Self-Assembled Monolayers of Symmetrical and Mixed Alkyl Fluoroalkyl Disulfides on Gold. 1. Synthesis of Disulfides and Investigation of Monolayer Properties

The synthesis of a variety of symmetrical bis(alkyl) and bis(fluoroalkyl) disulfides as well as mixed alkyl fluoroalkyl disulfides containing ester or amide groups is described. Self-assembled monolayers of these compounds on gold formed by spontaneous adsorption from solution are studied by contact angle measurements and polarized grazing incidence Fourier transform infrared spectroscopy (FTIR). The contact angles indicate tight packing of the molecules and the incorporation of both alkyl and fluoroalkyl chains in the monolayers. By means of FTIR, the typical tilted orientation of the alkyl chains is confirmed for monolayers derived from symmetrical alkyl disulfides, whereas, in self-assembled monolayers of the symmetrical fluorocarbon and the mixed disulfides, the molecules are oriented much closer to the surface normal direction. The wetting properties and the FTIR spectra of monolayers formed by coadsorption of an n-alkanethiol and a perfluorinated thiol are comparable to those formed by the self-assembly of the corresponding mixed disulfide. There is no indication for phase separation in any of the systems studied at room temperature. The mixed alkyl fluoroalkyl disulfides promise to form suitable monolayers on gold for the investigation of heat-induced phase separation on the gold surface

Coiling Instability of Multilamellar Membrane Tubes with Anchored Polymers

We study experimentally a coiling instability of cylindrical multilamellar stacks of phospholipid membranes, induced by polymers with hydrophobic anchors grafted along their hydrophilic backbone. Our system is unique in that coils form in the absence of both twist and adhesion. We interpret our experimental results in terms of a model in which local membrane curvature and polymer concentration are coupled. The model predicts the occurrence of maximally tight coils above a threshold polymer occupancy. A proper comparison between the model and experiment involved imaging of projections from simulated coiled tubes with maximal curvature and complicated torsions.Comment: 11 pages + 7 GIF figures + 10 JPEG figure

Two-Component Fluid Membranes Near Repulsive Walls: Linearized Hydrodynamics of Equilibrium and Non-equilibrium States

We study the linearized hydrodynamics of a two-component fluid membrane near a repulsive wall, via a model which incorporates curvature- concentration coupling as well as hydrodynamic interactions. This model is a simplified version of a recently proposed one [J.-B. Manneville et al. Phys. Rev. E, 64, 021908 (2001)] for non-equilibrium force-centres embedded in fluid membranes, such as light-activated bacteriorhodopsin pumps incorporated in phospholipid (EPC) bilayers. The pump/membrane system is modeled as an impermeable, two-component bilayer fluid membrane in the presence of an ambient solvent, in which one component, representing active pumps, is described in terms of force dipoles displaced with respect to the bilayer midpoint. We first discuss the case in which such pumps are rendered inactive, computing the mode structure in the bulk as well as the modification of hydrodynamic properties by the presence of a nearby wall. We then discuss the fluctuations and mode structure in steady state of active two-component membranes near a repulsive wall. We find that proximity to the wall smoothens membrane height fluctuations in the stable regime, resulting in a logarithmic scaling of the roughness even for initially tensionless membranes. This explicitly non-equilibrium result, a consequence of the incorporation of curvature-concentration coupling in our treatment, also indicates that earlier scaling arguments which obtained an increase in the roughness of active membranes near repulsive walls may need to be reevaluated.Comment: 39 page Latex file, 3 encapsulated Postscript figure

Tumour-targeted nanomedicines: principles and practice

Drug targeting systems are nanometre-sized carrier materials designed for improving the biodistribution of systemically applied (chemo)therapeutics. Various different tumour-targeted nanomedicines have been evaluated over the years, and clear evidence is currently available for substantial improvement of the therapeutic index of anticancer agents. Here, we briefly summarise the most important targeting systems and strategies, and discuss recent advances and future directions in the development of tumour-targeted nanomedicines

