Reentrant morphological transitions in copolymer micelles with pH-sensitive corona

In contrast to self-assembled aggregates of conventional ionic (including polymeric) surfactants the equilibrium micelles of diblock copolymer with a pH-sensitive polyelectrolyte block can exhibit two inverse sequences of morphological transitions triggered by an increase in solution salinity. The direct sequence of the sphere-cylinder-lamella transitions is similar to that for the copolymer with a strongly dissociating ionic block and occurs at a high salt concentration in solution. The abnormal reversed sequence of the lamella-cylinder-sphere transitions is predicted to occur at relatively low ionic strength in solution. The origin of the reentrant transitions is coupling between aggregation and ionization in copolymer micelles.     

Refinement of the crystal structure of (RS)-carnitine hydrochloride

A single crystal of (RS)-carnitine hydrochloride has been obtained, and its crystal structure has been refined by an x-ray structural experiment.Tashkent Pharmaceutical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 842–844, November–December, 1991.     

Polyelectrolyte brushes

The simple scaling theory of weakly-charged polyelectrolyte brush (the layer of polyelectrolyte chains grafted at one end onto an impermeable surface) immersed into a good solvent has been developed.The asymptotic scaling dependences of the free layer thickness on charge density and solvent strength are obtained. The behavior of polyelectrolyte brush subjected to normal and tangential external forces is considered. New “polyelectrolyte effect” is predicted: shear of a free polyelectrolyte brush leads to a decrease in brush thickness in contrast to the case of a free neutral brush. Such behavior is equivalent to that of a neutral brush subjected to external normal stretching force. This force in the case of polyelectrolyte brush is created by the osmotic pressure of mobile counterions neutralizing grafted chain charges.     

Annealing polyelectrolytes at charged interfaces

The conformation of a weakly dissociating (annealing) polyelectrolyte chain end-tethered to a similarly or oppositely charged planar surface is analyzed in the framework of scaling arguments. For a similarly charged interface an analytical model is also utilized. We demonstrate that at low salt concentration in bulk solution there is a strong coupling between the polyelectrolyte conformation and its degree of ionization. In the case of an oppositely charged (adsorbing) surface, adsorption promotes ionization of the annealing polyelectrolyte. As a result, the adsorbed layer thickness decreases as a function of surface charge density more rapidly for an annealing polyelectrolyte than for a quenched one. In the case of a similarly charged (repulsive) surface the chain ionization is suppressed, and the annealing polyelectrolyte chain is less extended than the quenched one. Moreover, an increase in surface charge density leads to non-monotonous extension of the tethered polyelectrolyte.Received: 16 September 2003, Published online: 5 February 2004PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 82.35.Gh Polymers on surfaces; adhesion - 82.35.Rs Polyelectrolytes     

Poisson-Boltzmann theory of pH-sensitive (annealing) polyelectrolyte brush

We present a self-consistent field analytical theory of a polymer brush formed by weakly charged pH-sensitive (annealing) polyelectrolytes tethered to a solid-liquid interface and immersed in buffer solution of low molecular weight salt. We use the Poisson-Boltzmann framework, applied by us previously to polyelectrolyte (PE) brushes with quenched charge (Zhulina, E. B.; Borisov, O. V. J. Chem. Phys. 1997, 107, 5952). This approach allows for detailed analysis of the internal structure of annealing PE brush in terms of polymer density distribution, profiles of electrostatic potential and of local degree of chain ionization as a function of buffer ionic strength and pH without any assumptions on mobile ion distribution imposed in earlier scaling-type models. The presented analytical theory recovers all major asymptotic dependences for average brush properties predicted earlier. In particular, a nonmonotonic dependence of brush thickness on ionic strength and grafting density is confirmed and specified with accuracy of numerical coefficients including crossover regions. Moreover, the theory predicts qualitatively new effects, such as, e.g., disproportionation of tethered polyions into weakly charged concentrated proximal and strongly charged sparse distal brush domains at low salt and moderate grating densities. The presented results allow us to quantify responsive features of annealing PE brushes whose large-scale and local conformational properties can be manipulated by external stimuli.     

Helicoidal Patterning of Nanorods with Polymer Ligands

Chiral packing of ligands on the surface of nanoparticles (NPs) is of fundamental and practical importance, as it determines how NPs interact with each other and with the molecular world. Herein, for gold nanorods (NRs) capped with end‐grafted nonchiral polymer ligands, we show a new mechanism of chiral surface patterning. Under poor solvency conditions, a smooth polymer layer segregates into helicoidally organized surface‐pinned micelles (patches). The helicoidal morphology is dictated by the polymer grafting density and the ratio of the polymer ligand length to nanorod radius. Outside this specific parameter space, a range of polymer surface structures was observed, including random, shish‐kebab, and hybrid patches, as well as a smooth polymer layer. We characterize polymer surface morphology by theoretical and experimental state diagrams. The helicoidally organized polymer patches on the NR surface can be used as a template for the helicoidal organization of other NPs, masked synthesis on the NR surface, as well as the exploration of new NP self‐assembly modes.     

Refinement of the crystal structure of (RS)-carnitine hydrochloride

A single crystal of (RS)-carnitine hydrochloride has been obtained, and its crystal structure has been refined by an x-ray structural experiment.     

Staged Surface Patterning and Self‐Assembly of Nanoparticles Functionalized with End‐Grafted Block Copolymer Ligands

Using two orthogonal external stimuli, programmable staged surface patterning and self‐assembly of inorganic nanoparticles (NPs) was achieved. For gold NPs capped with end‐grafted poly(styrene‐block‐(4‐vinylbenzoic acid)), P(St‐block‐4VBA), block copolymer ligands, surface‐pinned micelles (patches) formed from NP‐adjacent PSt blocks under reduced solvency conditions (Stimulus 1); solvated NP‐remote P(4VBA) blocks stabilized the NPs against aggregation. Subsequent self‐assembly of patchy NPs was triggered by crosslinking the P(4VBA) blocks with copper(II) ions (Stimulus 2). Block copolymer ligand design has a strong effect on NP self‐assembly. Small, well‐defined clusters assembled from NPs functionalized with ligands with a short P(4VBA) block, while NPs tethered with ligands with a long P(4VBA) block formed large irregularly shaped assemblies. This approach is promising for high‐yield fabrication of colloidal molecules and their assemblies with structural and functional complexity.