Mohammad Changez

Reversible and pH-Sensitive Vesicles from Amphiphilic Homopolymer Poly(2-(4-vinylphenyl)pyridine)†

The self-assembly of amphiphiles in varying sizes is of great importance to material and biomedical sciences due to their spontaneous generation of well-defined structures under thermodynamic equilibrium conditions. Polymeric amphiphiles form stable structures with a broader range of properties than small-molecule surfactants. In addition to long-term stability and enhanced loading capacity for guest molecules, self-assembling systems have demonstrated the capability to promptly and appropriately respond to external stimuli, such as pH, solvent polarity, and temperature. In this regard, amphiphilic block copolymerswithmicrometerto nanometersize aggregated structures warrant further investigation to prove their effectiveness in the encapsulation of a variety of guest molecules and their ability to spontaneously respond to external stimuli. Reversibility of the vesicles of diblock and triblock copolymers with pH has also been recently reported in a selective solvent. In the chemical architecture of block copolymer colloidal aggregates, the polarity of the block polymer segments and solvent plays a major role in defining their physicochemical characteristics. Recently, a new class of graft copolymer of polystyrene or polyacrylamide with miktoarm hydrophilic and hydrophobic substitution has been utilized to form various colloidal aggregates in selective solvents. Thayumanavan et al. demonstrated the effects of miktoarm side-chain length on the formationofnanometer-sizeaggregates fromagraftpolymerof polyacrylamide. The polyacrylamide derivative, in which the nitrogen of the acrylamide functionality and the nonglycine carboxylate functionality are separated by five or seven methylene units, formed reverse micelles. On the other hand,

Effect of solvent composition on transformation of micelles to vesicles of rod-coil poly(n-hexyl isocyanate-block-2-vinylpyridine) diblock copolymers.

The self-aggregation behavior of an amphiphilic rod-coil block copolymer of poly(n-hexyl isocyanate-block-2-vinylpyridine) (PHIC(189)-b-P2VP(228)) (f(P2VP) = 0.78, M(n) = 24.5K) in a tetrahydrofuran (THF)/water system was examined using dynamic light scattering (DLS), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM). The presence of a certain amount of water in the THF-based polymer solution induced a morphological transition from spherical solid micelles to open mouth platelike vesicles. The size of the aggregates increased with an increase in water content in the mixed solvent of THF/water. In the range of 30-40% water, the polymer formed vesicles with an interdigitated architecture of poly(n-hexyl isocyanate) (PHIC) at the center of the membrane and with the poly(2-vinylpyridine) (P2VP) block forming the outer layers and pointing toward the solvent. However, at higher water contents, the thickness of the bilayer increased due to the rearrangement of the vesicle membrane from a flip-flop to a lamellar architecture. After the degradation of the PHIC from the vesicles at basic pH, hollow spherical aggregates remained stable. After removing the THF from the mixed solvent using dialysis, large-sized compound vesicles were formed.

Preparation of Ag-Embedded Polystyrene Nanospheres and Nanocapsules by Miniemulsion Polymerization

An isopropyl myristate (IPM) biocompatible oil and an IPM solution of dodecanethiol-capped Ag nanoparticles (NPs, 4.5 nm) were used as hydrophobes to suppress the Ostwald ripening of monomer/hydrophobe miniemulsified droplets in a surfactant-stabilized water phase. The formation of non-IPM-encapsulated nanospheres (48 nm) and IPM-encapsulated nanocapsules (90 nm) were precisely controlled by using a water-soluble and an oil-soluble initiator, respectively, in the presence of a pure IPM as a hydrophobe in miniemulsion polymerization. Well-defined PS nanospheres, on which surfaces were coated with Ag NPs (Ag/PS nanospheres, 65 nm), and nanocapsules encapsulating both NPs and IPM liquid phase (Ag-IPM/PS nanocapsules, 115 nm) were made by replacing the hydrophobe from pure IPM with Ag/IPM solution. These nanostructures were characterized by transmission and scanning electron microscopes.

Synthesis of Well-defined Amphiphilic Block Copolymers by Organotellurium-Mediated Living Radical Polymerization (TERP)

Low-molecular weight amphiphilic diblock copolymers, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and (P2VP-b-PS) with different block ratios were synthesized for the first time via organotellurium-mediated living radical polymerization (TERP). For both the homo- and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2 ) is presented using a site-selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP-b-PS in toluene through the sol-gel method.

Formation of Intermicellar-Chained and Cylindrical Micellar Networks From an Amphiphilic Rod—Coil Block Copolymer: Poly(n-hexyl isocyanate)-block-poly(2-vinylpyridine)

Morphologies of the poly(n-hexyl isocyanate)-block-poly(2-vinylpyridine) (PHIC-b-P2VP, fP2VP=0.3) amphiphilic rod-coil block copolymer were studied in rod-selective chloroform (CHCl3), both-block-soluble tetrahydrofuran (THF), and CHCl3/THF mixed solvent systems. Spherical, solid micelles with a P2VP core and PHIC shell were formed in CHCl3, whereas a microphase-separated liquid crystalline morphology was prominent in the presence of THF. In the CHCl3/THF mixed solvent system, a unique long-range intermicellar-chained network (v/v=7/3) and a more evolved cylindrical micellar network (v/v=3/7) were remarkably formed, respectively. PHIC-b-P2VP network nanostructures were used as a template for the in situ synthesis of Au nanoparticles (8 nm) selectively within the functional P2VP core domains.

Uni-molecular hollow micelles from amphiphilic homopolymer poly(2-(4-vinylphenyl)pyridine).

Amphiphilic homopolymer poly(2-(4-vinylphenyl)pyridine) (PVPPy) forms hollow micelles with uni-molecular thickness in a tetrahydrofuran/water (95/5 v/v) azeotropic solvent. Depending on the pH of the media, the micelles may be transformed to vesicles.

Molecular Level Ordering in Poly(2-vinylpyridine)

The reaction between atactic poly(2-vinylpyridine) and 1,4-dibromobutane leads to formation of long-range 3D molecular ordering in polymer chains mainly because the side group (pyridine) of the polymer chain changes to a syndotactic configuration. This may enable the production of functional molecular devices that operate on a 3D atomic scale.

Au/CdS Hybrid Nanoparticles in Block Copolymer Micellar Shells

A polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) micellar structure with a P2VP core containing 5 nm CdS nanoparticles (NPs) and a PS shell formed in toluene that is a good solvent for PS block undergoes the core-shell inversion by excess addition of methanol that is a good solvent for P2VP block. It leads to the formation of micellar shell-embedded CdS NPs in the methanol major phase. The spontaneous crystalline growth of Au NPs on the CdS surfaces positioned at micellar shells without a further reduction process is newly demonstrated. The nanostructure of Au/CdS/PS-b-P2VP hybrid NPs is confirmed by transmission electron microscopy, energy-dispersive X-ray, and UV-Vis absorption.