Covalent assembly-disassembly of poly(ether imine) dendritic macromolecular monomers and megamers

Abstract

Poly(ether imine) dendritic macromolecules were undertaken to study the reversible dendrimer monomer-megamer assembly-disassembly in aqueous solutions. Synthesis of thiol functionalized poly(ether imine) (PETIM) dendrimers and their covalent aggregation behavior in the aqueous solution of ethanol/water (2:1) is demonstrated. The dendritic megamers were characterized using microscopic techniques. Kinetics of the aggregation behavior was followed using turbidity measurements, light-scattering and atomic force microscopic techniques. Inherent luminescence behavior of PETIM dendrimer monomers was retained in the dendrimer megamers also, which allowed visualization of the megamers through confocal microscopy. Extent of thiol functionalities that remained after the megamer assembly was estimated through Ellman's assay. Subsequent to megamer assembly, disassembly of megamers to dendrimer monomers was conducted, using dithiothreitol reagent. Water-insoluble sudan I dye was encapsulated in dendrimer megamer and subsequent release profile was assessed during the disassembly in aqueous solutions. The studies were conducted using first, second and third generations, representing 4, 8 and 16 sulfhydryl groups at their peripheries of dendrimers, respectively.     

Surface Density of Ligands Controls In-Plane and Aggregative Modes of Multivalent Glycovesicle-Lectin Recognitions

Glycovesicles are ideal tools to delineate finer mechanisms of the interactions at the biological cell membranes. Multivalency forms the basis which, in turn, should surpass more than one mechanism in order to maintain multiple roles that the ligand-lectin interactions encounter. Ligand densities hold a prime control to attenuate the interactions. In the present study, mannose trisaccharide interacting with a cognate receptor, namely, Con A, is assessed at the vesicle surface. Synthetic (1→3)(1→6)-branched mannose trisaccharides tethered with a diacetylene monomer and glycovesicles of varying sugar densities were prepared. The polydiacetylene vesicles were prepared by maintaining uniform lipid concentrations. The interactions of the glycovesicles with the lectin were probed through dynamic light scattering and UV-Vis spectroscopy techniques. Binding efficacies were assessed by surface plasmon resonance. Aggregative and in-plane modes of interactions show ligand-density dependence at the vesicle surface. Vesicles with sparsely populated ligands engage lectin in an aggregative mode (trans-), leading to a cross-linked complex formation. Whereas glycovesicles embedded with dense ligands engage lectin interaction in an in-plane mode intramolecularly (cis-). Sub-nanomolar dissociation constants govern the intramolecular interaction occurring within the plane of the vesicle, and are more efficacious than the aggregative intermolecular interactions.     

Porous alumina templates and nanostructured CdS for thin film solar cell applications

Nanostructured CdS was grown by electrodeposition of cadmium sulfide inside a porous alumina template. Uniform pore size and spacing in the template was achieved when the starting material for the template was aluminum foil. Typical pore size was 45 nm. Nanostructured CdS was also deposited by electrodeposition on indium tin oxide (ITO)-coated glass and by solution growth on ITO-coated glass. Schottky diodes were formed on nanocrystalline CdS and the analysis of their current–voltage characteristics yielded a diode ideality factor (n) of 2.6 and a reverse saturation current density (J_S) of 1.00×10⁻⁵ A/cm². Corresponding values for the Schottky diode on polycrystalline CdS were 3.4 and 1.93×10⁻⁶ A/cm².     

Molecularly self-assembled nucleic acid nanoparticles for targeted in vivo siRNA delivery

Nanoparticles are used for delivering therapeutics into cells. However, size, shape, surface chemistry and the presentation of targeting ligands on the surface of nanoparticles can affect circulation half-life and biodistribution, cell-specific internalization, excretion, toxicity and efficacy. A variety of materials have been explored for delivering small interfering RNAs (siRNAs)--a therapeutic agent that suppresses the expression of targeted genes. However, conventional delivery nanoparticles such as liposomes and polymeric systems are heterogeneous in size, composition and surface chemistry, and this can lead to suboptimal performance, a lack of tissue specificity and potential toxicity. Here, we show that self-assembled DNA tetrahedral nanoparticles with a well-defined size can deliver siRNAs into cells and silence target genes in tumours. Monodisperse nanoparticles are prepared through the self-assembly of complementary DNA strands. Because the DNA strands are easily programmable, the size of the nanoparticles and the spatial orientation and density of cancer-targeting ligands (such as peptides and folate) on the nanoparticle surface can be controlled precisely. We show that at least three folate molecules per nanoparticle are required for optimal delivery of the siRNAs into cells and, gene silencing occurs only when the ligands are in the appropriate spatial orientation. In vivo, these nanoparticles showed a longer blood circulation time (t(1/2) ≈ 24.2 min) than the parent siRNA (t(1/2) ≈ 6 min).     

Consolidation and relaxation behavior of continuous strand random glass mats with thermoplastic binders

The consolidation and relaxation characteristics of glass mat reinforcements with a thermoplastic polyester binder have been studied. Attention has been given to the effect of preforming conditions on binder flow around the fibers, and on the rearrangement of fiber tows making up the preform. An instrumented hydraulic press was used to compress stacks of glass mat over a wide range of temperatures (51.7 to 176.7°C) and a range of platen closing speeds (0.02 to 2.00 mm/s). Scanning electron microscopy was used to examine the fiber tows after deformation. Individual fiber tows were observed to flatten during compression, more so at higher temperatures and slower closing speeds. The scanning electron micrographs also reveal changes in binder distribution around the fiber tows that are closely related to the degree of flattening of the fiber tows. This is because small gaps are opened up within the tow as it is flattened. Flow of binder along such gaps is predominantly due to the squeezing force, with only a minor contribution from capillary forces. The redistribution of binder then facilitates further compaction. The extent of binder redistribution is also governed by the binder viscosity, which was found to be a strong function of strain rate and temperature. The shear thinning viscosity of the binder leads to greater compressibility at the highest closing speed of 2 mm/s, although the compressibility of the mats was lower at moderately higher closing speeds. The compressibility was also higher at higher temperatures as expected. The loft was greater for stacks pressed at higher temperatures; this is a consequence of the lower binder viscosity at higher temperatures allowing more rearrangement of the tows. There was no loss of binder from the stacks in these runs.