Mass spectrometry sampling under ambient conditions with desorption electrospray ionization

A new method of desorption ionization is described and applied to the ionization of various compounds, including peptides and proteins present on metal, polymer, and mineral surfaces. Desorption electrospray ionization (DESI) is carried out by directing electrosprayed charged droplets and ions of solvent onto the surface to be analyzed. The impact of the charged particles on the surface produces gaseous ions of material originally present on the surface. The resulting mass spectra are similar to normal ESI mass spectra in that they show mainly singly or multiply charged molecular ions of the analytes. The DESI phenomenon was observed both in the case of conductive and insulator surfaces and for compounds ranging from nonpolar small molecules such as lycopene, the alkaloid coniceine, and small drugs, through polar compounds such as peptides and proteins. Changes in the solution that is sprayed can be used to selectively ionize particular compounds, including those in biological matrices. In vivo analysis is demonstrated.     

Temperature-induced hydrophobic-hydrophilic transition observed by water adsorption

The properties of nanoconfined and interfacial water in the proximity of hydrophobic surfaces play a pivotal role in a variety of important phenomena such as protein folding. Water inside single-walled carbon nanotubes (SWNTs) can provide an ideal system for investigating such nanoconfined interfacial water on hydrophobic surfaces, provided that the nanotubes can be opened without introducing excess defects. Here, we report a hydrophobic-hydrophilic transition upon cooling from 22 degrees C to 8 degrees C via the observation of water adsorption isotherms in SWNTs measured by nuclear magnetic resonance. A considerable slowdown in molecular reorientation of such adsorbed water was also detected. The observed transition demonstrates that the structure of interfacial water could depend sensitively on temperature, which could lead to intriguing temperature dependences involving interfacial water on hydrophobic surfaces.     

Self-sorted, aligned nanotube networks for thin-film transistors

To find use in electronics, single-walled carbon nanotubes need to be efficiently separated by electronic type and aligned to ensure optimal and reproducible electronic properties. We report the fabrication of single-walled carbon nanotube (SWNT) network field-effect transistors, deposited from solution, possessing controllable topology and an on/off ratio as high as 900,000. The spin-assisted alignment and density of the SWNTs are tuned by different surfaces that effectively vary the degree of interaction with surface functionalities in the device channel. This leads to a self-sorted SWNT network in which nanotube chirality separation and simultaneous control of density and alignment occur in one step during device fabrication. Micro-Raman experiments corroborate device results as a function of surface chemistry, indicating enrichment of the specific SWNT electronic type absorbed onto the modified dielectric.     

汽车车身表面中的三角区域设计

车身表面的三角区域设计是一非常困难的问题。本文首先简介了车身表面中常用的三角区域的设计方法，并在对比这些方法的优缺点的基础上提出了一利用双三次Ｂ样条曲面插值四边形退化区域的简化模型。     

Chemical detection with a single-walled carbon nanotube capacitor

We show that the capacitance of single-walled carbon nanotubes (SWNTs) is highly sensitive to a broad class of chemical vapors and that this transduction mechanism can form the basis for a fast, low-power sorption-based chemical sensor. In the presence of a dilute chemical vapor, molecular adsorbates are polarized by the fringing electric fields radiating from the surface of a SWNT electrode, which causes an increase in its capacitance. We use this effect to construct a high-performance chemical sensor by thinly coating the SWNTs with chemoselective materials that provide a large, class-specific gain to the capacitance response. Such SWNT chemicapacitors are fast, highly sensitive, and completely reversible.     

基于CE-Bézier曲面的拖拉机造型设计

【目的】用多张含有形状参数的CE-Bézier曲面光滑拼接进行拖拉机造型曲面的表示,解决拖拉机造型设计中复杂曲面无法用单一曲面进行描述的问题。【方法】构建多张CE-Bézier曲面,对这些曲面进行光滑拼接,并在调整各曲面公共边界的位置及其形状参数的情况下,形成不同的拖拉机造型方案。【结果】快速得到多个拖拉机机身造型方案。【结论】该方法高效、易于操作,具有良好的应用前景。     

Platelet membrane glycoprotein IIb/IIIa: member of a family of Arg-Gly-Asp--specific adhesion receptors

Adhesive interactions of the platelet surface with plasma proteins such as fibrinogen and fibronectin play an important role in thrombosis and hemostasis. The binding of both of these proteins to platelets is inhibited by synthetic peptides containing the sequence Arg-Gly-Asp, which corresponds to the cell adhesion site in fibronectin and is also present in the alpha chain of fibrinogen. An affinity matrix made of an insolubilized heptapeptide containing the Arg-Gly-Asp sequence selectively binds the platelet membrane glycoprotein IIb/IIIa from detergent extracts of platelets. When incorporated into liposome membranes, the isolated protein confers to the liposomes the ability to bind to surfaces coated with fibrinogen, fibronectin, and vitronectin but not to surfaces coated with thrombospondin or albumin. This platelet receptor is related to the previously identified fibronectin and vitronectin receptors in that it recognizes an Arg-Gly-Asp sequence but differs from the other receptors in its wider specificity toward various adhesive proteins. These results establish the existence of a family of adhesion receptors that recognize the sequence Arg-Gly-Asp.     

