Hazrat Hussain

Self-Assembly of Brush-Like Poly[poly(ethylene glycol) methyl ether methacrylate] Synthesized via Aqueous Atom Transfer Radical Polymerization

Self-assembly of brush-like well-defined poly[poly(ethylene glycol) methyl ether methacrylate] homopolymers, abbreviated as P(PEGMA-475) and P(PEGMA-1100) is investigated in aqueous solution by employing dynamic/static light scattering (DLS/SLS) and transmission electron microscopy (TEM), whereas 475 and 1100 is molar mass of the respective PEGMA macromonomer. The mentioned brush-like homopolymers are synthesized by aqueous ATRP at room temperature. The critical association concentration (CAC) of the synthesized polymers in water depends on the length of the PEG side chains but not on the overall molar mass of the polymer. Thus, approximately the same CAC of approximately 0.35 mg/mL is estimated for various P(PEGMA-1100) samples, and approximately 0.7 mg/mL is estimated for P(PEGMA-475) series. All the investigated P(PEGMA-1100) samples form multimolecular micelles in aqueous solution, where the hydrodynamic size (Rh) and the aggregation number (Nagg) of micelles decreases as the molecular weight of P(PEGMA-1100) increases. This can be attributed to the increased steric hindrances between the PEG side chains in corona of micelles formed by higher molar mass P(PEGMA-1100). The tendency of micelle formation by samples of P(PEGMA-475) series is significantly lower than that of P(PEGMA-1100) series, as demonstrated by their significantly higher CAC and micelles of lower Nagg. The Rh of micelles does not depend strongly on polymer concentration, which suggests that these micelles are formed via the closed association model. Micelles formed by P(PEGMA-1100) series slightly shrink with increase in temperature from 25 to 60 degrees C, while those of P(PEGMA-475) series are found to be insensitive to the same temperature variation. Finally, TEM is carried out to visualize the formed micelles after transferring the aqueous solution to carbon film.

Stable Dispersions of Hybrid Nanoparticles Induced by Stereocomplexation between Enantiomeric Poly(lactide) Star Polymers

We report the formation and characterization of stable dispersions of hybrid nanoparticles in solution formed via stereocomplexation of enantiomeric poly(lactide) hybrid star polymers. The hybrid starlike polymers, having polyhedral oligomeric silsesquioxane (POSS) nanocages as the core and either poly(L-lactide) (PLLA) or poly(D-lactide) (PDLA) as the arms, are synthesized via ring-opening polymerization of lactide using octafunctional POSS as the macroinitiator. In the solid state, differential scanning calorimetry and wide-angle X-ray scattering measurements confirmed the formation of the stereocomplex in the mixture of POSS-star-PLLA and POSS-star-PDLA (50:50, wt %). In a solution of the same mixture in tetrahydrofuran (THF), sterocomplexation leads to formation of hybrid nanaoparticles. Detailed accounts of the nanoparticle formation and influence of aging and concentration have been presented. It was observed that at low concentration the stereocomplexed nanaoparticles remain stable over 45 days and are not sensitive to dilution, suggesting the formation of a stable hybrid nanoparticle dispersion in solution. In contrast, the aggregates of the individual POSS-star-PLLA or POSS-star-PDLA in THF, formed via weak solvophobic interactions, tended to disintegrate into smaller aggregates on dilution. Exploiting the PLLA-PDLA stereocomplexation with an appropriate molecular design can be a versatile route to develop stable organic/inorganic hybrid nanoparticle dispersions.