Facile Preparation of Organic Nanoparticles by Interfacial Cross-Linking of Reverse Micelles and Template Synthesis of Subnanometer Au−Pt Nanoparticles

A single- and a double-tailed cationic surfactant with the triallylammonium headgroup formed reverse micelles (RMs) in heptane/chloroform containing a small amount of water. The reverse micelles were cross-linked at the interface upon UV irradiation in the presence of a water-soluble dithiol cross-linker and a photoinitiator. The resulting interfacially cross-linked reverse micelles (ICRMs) of the single-tailed surfactant aggregated in a solvent-dependent fashion, whereas those of the double-tailed were identical in size as the corresponding RMs. The ICRMs could extract anionic metal salts, such as AuCl4− and PtCl62−, from water into the organic phase. Au and Pt metal nanoparticles were produced upon reduction of metal salts. The covalent nature of the ICRMs made the template synthesis highly predictable, with the size of the metal particles controlled by the amount of the metal salt and the method of reduction. Nanoalloys were obtained by combining two metal precursors in the same reaction. Reduction of the ICRM-entrapped aurate also occurred without any external reducing agents, and the gold nanoparticles differed dramatically from those obtained through sodium borohydride reduction. The same template allowed the preparation of luminescent Au4, Au8, and Au13−Au23 clusters, as well as gold nanoparticles several nanometers in size, simply by using different amounts of gold precursor and reducing conditions

Controlled Release from Cleavable Polymerized Liposomes upon Redox and pH Stimulation

A gallate derivative with three propargyl groups was coupled to palmitoyl oleoyl phosphoethanolamine (POPE). The resulting anionic lipid was formulated with common lipids such as palmitoyl oleoyl phosphatidyl choline (POPC) to form large unilamellar vesicles (LUVs). Polymerization of the LUVs was accomplished by the Cu(I)-catalyzed click reaction between the propargyl groups and the azide groups in the cross-linker. When the cross-linker contained a disulfide or ketal group, the resulting polymerized liposomes depolymerized and released entrapped contents upon the addition of a reducing thiol or under weakly acidic conditions. The click reaction allowed simultaneous multivalent surface functionalization during cross-linking, making these cleavable polymerized liposomes (CPLs) potentially very useful in the delivery and controlled release of pharmaceutical agents

Modeling morphological instabilities in lipid membranes with anchored amphiphilic polymers

Anchoring molecules, like amphiphilic polymers, are able to dynamically regulate membrane morphology. Such molecules insert their hydrophobic groups into the bilayer, generating a local membrane curvature. In order to minimize the elastic energy penalty, a dynamic shape instability may occur, as in the case of the curvature-driven pearling instability or the polymer-induced tubulation of lipid vesicles. We review recent works on modeling of such instabilities by means of a mesoscopic dynamic model of the phase-field kind, which take into account the bending energy of lipid bilayers

Multifunctional poly[N-(2-hydroxypropyl)methacrylamide] copolymers via postpolymerization modification and sequential thiol–ene chemistry

Poly[N-(2-hydroxypropyl)methacrylamide] is a promising candidate material for biomedical applications. However, synthesis of functional pHPMA via compolymerization results can lead to variations in monomer composition, molar mass, and dispersity making comparison difficult. Postpolymerization modification routes, most commonly aminolysis of poly[active ester methacrylates], have alleviated some of these problems, but ester hydrolysis can lead to other problems. Here we report the synthesis of multifunctional pHPMA via a simple two-step derivatization of pHPMA homopolymer using readily available standard reagents and atom-efficient procedures. First, treatment with allyl isocyanate yields the corresponding carbamate with predictable incorporation of side-chain functionality. Allyl-pHPMA can then be derivatized further via radical thiol–ene reactions to generate pHPMA with multiple diverse functionalities but without adverse effects on the molecular weight and dispersity of the polymer. The applicability of the method to production of biologically relevant materials is demonstrated by cytocompatibility and cell labeling experiments with easily prepared ligand-functionalized pHPMA in the HCT 116 model cell line