Macroscopic, neat, single-walled carbon nanotube fibers

Well-aligned macroscopic fibers composed solely of single-walled carbon nanotubes (SWNTs) were produced by conventional spinning. Fuming sulfuric acid charges SWNTs and promotes their ordering into an aligned phase of individual mobile SWNTs surrounded by acid anions. This ordered dispersion was extruded via solution spinning into continuous lengths of macroscopic neat SWNT fibers. Such fibers possess interesting structural composition and physical properties.     

Crystalline Ropes of Metallic Carbon Nanotubes

Fullerene single-wall nanotubes (SWNTs) were produced in yields of more than 70 percent by condensation of a laser-vaporized carbon-nickel-cobalt mixture at 1200degreesC. X-ray diffraction and electron microscopy showed that these SWNTs are nearly uniform in diameter and that they self-organize into "ropes," which consist of 100 to 500 SWNTs in a two-dimensional triangular lattice with a lattice constant of 17 angstroms. The x-ray form factor is consistent with that of uniformly charged cylinders 13.8 +/- 0.2 angstroms in diameter. The ropes were metallic, with a single-rope resistivity of <10(-4) ohm-centimeters at 300 kelvin. The uniformity of SWNT diameter is attributed to the efficient annealing of an initial fullerene tubelet kept open by a few metal atoms; the optimum diameter is determined by competition between the strain energy of curvature of the graphene sheet and the dangling-bond energy of the open edge, where growth occurs. These factors strongly favor the metallic (10,10) tube with C5v symmetry and an open edge stabilized by triple bonds.     

Covalently bridging gaps in single-walled carbon nanotubes with conducting molecules

Molecular electronics is often limited by the poorly defined nature of the contact between the molecules and the metal surface. We describe a method to wire molecules into gaps in single-walled carbon nanotubes (SWNTs). Precise oxidative cutting of a SWNT produces carboxylic acid-terminated electrodes separated by gaps of 相似文献   

Designing superoleophobic surfaces

Understanding the complementary roles of surface energy and roughness on natural nonwetting surfaces has led to the development of a number of biomimetic superhydrophobic surfaces, which exhibit apparent contact angles with water greater than 150 degrees and low contact angle hysteresis. However, superoleophobic surfaces-those that display contact angles greater than 150 degrees with organic liquids having appreciably lower surface tensions than that of water-are extremely rare. Calculations suggest that creating such a surface would require a surface energy lower than that of any known material. We show how a third factor, re-entrant surface curvature, in conjunction with chemical composition and roughened texture, can be used to design surfaces that display extreme resistance to wetting from a number of liquids with low surface tension, including alkanes such as decane and octane.     

Design of a surface alloy catalyst for steam reforming

Detailed studies of elementary chemical processes on well-characterized single crystal surfaces have contributed substantially to the understanding of heterogeneous catalysis. Insight into the structure of surface alloys combined with an understanding of the relation between the surface composition and reactivity is shown to lead directly to new ideas for catalyst design. The feasibility of such an approach is illustrated by the synthesis, characterization, and tests of a high-surface area gold-nickel catalyst for steam reforming.     

A reversibly switching surface

We report the design of surfaces that exhibit dynamic changes in interfacial properties, such as wettability, in response to an electrical potential. The change in wetting behavior was caused by surface-confined, single-layered molecules undergoing conformational transitions between a hydrophilic and a moderately hydrophobic state. Reversible conformational transitions were confirmed at a molecular level with the use of sum-frequency generation spectroscopy and at a macroscopic level with the use of contact angle measurements. This type of surface design enables amplification of molecular-level conformational transitions to macroscopic changes in surface properties without altering the chemical identity of the surface. Such reversibly switching surfaces may open previously unknown opportunities in interfacial engineering.     

Designed protein-protein association

The analysis of natural contact interfaces between protein subunits and between proteins has disclosed some general rules governing their association. We have applied these rules to produce a number of novel assemblies, demonstrating that a given protein can be engineered to form contacts at various points of its surface. Symmetry plays an important role because it defines the multiplicity of a designed contact and therefore the number of required mutations. Some of the proteins needed only a single side-chain alteration in order to associate to a higher-order complex. The mobility of the buried side chains has to be taken into account. Four assemblies have been structurally elucidated. Comparisons between the designed contacts and the results will provide useful guidelines for the development of future architectures.     

