two directions, depending also on the angle that the setae subtend with respect to the surface. Thus, dragging the setal arrays along the gripping direction leads to strong adhesion and friction forces (as required during contact and attachment), whereas when shearing along the releasing direction, both forces fall to almost zero (as desired during rapid detachment). The results and analysis provide new insights into the biomechanics of adhesion and friction forces in animals, the coupling between these two forces, and the specialized structures that allow them to optimize these forces along different directions during movement. Our results also have practical implications and criteria for designing reversible and responsive adhesives and articulated robotic mechanisms.     

Supramolecular metal-polypyridyl and Ru(II) porphyrin complexes: photophysical, electron paramagnetic resonance, and electrochemical studies

A series of mixed-metal supramolecular porphyrin arrays in which the geometry of the central metal-polypyridyl moiety defines the spatial arrangement of two or more Ru(II)-porphyrin units through axial coordination have been prepared by employing self-assembly based protocols, and their photophysical and electrochemical properties have been studied. The electrochemical properties of the constituent parts of these arrays depend only on their own chemical environment, regardless of the nuclearity and the overall charge of the compound; in this way species with predetermined redox patterns can be obtained via the synthetic control of the self-assembly process. Interestingly, several of these arrays are luminescent both at room and at low temperatures, and in many cases core-to-periphery or periphery-to-core intramolecular energy transfer processes take place according to the nature of the central metal template.     

Estimating the chemical rank of three-way data arrays by a simple linear transform incorporating Monte Carlo simulation

Estimating an appropriate chemical rank of a three-way data array is very important to second-order calibration. In this paper, a simple linear transform incorporating Monte Carlo simulation approach (LTMC) to estimate the chemical rank of a three-way data array was suggested. The new method determines the chemical rank through performing a simple linear transform procedure on the original cube matrix to produce two subspaces by singular value decomposition. One of two subspaces is derived from the original three-way data array itself and the other is derived from a new three-way data array produced by the linear transformation of the original one. Projection technique incorporating the Monte Carlo approach acts as distinguishing criterion to choose the appropriate component number of the system. Simulated three-way trilinear data arrays with different noise types (homoscedastic and heteroscedastic), various noise level as well as high collinearity are used to illustrate the feasibility of the new method. The results have shown that the new method could yield accurate results with different conditions appended. The feasibility of the new method is also confirmed by two real arrays, HPLC-DAD data and excitation-emission fluorescent data. All the results are compared with the other three factor-determining methods: factor indicator function (IND), core consistency diagnostic (CORCONDIA) and two-mode subspace comparison (TMSC) approach. It shows that the newly proposed algorithm can objectively and quickly determine the chemical rank to fit the trilinear model.     

Multicolour Fluorescent Memory Based on the Interaction of Hydroxy Terphenyls with Fluoride Anions

Memory operations based on variation of a molecule’s properties are important because they may lead to device miniaturization to the molecular scale or increasingly complex information processing protocols beyond the binary level. Molecular memory also introduces possibilities related to information‐storage security where chemical information (or reagents) might be used as an encryption key, in this case, acidic/basic reagents. Chemical memory that possesses both volatile and non‐volatile functionality requires reversible conversion between at least two chemically different stable or quasi‐stable states. Here we have developed the phenol–phenoxide equilibrium of phenol fluorophores as a data storage element, which can be used to write or modulate data using chemical reagents. The properties of this system allow data to be stored and erased either in non‐volatile or volatile modes. We also demonstrate non‐binary switching of states made possible by preparation of  a composite containing the molecular memory elements.     

Synthesis and characterization of axial heterojunction inorganic-organic semiconductor nanowire arrays

The end-to-end P-N heterojunction nanowire arrays combined organic (poly[1,4-bis(pyrrol-2-yl)benzene], BPB) and inorganic (CdS) molecules have been successfully designed and fabricated. The electrical properties of P-N heterojunctions of organic-inorganic nanowire arrays were investigated. The diode nature and rectifying feature of P-N heterojunction nanowire arrays were observed. The rectification ratio of the diode increased from 29.9 to 129.7 as the illumination intensity increased. The material exhibits a new property, which is an improvement in the integration of the physical and chemical properties of the two independent components.     