Direct Patterning of TiO2 Using Step-and-Flash Imprint Lithography

Although step-and-flash imprint lithography, or S-FIL, has brought about tremendous advancement in wafer-scale fabrication of sub-100 nm features of photopolymerizable organic and organo-silicon-based resists, it has not been successful in direct patterning of inorganic materials such as oxides because of the difficulties associated with resist formulation and its dispensing. In this paper, we demonstrate the proof-of-concept S-FIL of titanium dioxide (TiO(2)) carried by an acrylate-based formulation containing an allyl-functionalized titanium complex. The prepolymer formulation contains 48 wt % metal precursor, but it exhibits low enough viscosity (∼5 mPa·s) to be dispensed by an automatic dispensing system, adheres and spreads well on the substrate, is insensitive to pattern density variations, and rapidly polymerizes when exposed to broadband UV radiation to give a yield close to 95%. Five fields, each measuring 1 cm × 1 cm, consisting of 100 nm gratings were successively imprinted. Heat-treatment of the patterned structures at 450 °C resulted in the loss of organics and their subsequent shrinkage without the loss of integrity or aspect ratio and converted them to TiO(2) anatase nanostructures as small as 30 nm wide. With this approach, wafer-scale direct patterning of functional oxides on a sub-100 nm scale using S-FIL can become a distinct possibility.

Synthesis and characterization of poly(ethylene oxide) and poly(perfluorohexylethyl methacrylate) containing triblock copolymers

A new series of poly(perfluorohexylethylmethacrylate)-block-poly(ethylene oxide)-block-poly(perfluorohexylethyl methacrylate), PFMA-b-PEO-b-PFMA triblock copolymers has been synthesized by atom transfer radical polymerization using bifunctional PEO macroinitiators. The molecular structure of the block copolymers was confirmed by 1 H NMR spectroscopy and SEC. X-ray scattering studies have been carried out to investigate their bulk properties. SAXS has shown cubic arrangement of spheres (bcc), hexagonally packed cylinders (hpc) and lamellar microdomain formation in the melt of triblock copolymers investigated, depending on composition. Crystallization was, however, found to destroy the ordered melt morphology and imposes a lamellar crystalline structure. WAXS, DSC and polarized light microscopy measurements confirmed the crystallization of PEO segments in block copolymers. Long PFMA blocks were found to have significant effect on PEO crystallization.

Tuning self-assembly of hybrid PLA-P(MA-POSS) block copolymers in solution via stereocomplexation

We demonstrate the formation of stable hybrid nanoparticles in solution through self-assembly driven by the stereocomplexation between enantiomeric poly(lactide) (PLA) chains in organic–inorganic hybrid diblock copolymers. The well-defined hybrid diblock copolymers (PLLA-b-P(MA-POSS) and PDLA-b-P(MA-POSS)) are synthesized via atom transfer radical polymerization of methacrylisobutyl POSS (MA-POSS) using either PLLA or PDLA as a macroinitiator. The structure of the block copolymers is confirmed by 1H NMR and GPC. The mixture of PLLA-b-P(MA-POSS) and PDLA-b-P(MA-POSS) in THF solution resulted in the formation of self-assembled nanoparticles as confirmed by the light scattering data. It is further verified that the only driving force for self-assembly in THF solution is the ‘stereocomplexation’ between the PLLA and PDLA blocks as no aggregation could be observed in THF solutions of homochiral polylactides at low concentration (∼1 mg mL−1). A solution mixture of 50:50 weight% of PLLA-b-P(MA-POSS) and PDLA-b-P(MA-POSS) for all the samples yields the best stereocomplexation results in terms of particles size and aggregation numbers. For a given composition, the size of the stereocomplexed hybrid nanoparticles, however, decreases with the increasing length of the (MA-POSS) block in the copolymer. As an example, for a 50:50 weight% mixture, the mean hydrodynamic radius Rh and apparent aggregation number Nagg of the particles decreased from 220 nm and 890, respectively, to 72 nm and 290, when the degree of polymerization of P(MA-POSS) increased from ∼2 to 11–12. It is assumed that the bulky POSS nanocages of P(MA-POSS) in the PLA-b-P(MA-POSS) block copolymer sterically hinder the formation of larger nanoparticles by block copolymers with longer P(MA-POSS) blocks. The stereocomplexed nanoparticles remain stable over 30 days and are not sensitive to dilution, suggesting the formation of stable hybrid nanoparticles dispersion. In contrast, the homopolymer mixture of PLLA and PDLA turned cloudy and was no longer stable after 12 days due to the formation of larger macroscopic aggregates. This interesting finding opens up new opportunities to tune the size and stability of the stereocomplexed nanoparticles in solution by manipulating the block length of the inorganic P(MA-POSS) segment.

