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

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

Columnar Liquid Crystals in Cylindrical Nanoconfinement

Axial orientation of discotic columnar liquid crystals in nanopores of inorganic templates, with the columns parallel to the axis of the nanochannels, is considered desirable for applications such as production of molecular wires. Here, we evaluate experimentally the role of the rigidity of the LC columns in achieving such orientation in nanopores where the planar anchoring (i.e., columns parallel to wall surface) is enforced. We studied the columnar phase of several discotic compounds with increasing column rigidity in the following order: dendronized carbazole, hexakis(hexyloxy)triphenylene (HAT6), a 1:1 HAT6-trinitrofluorenone (TNF) complex, and a helicene derivative. Using 2-D X-ray diffraction, AFM, grazing incidence diffraction, and polarized microscopy, we observed that the orientation of the columns changes from circular concentric to axial with increasing column rigidity. Additionally, when the rigidity is borderline, increasing pore diameter can change the configuration from axial back to circular. We derive expressions for distortion free energy that suggest that the orientation is determined by the competition between, on the one hand, the distortion energy of the 2-d lattice and the mismatch of its crystallographic facets with the curved pore wall in the axial orientation and, on the other hand, the bend energy of the columns in the circular configuration. Furthermore, the highly detailed AFM images of the core of the disclinations of strength +1 and +1/2 in the center of the pore reveal that the columns spiral down to the very center of the disclination and that there is no amorphous or misaligned region at the core, as suggested previously