Sol-gel route to zirconia-Pt-nanoelectrode arrays 8 nm in radius: their geometrical impact in mass transport

The fabrication of advanced nanoelectrode arrays and their electrochemical characterization are presented. These nanoelectrode arrays are constituted of nanoperforations of 8 nm in radius leading to platinum and protected by an inorganic matrix made of crystalline zirconia. These nanoelectrodes arrays provide a ceramic support with a high thermal and chemical stability. These devices present a well characterized structure with a control of size, shape, and spacing of the nanoelectrodes, allowing studying in depth both the mass transport and the charge transfer properties in the nanometer range. The radial diffusion occurs when the experimental scan rate is superior to a theoretical scan rate estimated from the model proposed by Amatore and colleagues. The coupling between electrochemical analysis and nanoscale structural characterizations successfully demonstrates that the theory defined for microelectrode arrays can be directly transposed for well-defined metal-ceramic nanocomposite nanoelectrodes.     

Combining rails and anchors with laser forcing for selective manipulation within 2D droplet arrays

We demonstrate the combination of a rails and anchors microfluidic system with laser forcing to enable the creation of highly controllable 2D droplet arrays. Water droplets residing in an oil phase can be pinned to anchor holes made in the base of a microfluidic channel, enabling the creation of arrays by the appropriate patterning of such holes. The introduction of laser forcing, via laser induced thermocapillary forces to anchored droplets, enables the selective extraction of particular droplets from an array. We also demonstrate that such anchor arrays can be filled with multiple, in our case two, droplets each and that if such droplets have different chemical contents, the application of a laser at their interface triggers their merging and a chemical reaction to take place. Finally by adding guiding rails within the microfluidic structure we can selectively fill large scale arrays with monodisperse droplets with significant control over their contents. In this way we make a droplet array filled with 96 droplets containing different concentrations of fluorescent microparticles.     

A chemometric approach based on a novel similarity/diversity measure for the characterisation and selection of electronic nose sensors

Electronic nose sensor signals provide a digital fingerprint of the product in analysis, which can be subsequently investigated by means of chemometrics. In this paper, the fingerprint characterisation of electronic nose data has been studied by means of a novel chemometric approach based on the partial ordering technique and the Hasse matrix. This matrix can be associated to each data sequence and the similarity between two sequences can be evaluated with the definition of a distance between the corresponding Hasse matrices. Since all the signals achieved along time are intrinsically ordered, the data provided by electronic nose can be also considered as sequential data and consequently characterized by means of the proposed approach. The similarity/diversity measure has been here applied in order to characterize the class discrimination capability of each electronic nose sensor: extra virgin olive oil samples of different geographical origin have been considered and Hasse distances have been used to select the sensors which appear more able to discriminate the olive oil origins. The distance based on the Hasse matrix has showed some useful properties and proved to be able to link each electronic nose time profile to a meaningful mathematical term (the Hasse matrix), which can be consequently studied by multivariate analysis.     

Aligned Nanorod Arrays: Additive and Emergent Properties

Studies of one-dimensional nanostructures of various types (such as quantum wires, nanorods, nanotubes and nanobelts) have progressed substantially during the past decade and have been reviewed by a number of authors. Here, we provide a concise overview of the synthesis and special properties of arrays of parallel nanorods, whose behavior is often quite distinct from that of individual nanorods of the same material. We show that the distinctive behavior of such nanorod arrays may occur due to their exhibiting either additive or emergent properties. The former originates from a simple amplification of some advantageous property shown by a single nanorod, thus making it usable in a practical device; while the latter necessarily involves the presence of the array, and would not be observable from a single nanorod. Nanorod arrays have been shown to have possible applications in diverse areas that include nanolasers, microcavities, surface enhanced Raman effect, photovoltaic cells, field emission sources, gas sensing, electrical discharge and in hydrophobic surfaces. We first present an overview of some of the physical and chemical synthesis strategies for nanorod arrays, followed by a brief review of their applications in the areas just mentioned.     

