Ca2+ Efflux from Temperature Sensitive Liposomes and In Situ Formation of Metal Cholate Liposome Gels: Basic Studies and Potentials for Sustained Site-Specific Drug Delivery

Liposomes or vesicles are biomimetic close containers for the delivery of drugs at the local site for an extended period of time. On the other hand hydrogels which are three-dimensional hydrophilic matrices are another class of popular materials for sustained release. Such hybrids combine the features of liposomes and polymer to ensure a sustained local drug delivery. In the present work a novel liposome/hydrogel soft assembly is explored which may be potentially useful for drug delivery applications. We report thermally triggered release of Ca+2 from temperature sensitive liposomal  compartments constituted as 90 mol% DPPC and 10 mol% DMPC to induce rapid gelation of a solution of calcium cholate and AgNO3 (extravesicular precursor fluid). Calcium chloride loaded liposomes were prepared using the lipid film rehydration method. The formation of unilamellar bilayer were supported by the fluorometric studies using a compatible and labeled fluoropore (NBD-PS). Hydrogels were obtained by mixing Ca+2 loaded liposome with extravesicular precursor fluid and incubating the content at 37oC. The concentration of the cholate during gelation was sublytic in order to avoid vesicle solubilization. The integrity of liposomes within the hydrogels were preserved during gelation as confirmed by transmission electron microscopy (TEM). The presence of low concentration of cholate (for example 0.05 mM) also permitted spectrophotometric monitoring of Ca+2 efflux for Ca-vesicles employing calcium sensitive dye, Arsenazo III.  We expect that this simple experiment may also be useful for developing implantable as well as rapidly gelling injectable biomaterials for site-specific drug delivery. The present work is also significant as the antimicrobial properties of hydrogels containing silver has been widely recognized for its therapeutic profile.   Keywords: Liposome, triggered release, metal cholate liposome gel, site-specific delivery

Atomic and electronic structure of neutral and charged SinOm clusters

Using molecular orbital approach and the generalized gradient approximation in the density functional theory, we have calculated the equilibrium geometries, binding energies, ionization potentials, and vertical and adiabatic electron affinities of SinOm clusters (n⩽6,m⩽12). The calculations were carried out using both Gaussian and numerical form for the atomic basis functions. Both procedures yield very similar results. The bonding in SinOm clusters is characterized by a significant charge transfer between the Si and O atoms and is stronger than in conventional semiconductor clusters. The bond distances are much less sensitive to cluster size than seen for metallic clusters. Similarly, calculated energy gaps between the highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) of (SiO2)n clusters increase with size while the reverse is the norm in most clusters. The HOMO-LUMO gap decreases as the oxygen content of a SinOm cluster is lowered eventually approaching the visible range. The photoluminescence and strong size dependence of optical properties of small silica clusters could thus be attributed to oxygen defects

First-principles study of interaction of molecular hydrogen with Li-doped carbon nanotube peapod structures

Using first-principles density functional theory based on gradient corrected approach, we have studied interaction of H2 molecule with Li-doped carbon nanotube and nanotube based peapod structures. We find that H2 physisorbs on pure carbon nanotube, which is in agreement with earlier studies, and this binding increases when H2 binds to Li-decorated on carbon nanotube surfaces: the binding is further enhanced with Li atoms deposited on C60 doped nanotube peapod structures. The increase in binding in the latter structures arises due to charge transfer between the nanotube and C60, which further facilitates charge transfer from Li to the nanotube. Encapsulating fullerene molecule inside the nanotube provides a different way of increasing charge concentration on Li atom adsorbed outside the nanotube. The increase in H2 binding energy due to C60 encapsulation, compared to recently engineered metal doped nanotube structures, may lead to different carbon based materials for hydrogen storage at room temperature

Dynamics and instabilities near the glass transition: From clusters to crystals

Molecular dynamics simulation has been used to explore the evolution, kinetics, and dynamics of a liquid–glass transition in clusters and bulk matter. We demonstrate a dynamical indicator that characterizes the onset of the glass transition in clusters and is consistent with other indicators of glass transitions in bulk systems. This criterion, based on changes in chaotic behavior as measured by the largest Liapunov exponent, reveals aspects of the microscopic processes associated with the phase change from liquid to glass, and provides a connection between the thermodynamic and dynamical behavior of systems and their multidimensional potential surfaces

Dynamical signatures of ‘phase transitions’: chaos in finite clusters

Finite clusters of atoms or molecules, typically composed of about 50 particles (and often as few as 13 or even less) have proved to be useful prototypes of systems undergoing phase transitions. Analogues of the solid-liquid melting transition, surface melting, structural phase transitions and the glass transition have been observed in cluster systems. The methods of nonlinear dynamics can be applied to systems of this size, and these have helped elucidate the nature of the microscopic dynamics, which, as a function of internal energy (or ‘temperature’) can be in a solidlike, liquidlike, or even gaseous state. The Lyapunov exponents show a characteristic behaviour as a function of energy, and provide a reliable signature of the solid-liquid melting phase transition. The behaviour of such indices at other phase transitions has only partially been explored. These and related applications are reviewed in the present article

Accurate six-band nearest-neighbor tight-binding model for the pi-bands of bulk graphene and graphene nanoribbons

Accurate modeling of the pi-bands of armchair graphene nanoribbons (AGNRs) requires correctly reproducing asymmetries in the bulk graphene bands as well as providing a realistic model for hydrogen passivation of the edge atoms. The commonly used single-pz orbital approach fails on both these counts. To overcome these failures we introduce a nearest-neighbor, three orbital per atom p/d tight-binding model for graphene. The parameters of the model are fit to first-principles density-functional theory (DFT) - based calculations as well as to those based on the many-body Green's function and screened-exchange (GW) formalism, giving excellent agreement with the ab initio AGNR bands. We employ this model to calculate the current-voltage characteristics of an AGNR MOSFET and the conductance of rough-edge AGNRs, finding significant differences versus the single-pz model. These results show that an accurate bandstructure model is essential for predicting the performance of graphene-based nanodevices.Comment: 5 figure