Nanotube surface arrays: Weaving, bending, and assembling on patterned silicon

The fabrication of ordered arrays of oriented and bent carbon nanotube on a patterned silicon surface with a micron scale spacing extending over millimeter size surface areas, was presented. A combination of multistep purification and oxidation procedures were used to generate bundles containing 3-20 nanotubes of high purity. The patterned surface was composed of alternating hydrophilic and hydrophobic stripes. The results suggest that the patterning is controlled by the hydrodynamic behavior of a fluid front and orientation and bending mechanisms are facilitated by the pinned carbon nanotubes trapped by the liquid-solid-vapor contact line.open849

High-resolution Raman microscopy of curled carbon nanotubes

The use of confocal Raman imaging spectroscopy and atomic force microscopy for identifying conditions of carbon nanotubes with bent nanotube bundles in the bent state was described. It was found that the tangential G mode on Raman spectra systemically shifts downward upon nanotube bending. The frequency shifts observed in the nanotubes were due to tensile strain of the bending nanotube arrays, which resulted in the loosening of C-C bonds in the outer walls. It was speculated that the frequency shift in Raman spectra was used for fast monitoring of the bending state of the standing carbon nanotube in gas and fluid flow nanosensors.open282

Thermoresponsive reversible behavior of multistimuli pluronic-based pentablock copolymer at the air-water interface

Surface behavior of the pH- and thermoresponsive amphiphilic ABCBA pentablock copolymer has been studied with respect to the environmental conditions. We demonstrate that the pentablock copolymer poly((diethylaminoethyl methacrylate)-b-(ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)-b-(diethylaminoethyl methacrylate)) possesses reversible temperature changes at the air-water interface in a narrow pH range of the water subphase. Significant diversity in the surface morphology of pentablock copolymer monolayers at different pH and temperatures observed were related to the corresponding reorganization of central and terminal blocks. Remarkable reversible variations of the surface pressure observed for the Langmuir monolayers at pH 7.4 in the course of heating and cooling between 27 and 50°C is associated with conformational transformations of terminal blocks crossing the phase line in the vicinity of the lower critical solution temperature point. The observed thermoresponsive surface behavior can be exploited for modeling of the corresponding behavior of pentablock copolymers adsorbed onto various biointerfaces for intracellular delivery for deeper understanding of stimuli-responsive transformations relevant to controlled drug and biomolecules release and retention

Atomic Force Microscopy and Optical Studies of Organic Thin Films with Hydrogen-Bonded Networks

Brewster angle microscopy and atomic force microscopy were used to characterize the surface morphology of thin films in situ or after transfer onto solid supports. Two acids were studied, differing in carboxylic acid head groups, resulting in significantly different morphological features for thin films formed from these two amphiphiles on a Langmuir trough. Differences in self-assembly and domain sizes were correlated with the formation of hydrogen-bonded networks. The influence of surface hydrophobicity or hydrophilicity during deposition on morphology was also characterized, with spherulitic features appearing in some samples

Plasmonic Library Based on Substrate-Supported Gradiential Plasmonic Arrays

We present a versatile approach to produce macroscopic, substrate-supported arrays of plasmonic nanoparticles with well-defined interparticle spacing and a continuous particle size gradient. The arrays thus present a “plasmonic library” of locally noncoupling plasmonic particles of different sizes, which can serve as a platform for future combinatorial screening of size effects. The structures were prepared by substrate assembly of gold-core/poly(<i>N</i>-isopropylacrylamide)-shell particles and subsequent post-modification. Coupling of the localized surface plasmon resonance (LSPR) could be avoided since the polymer shell separates the encapsulated gold cores. To produce a particle array with a broad range of well-defined but laterally distinguishable particle sizes, the substrate was dip-coated in a growth solution, which resulted in an overgrowth of the gold cores controlled by the local exposure time. The kinetics was quantitatively analyzed and found to be diffusion rate controlled, allowing for precise tuning of particle size by adjusting the withdrawal speed. We determined the kinetics of the overgrowth process, investigated the LSPRs along the gradient by UV–vis extinction spectroscopy, and compared the spectroscopic results to the predictions from Mie theory, indicating the absence of local interparticle coupling. We finally discuss potential applications of these substrate-supported plasmonic particle libraries and perspectives toward extending the concept from size to composition variation and screening of plasmonic coupling effects