Rutile TiO2 nano-branched arrays on FTO for dye-sensitized solar cells

Hierarchical TiO(2) nanostructures would be desirable for preparing dye-sensitized solar cells because of their large amount of dye adsorption and superior light harvesting efficiency, as well as efficient charge separation and transport properties. In this study, rutile TiO(2) nano-branched arrays grown directly on transparent conductive glass (FTO) were prepared by a facile two-step wet chemical synthesis process, using a simple aqueous chemical growth method involving immersing the TiO(2) nanorod arrays in an aqueous TiCl(4) solution as seeds, which were prepared by a hydrothermal method. The dye-sensitized solar cells based on the TiO(2) nano-branched arrays which were only about 3 μm in length show a short-circuit current intensity of 10.05 mA cm(-2) and a light-to-electricity conversion efficiency of 3.75%, which is nearly three times as high as that of bare nanorod arrays, due to the preferable nanostructure, which not only retains the efficient charge separation and transport properties of the nanorod arrays, but also can improve the amount of dye adsorption due to the increased specific surface area from the nanobranches.     

Supramolecular squares of porphyrazines

The design, self-assembly, and characterization of discrete arrays of porphyrazine (Pz) squares are presented to illustrate the supramolecular chemistry of these macrocycles, and to highlight that these arrays have physical chemical properties that are different from similar arrays of porphyrinic systems.     

X-ray spectrometry and chemometrics in sugar classification, correlation with degree of sweetness and specific rotation of polarized light

This work presents correlations of conventional energy dispersive X-ray fluorescence spectra of common sugars with degrees of sweetness obtained via sensorial tests and specific rotations of polarized light, both data from the literature. Also, classifications of sugars are achieved based on their specific structures. Principal component analysis and partial least square chemometric tools are used to establish these modelings. Once again it is demonstrated that a common bench-top X-ray spectrometer can be used not only for inorganic analysis, but also shows potential in studies of organic constituents.     

Construction of multiporphyrin arrays using ruthenium and rhodium coordination to phosphines

The synthesis of linear multiporphyrin arrays with mono- and bisphosphine-substituted porphyrins as ligand donors and ruthenium(II) or rhodium(III) porphyrins as ligand acceptors is described. With appropriate amounts of the building blocks mixed, linear dimeric and trimeric arrays have been synthesized and analyzed by (1)H NMR and (31)P NMR spectroscopy. The Ru/Rh acceptor porphyrins can be located either at the periphery or in the center of the array. Likewise, the monophosphine porphyrins can be positioned at the periphery, thus allowing a high degree of freedom in the overall composition of the arrays. This way, both donor and acceptor porphyrins can act as chain extenders or terminators. One of the trimeric complexes with two nickel and one ruthenium porphyrin has also been analyzed by X-ray crystallography. Attempts have also been made to synthesize higher order arrays by mixing appropriate amounts of the porphyrins; however, from the NMR data it cannot be concluded if monodisperse five, seven, or nine porphyrin arrays are present or if the solutions are composed of a statistical mixture of smaller and larger arrays.     

智能蜂窝状有序多孔薄膜：体系构建、响应性能及应用探索

蜂窝状有序多孔膜是一种典型的具有微、纳米尺寸的图案化高分子薄膜材料,在超疏水表面、光电材料、组织工程、生物医学、传感器等领域都具有良好的应用前景。表面形貌或性质具有可逆刺激响应特性的智能型多孔膜不仅拥有常规多孔膜的性能,而且还拥有独特的"开-关"功能,因此受到广泛关注。本文回顾了智能有序多孔膜近年的研究进展,重点对其体系构建、响应方式、机理、性能和相关应用进行了归纳与分析,评述了不同刺激响应多孔膜的特点及优劣势,探讨了智能多孔膜的优化设计及提高响应性能等问题,指出了目前面临的挑战,并展望了未来的发展方向。     

