Synthesis and Self-Aggregation of Poly(2-ethyl-2-oxazoline)-Based Photocleavable Block Copolymer: Micelle, Compound Micelle, Reverse Micelle, and Dye Encapsulation/Release.

We report on the synthesis of photocleavable poly(2-ethyl-2-oxazoline)-block-poly(2-nitrobenzyl acrylate) (PEtOx-b-PNBA) block copolymers (BCPs) with varying compositions via combination of microwave-assisted cationic ring-opening polymerization (CROP) and atom transfer radical polymerization (ATRP) using α-bromoisobutyryl bromide as an orthogonal initiator. The amphiphilic nature of this BCP causes them to self-assemble into primary micelles in THF/H2O, which further undergo secondary aggregation into nanostructured compound micelles as established through DLS, FESEM, and TEM. Upon UV irradiation (λ = 350 nm), the photocleavage of the PNBA block of the PEtOx-b-PNBA BCP takes place, and that leads to the formation of the doubly hydrophilic poly(2-ethyl-2-oxazoline)-b-poly(acrylic acid) (PEtOx-b-PAA) BCP causing the rupture of compound micelles as confirmed by spectroscopic and microscopic techniques. Encapsulation of a model hydrophobic guest molecule, nile red (NR), into the photocleavable BCP micellar core in aqueous solution and its UV-induced release is also investigated by fluorescence emission measurements. PEtOx-b-PNBA BCP amphiphiles are also shown to self-assemble into spherical nanostructures (∼90 nm) in dichloromethane as established by DLS and TEM analysis. These are referred to as reverse micelles and are able to encapsulate anionic hydrophilic dye, Eosin B, and facilitate its solubilization in organic media.

Fluorescent amphiphilic PEG-peptide-PEG triblock conjugate micelles for cell imaging.

A fluorescent amphiphilic poly(ethylene glycol)-peptide-fluorophore-peptide-poly(ethylene glycol) (PEG-Pep-F-Pep-PEG) triblock conjugate with a hydrophobic fluorophore moiety at the centre of the chain is synthesized by "grafting to" technique based on Schiff-base coupling chemistry. The conjugate is characterized by nuclear magnetic resonance (NMR), circular dichroism (CD), and fluorescence spectroscopy techniques. The aqueous solution of the triblock conjugate emits blue light and exhibits a fluorescence emission band at 430 nm. The amphiphilic conjugate molecules undergo self-assembly into micelles (D ≈ 15-20 nm) in aqueous solution as confirmed from transmission electron microscopy (TEM) and dynamic light scattering (DLS). The critical aggregation concentration is determined by pyrene fluorescence assay and is found to be 0.051 mg mL(-1) . The highly stable and low toxic fluorescent PEG-Pep-F-Pep-PEG conjugate micelles are used for imaging of HeLa cells.

Amino-acid-based zwitterionic polymer and its Cu(II)-induced aggregation into nanostructures: a template for CuS and CuO nanoparticles.

A convenient and water-based approach is described for the synthesis of an l-lysine-based zwitterionic polymer, poly(ε-l-lysinyl acrylamide) (PLAM), without using protecting group chemistry, chromatographic purifications, and organic solvents as the reaction media. PLAM contains both amine and carboxylic acid groups in each repeating unit, which can either be protonated or deprotonated just by altering the pH of the solution to obtain overall positive or negative charge. PLAM is tested for its applicability as a zwitterionic polymeric buffer in water. Cu(II) ion-induced aggregation of PLAM as a function of solution pH is studied. Spherical nanogel aggregates are formed at pH 9.5 due to aggregation of PLAM through its complexation with Cu(II) ion. Spherical aggregates appear to dissociate via breaking of the complexation at a pH < 5.5 resulting in molecular dissolution of PLAM. This aggregation process is pH reversible. The Cu(II)-PLAM aggregates are used as a template for fabrication of CuO and CuS nanoparticles.

Ascorbate-assisted growth of hierarchical ZnO nanostructures: sphere, spindle, and flower and their catalytic properties.

A simple solution-based method to prepare mainly flowerlike zinc oxide (ZnO) nanostructures using the ascorbate ion as a shape-directing/capping agent at relatively low temperature (ca. 30 and 60 degrees C) was described. However, we observed that different shapes of hierarchical ZnO nanostructures such as flowerlike, spindlelike, and spherical could be obtained with an increase in the synthesis temperature from 60 to 90 degrees C. The effects of other organic capping agents on the shape of hierarchical ZnO nanostructures were also studied. FTIR, FESEM, and XRD characterization were performed on the formed ZnO nanostructures to understand the role of ascorbate in the growth of flowerlike morphology. The nucleation and growth process can regulate by changing the metal precursor and ascorbate ion concentrations. We were able to identify intermediate nanostructures such as spherical/quasi-spherical and spindle that are very much on the pathway of formation of large, flowerlike ZnO nanostructures. Electron microscopy results indicated that these spherical/quasi-spherical ZnO nanoparticles might aggregate through oriented attachment to produce spindlelike and flowerlike nanostructures. On the basis of these results, a possible growth mechanism for the formation of flowerlike ZnO nanostructures was described. The optical properties of these differently shaped ZnO nanostructures were also described. The catalytic activities of the as-synthesized spherical and flowerlike ZnO nanostructures were tested in the Friedel-Crafts acylation reaction of anthracene with benzoyl chloride. The catalysis results indicated that the catalytic activity of flowerlike ZnO nanostructures is slightly higher than the spherical counterpart.

Ultrasound-induced in situ formation of coordination organogels from isobutyric acids and zinc oxide nanoparticles.

The discovery of ultrasound-induced in-situ formation of coordination organogels using various isobutyric acids (such as isobutyric acid or 2-methylisobutyric acid or 2-bromoisobutyric acid) and zinc oxide nanoparticles was described. FTIR and XRD results suggest that ultrasound irradiation triggers the quick dissolution of zinc oxide nanoparticles by isobutyric acids, resulting in the in-situ formation of zinc isobutyrate complexes that undergoes fast sonocrystallization into gel fibers. FESEM results clearly demonstrate the formation of well-defined networks of fibers with several micrometers in length, but the average diameter of the fiber ranges from 30 to 65 nm, depending upon the nature of the isobutyric acids used. A combination of single-crystal structure analysis and powder XRD result was used to envisage the molecular packing present in the gel state. This is probably a very rare case of ultrasound-induced organogelation where metal oxide NPs are used as the precursor.

Reversible self-assembly of carboxylated peptide-functionalized gold nanoparticles driven by metal-ion coordination.

Carboxylated peptide-functionalized gold nanoparticles (peptide-GNPs) self-assemble into two- and three-dimensional nanostructures in the presence of various heavy metal ions (i.e. Pb(2+), Cd(2+), Cu(2+), and Zn(2+)) in aqueous solution. The assembly process is monitored by following the changes in the surface plasmon resonance (SPR) band of gold nanoparticles in a UV/Vis spectrophotometer, which shows the development of a new SPR band in the higher-wavelength region. The extent of assembly is dependent on the amount of metal ions present in the medium and also the time of assembly. TEM analysis clearly shows formation of two- and three-dimensional nanostructures. The assembly process is completely reversible by addition of alkaline ethylenediaminetetraacetic acid (EDTA) solution. The driving force for the assembly of peptide-GNPs is mainly metal ion/carboxylate coordination. The color and spectral changes due to this assembly can be used for detection of these heavy-metal ions in solution.