Computer-aided molecular design

Theoretical chemistry, as implemented on fast computers, is beginning to yield accurate predictions of the thermodynamic and kinetic properties of large molecular assemblies. In addition to providing detailed insights into the origins of molecular activity, theoretical calculations can be used to design new molecules with specific properties. This article describes two types of calculations that show special promise as design tools, the thermodynamic cycle-perturbation method and the Brownian reactive dynamics method. These methods can be applied to calculate equilibrium and rate constants that describe many aspects of molecular recognition, stability, and reactivity.     

Electrically conductive metallomacrocyclic assemblies

The design, synthesis, and study of electrically conductive molecular and polymeric substances constitute a new scientific endeavor involving the interaction of chemists, physicists, and materials scientists. The strategies, developments, and challenges in these two closely related fields are analyzed via a class of materials that bridges both: assemblies of electrically conductive metallomacrocycles. It is seen that efforts to rationally synthesize tailored, "metal-like" molecular arrays lead logically to structure-enforced polymeric assemblies of linked molecular subunits such as metallophthalocyanines. The properties of these assemblies and fragments thereof provide information on the relationship between atomic-level local architecture, electronic structure, and macroscopic transport properties. Electrcally conductive, processable polymeric materals also follow from these results.     

Brownian motion of stiff filaments in a crowded environment

The thermal motion of stiff filaments in a crowded environment is highly constrained and anisotropic; it underlies the behavior of such disparate systems as polymer materials, nanocomposites, and the cell cytoskeleton. Despite decades of theoretical study, the fundamental dynamics of such systems remains a mystery. Using near-infrared video microscopy, we studied the thermal diffusion of individual single-walled carbon nanotubes (SWNTs) confined in porous agarose networks. We found that even a small bending flexibility of SWNTs strongly enhances their motion: The rotational diffusion constant is proportional to the filament-bending compliance and is independent of the network pore size. The interplay between crowding and thermal bending implies that the notion of a filament's stiffness depends on its confinement. Moreover, the mobility of SWNTs and other inclusions can be controlled by tailoring their stiffness.     

几种楼梯面可视化快速参数建模方法

楼梯面的智能化建模问题是建筑、装饰等行业的热点问题．以AutoCAD VBA作为开发工具．给出几种楼梯面可视化参数快速建模方法，并对楼梯面的生成算法进行了探讨．使楼梯面模型的设计更具敏捷化、智能化和可交互性．开发的设计程序可作为AutoCAD命令嵌入到的AutoCAD绘图软件中．以提高用户的设计效率。     

Self-assembly of highly phosphorylated silaffins and their function in biosilica morphogenesis

Silaffins are uniquely modified peptides that have been implicated in the biogenesis of diatom biosilica. A method that avoids the harsh anhydrous hydrogen fluoride treatment commonly used to dissolve biosilica allows the extraction of silaffins in their native state. The native silaffins carry further posttranslational modifications in addition to their polyamine moieties. Each serine residue was phosphorylated, and this high level of phosphorylation is essential for biological activity. The zwitterionic structure of native silaffins enables the formation of supramolecular assemblies. Time-resolved analysis of silica morphogenesis in vitro detected a plastic silaffin-silica phase, which may represent a building material for diatom biosilica.     

The effect of surface orientation on spray retention

Research in precision spraying investigates the means to reduce the amount of herbicide applied by directing droplets more accurately towards the weeds. The trend in the development of spot spraying equipment is an increase of the spatial resolution and new actuators that are able to target very small areas. However, there is a lack of methods for assigning rates of herbicides relating target to optimal droplet features. A wide range of droplet impact angles occurs during the spray application process because of droplet trajectories and the variability of leaf orientation. In this study, laboratory experiments were conducted to highlight the effect of surface orientation on droplet impact outcomes (adhesion, rebound or splashing) on two very difficult-to-wet surfaces: an artificial surface with a regular roughness pattern and an excised black-grass leaf with an anisotropic roughness pattern. Measurements were performed for different surface orientations with a high-speed camera coupled with backlighting LED. Droplets of two formulations (distilled water and distilled water + a surfactant) were produced with a moving flat-fan hydraulic nozzle to obtain a wide range of droplet sizes and velocities, which were measured by image analysis. Increasing surface angle reduces surface area available for droplet capture. Droplet impact behaviors are then modified since surface tilt induces a tangential velocity component at impact and, consequently, a reduction of the normal component. Impact modifications have also been observed due to the anisotropic roughness pattern of a black-grass leaf. The integration of droplet-surface interaction information offers a significant way to further improve the precision spraying efficiency by considering the optimal droplet size, speed and ejection angle depending on the target surface and architecture.