Synthetic and bio-hybrid nanoscale layers with tailored surface functionalities

Abstract We examine the prospective routes for the design of synthetic/biomacromolecular/inorganic film assemblies for photothermal cell based on biomimetic approach. We demonstrate examples of channel proteins immobilized onto surfaces of silicon single crystals modified with Langmuir-Blodgett and self-assembled monolayers. These proteins can be immobilized in intact, closed-pore conformation. Their state within photosensitive monolayers can be controlled by the photoisomerization reaction triggered by UV light

Geomechanical stability of the caprock during CO2 sequestration in deep saline aquifers

8 páginas, 5 figuras.Sequestration of carbon dioxide (CO2) in deep saline aquifers has emerged as a mitigation strategy for reducing greenhouse gas emissions to the atmosphere. The large amounts of supercritical CO2 that need to be injected into deep saline aquifers may cause large fluid pressure buildup. The resulting overpressure will produce changes in the effective stress field. This will deform the rock and may promote reactivation of sealed fractures or the creation of new ones in the caprock seal, which could lead to escape paths for CO2. To understand these coupled hydromechanical phenomena, we model an axisymmetric horizontal aquifer-caprock system. We study plastic strain propagation patterns using a viscoplastic approach. Simulations illustrate that plastic strain may propagate through the whole thickness of the caprock if horizontal stress is lower than vertical stress. In contrast, plastic strain concentrates in the contact between the aquifer and the caprock if horizontal stress is larger than vertical stress. Aquifers that present a low-permeability boundary experience an additional fluid pressure increase once the pressure buildup cone reaches the outer boundary. However, fluid pressure does not evolve uniformly in the aquifer. While it increases in the low-permeability boundary, it drops in the vicinity of the injection well because of the lower viscosity of CO2. Thus, caprock stability does not get worse in semi-closed aquifers compared to open aquifers. Overall, the caprock acts as a plate that bends because of pressure buildup, producing a horizontal extension of the upper part of the caprock. This implies a vertical compression of this zone, which may produce settlements instead of uplift in low-permeability (k≤10-18 m2) caprocks at early times of injection.V.V. would like to acknowledge the Spanish Ministry of Science and Innovation (MIC) for financial support through the “Formación de Profesorado Universitario” program. V.V. also wishes to acknowledge the “Colegio de Ingenieros de Caminos, Canales y Puertos – Catalunya” for their financial support. This project has been funded by the Spanish Ministry of Science and Innovation through the project CIUDEN (Ref.: 030102080014), and through the MUSTANG project, from the European Community’s Seventh Framework Programme FP7/2007-2013 under grant agreement nº 227286.Peer reviewe

Synthesis and electrical properties of fullerene-based molecular junctions on silicon substrate

We report the synthesis and the electrical properties of fullerene-based molecular junctions on silicon substrate in which the highly \pi-conjugated molecule C60 (\pi quantum well) is isolated from the electrodes by alkyl chains (\sigma tunnel barriers). Initially, the Si/SiO2/\sigmaC60 architecture was prepared either by sequential synthesis (3 different routes) or by direct grafting of the presynthesized C60-\sigma-Si(OEt)3 molecule. We described the chemical synthesis of these routes and the physico-chemical properties of the molecular monolayers. Then, the second \sigma tunnel barrier was added on the Si/SiO2/\sigma C60 junction by applying a hanging mercury drop electrode thiolated with an alkanethiol monolayer. We compared the electronic transport properties of the Si/SiO2/\sigma C60//Hg and Si/SiO2/\sigma C60//\sigmaHg molecular junctions, and we demonstrated by transition voltage spectroscopy that the fullerene LUMO - metal Fermi energy offset can be tailored from ~ 0.2 eV to ~ 1 eV by changing the length of the alkyl chain between the C60 core and the Hg metal electrode (i. e. from direct C60//Hg contact to 14 carbon atoms tunnel barrier).Comment: Single pdf file including: main text, figures, tables and supporting information