基于3d元素掺杂的石墨二炔分子传感材料性能调控

二维碳材料因其独特的性质成为凝聚态物理、纳米电子学、生物医药等领域的前沿研究热点。石墨二炔具有天然的半导体特性及独特的大孔网状结构,在纳米电子器件和生物传感方面比石墨烯更具优势。本文使用第一性原理计算研究了单层石墨二炔的纳米带电子输运性质和及石墨二炔对小分子的吸附。我们考虑用掺杂3d金属原子的方法来增强对分子的吸附力。选择在石墨二炔表面吸附能较大的钪(Sc)、钛(Ti)原子,确定石墨二炔表面Sc、Ti单原子在室温下的稳定性,研究了Sc、Ti掺杂石墨二炔用于分子检测的潜在可能。从能带、载流子浓度等方面全面探讨了Sc、Ti掺杂石墨二炔对甲醛分子(HCHO)的响应。又进一步研究了石墨二炔与氨基酸分子间相互作用,发现色散力在相互作用中占主导地位。研究了吸附氨基酸对石墨二炔电子输运的影响,探讨石墨二炔在生物传感方面的潜在应用。     

WO3纳米管的模板法制备及表征

0引言 WO3纳米材料具有光致变色、电致变色、气致变色等特性,可用于光学信息和储存显示器、pH值探测器、气敏传感器、灵敏窗口等[1,2];并且在太阳能的储存与利用、光电转换、光催化降解大气和水中的污染物等方面有着广阔的应用前景[3,4],成为近几年重点研究的半导体材料之一.以前纳米WO3的制备主要集中在薄膜上,其薄膜的制备工艺已经相当成熟,主要包括蒸发法、溅射法、CVD法、喷涂法、阳极氧化法、溶胶-凝胶法等[3].     

A novel efficient way to estimate the chemical rank of high-way data arrays

A novel method, a subspace projection of pseudo high-way data array (SPPH), was developed for estimating the chemical rank of high-way data arrays. The proposed method determines the chemical rank through performing singular value decomposition (SVD) on the slice matrices of original high-way data array to produce a pseudo high-way data array and employing the idea of the difference of the original truncated data set and the pseudo one. Compared with traditional methods, it uses the information from eigenvectors combined with the projection residual to estimate the rank of the three-way data arrays instead of using the eigenvalue. In order to demonstrate the excellent performance of the new method, simulated and real three-way data arrays were carried out by the proposed method. The results showed that the proposed method could accurately and quickly determine the chemical rank to fit the trilinear model. Moreover, the newly proposed method was compared with the other four factor-determining methods, i.e. factor indicator function (IND), ADD-ONE-UP, core consistency diagnostic (CORCONDIA) and two-mode subspace comparison (TMSC) approaches. It was found that the proposed method can deal with more complex situations with existence of severe collinearity and trace concentration than many other methods can and performs well in practical applications.     

Nanostructured optical fibre arrays for high-density biochemical sensing and remote imaging

Optical fibre bundles usually comprise a few thousand to tens of thousands of individually clad glass optical fibres. The ordered arrangement of the fibres enables coherent transmission of an image through the bundle and therefore enables analysis and viewing in remote locations. In fused bundles, this architecture has also been used to fabricate arrays of various micro to nano-scale surface structures (micro/nanowells, nanotips, triangles, etc.) over relatively large areas. These surface structures have been used to obtain new optical and analytical capabilities. Indeed, the imaging bundle can be thought of as a “starting material” that can be sculpted by a combination of fibre drawing and selective wet-chemical etching processes. A large variety of bioanalytical applications have thus been developed, ranging from nano-optics to DNA nanoarrays. For instance, nanostructured optical surfaces with intrinsic light-guiding properties have been exploited as surface-enhanced Raman scattering (SERS) platforms and as near-field probe arrays. They have also been productively associated with electrochemistry to fabricate arrays of transparent nanoelectrodes with electrochemiluminescent imaging properties. The confined geometry of the wells has been loaded with biosensing materials and used as femtolitre-sized vessels to detect single molecules. This review describes the fabrication of high-density nanostructured optical fibre arrays and summarizes the large range of optical and bioanalytical applications that have been developed, reflecting the versatility of this ordered light-guiding platform.