Geometry dominated fluid adsorption on sculptured substrates

Experimental methods allow the shape and chemical composition of solid surfaces to be controlled at a mesoscopic level. Exposing such structured substrates to a gas close to coexistence with its liquid can produce quite distinct adsorption characteristics compared to that occuring for planar systems, which may well play an important role in developing technologies such as super-repellent surfaces or micro-fluidics. Recent studies have concentrated on adsorption of liquids at rough and heterogeneous substrates and the characterisation of nanoscopic liquid films. However, the fundamental effect of geometry has hardly been addressed. Here we show that varying the shape of the substrate can exert a profound influence on the adsorption isotherms allowing us to smoothly connect wetting and capillary condensation through a number of novel and distinct examples of fluid interfacial phenomena. This opens the possibility of tailoring the adsorption properties of solid substrates by sculpturing their surface shape.Comment: 6 pages, 4 figure

Conservation of energy and momenta in nonholonomic systems with affine constraints

We characterize the conditions for the conservation of the energy and of the components of the momentum maps of lifted actions, and of their `gauge-like' generalizations, in time-independent nonholonomic mechanical systems with affine constraints. These conditions involve geometrical and mechanical properties of the system, and are codified in the so-called reaction-annihilator distribution

HIV-1 Tat protein directly induces mitochondrial membrane permeabilization and inactivates cytochrome c oxidase

The Trans-activator protein (Tat) of human immunodeficiency virus (HIV) is a pleiotropic protein involved in different aspects of AIDS pathogenesis. As a number of viral proteins Tat is suspected to disturb mitochondrial function. We prepared pure synthetic full-length Tat by native chemical ligation (NCL), and Tat peptides, to evaluate their direct effects on isolated mitochondria. Submicromolar doses of synthetic Tat cause a rapid dissipation of the mitochondrial transmembrane potential (ΔΨm) as well as cytochrome c release in mitochondria isolated from mouse liver, heart, and brain. Accordingly, Tat decreases substrate oxidation by mitochondria isolated from these tissues, with oxygen uptake being initially restored by adding cytochrome c. The anion-channel inhibitor 4,4′-diisothiocyanostilbene-2,2′-disulfonic acid (DIDS) protects isolated mitochondria against Tat-induced mitochondrial membrane permeabilization (MMP), whereas ruthenium red, a ryanodine receptor blocker, does not. Pharmacologic inhibitors of the permeability transition pore, Bax/Bak inhibitors, and recombinant Bcl-2 and Bcl-XL proteins do not reduce Tat-induced MMP. We finally observed that Tat inhibits cytochrome c oxidase (COX) activity in disrupted mitochondria isolated from liver, heart, and brain of both mouse and human samples, making it the first described viral protein to be a potential COX inhibitor

Direct observation of ion dynamics in supercapacitor electrodes using in situ diffusion NMR spectroscopy

Ionic transport inside porous carbon electrodes underpins the storage of energy in supercapacitors and the rate at which they can charge and discharge, yet few studies have elucidated the materials properties that influence ion dynamics. Here we use in situ pulsed field gradient NMR spectroscopy to measure ionic diffusion in supercapacitors directly. We find that confinement in the nanoporous electrode structures decreases the effective self-diffusion coefficients of ions by over two orders of magnitude compared with neat electrolyte, and in-pore diffusion is modulated by changes in ion populations at the electrode/electrolyte interface during charging. Electrolyte concentration and carbon pore size distributions also affect in-pore diffusion and the movement of ions in and out of the nanopores. In light of our findings we propose that controlling the charging mechanism may allow the tuning of the energy and power performances of supercapacitors for a range of different applications

Characterization of Micro-Mesoporous Materials from Nitrogen and Toluene Adsorption: Experiment and Modeling

Universal mechanisms of adsorption and capillary condensation of toluene and nitrogen on ordered MCM-41 and PHTS materials are studied by means of high-resolution experiments and Monte Carlo molecular simulations. A molecular simulation model of toluene adsorption in silica nanopores, which accounts for surface heterogeneity, and a hybrid molecular-macsroscopic method for pore size distribution (PSD) calculations have been developed. For a range of reference materials, the PSD results obtained from toluene isotherms are consistent with the results of nitrogen adsorption using the nonlocal density functional theory method

Plugged hexagonal templated silica: a unique micro- and mesoporous material with internal silica nanocapsules

We describe in this paper the development of plugged hexagonal templated silicas (PHTS) which are hexagonally ordered materials, with internal microporous silica nanocapsules; they have a combined micro- and mesoporosity and a tuneable amount of both open and encapsulated mesopores and are much more stable than other tested micellar templated structures