Barnacle repellent nanostructured surfaces formed by the self-assembly of amphiphilic block copolymers.

Well-defined nanostructured surface with domains of dimension ∼20 nm was formed by the self-assembly of brush-type amphiphilic block copolymers of poly[poly(ethylene glycol)methyl ether methacrylate]-block-poly(2,3,4,5,6-pentafluorostyrene) (P(PEGMA)-b-PPFS) which demonstrate promise in discouraging barnacle settlement as proven using laboratory settlement assays and marine field tests.

Synthesis and Self‐Assembly of pH‐Responsive Amphiphilic Poly(dimethylaminoethyl methacrylate)‐block‐Poly(pentafluorostyrene) Block Copolymer in Aqueous Solution

We report the synthesis of a novel pH-responsive amphiphilic block copolymer poly(dimethylaminoethyl methacrylate)-block-poly(pentafluorostyrene) (PDMAEMA-b-PPFS) using RAFT-mediated living radical polymerization. Copolymer micelle formation, in aqueous solution, was investigated using fluorescence spectroscopy, static and dynamic light scattering (SLS and DLS), and transmission electron microscopy (TEM). DLS and SLS measurements revealed that the diblock copolymers form spherical micelles with large aggregation numbers, N(agg)  ≈ 30 where the dense PPFS core is surrounded by dangling PDMAEMA chains as the micelle corona. The hydrodynamic radii, R(h) of these micelles is large, at pH 2-5 as the protonated PDMAEMA segments swell the micelle corona. Above pH 5, the PDMAEMA segments are gradually deprotonated, resulting in a lower osmotic pressure and enhanced hydrophobicity within the micelle, thus decreasing the R(h) . However, the radius of gyration, R(g) remains independent of pH as the dense PPFS cores predominate.

Micelle Formation of Amphiphilic Polystyrene-b-poly(N-vinylpyrrolidone) Diblock Copolymer in Methanol and Water−Methanol Binary Mixtures

The micelle formation by the amphiphilic polystyrene-block-poly(N-vinylpyrrolidone) (PS48-b-PNVP99) copolymer is investigated in methanol and water-methanol binary mixtures of various compositions using 1H NMR, fluorescence spectroscopy, static/dynamic light scattering (SLS/DLS), and transmission electron microscopy (TEM). Critical micelle concentrations (cmc) are determined by employing fluorescence spectroscopy and DLS measurements. The cmc of the PS48-b-PNVP99 block copolymer increases with increasing methanol content in the water-methanol binary mixtures, suggesting that methanol is a better solvent for the PS48-b-PNVP99 block copolymer than water-methanol mixtures or pure water. The amphiphilic PS48-b-PNVP99 diblock copolymer forms spherical micelles of Rh approximately 16 nm in pure methanol solution as revealed by DLS measurements. In contrast, significantly larger micelles having higher aggregation numbers are formed in water-methanol binary mixtures. Temperature dependent data reveal an increase in aggregation number and radius of gyration (Rg) concomitantly with temperature (10-40 degrees C). In contrast, the overall size (Rh) of the micelles remains almost constant over the same temperature range. An explanation is tendered that PNVP coronas dehydrate/desolvate at higher temperatures counteracting the increase in micelle size (Rh) caused by increased aggregation numbers (Nagg).

pH-responsive amphiphilic hybrid random-type copolymers of poly(acrylic acid) and poly(acrylate-POSS): synthesis by ATRP and self-assembly in aqueous solution

The synthesis and subsequent self-assembly of novel, random-type amphiphilic pH-responsive hybrid copolymers, having acrylic acid as pH-responsive hydrophilic and acrylate-polyhedral oligomeric silsesquioxane (POSS) as hydrophobic constituents are reported. The synthesis was carried out in two steps: first, t-butylacrylate and acrylate-POSS are copolymerized by ATRP, followed by the acid hydrolysis of t-butyl acrylate constituents of the synthesized poly(t-butylacrylate)-co-poly(acrylate-POSS) copolymers to achieve poly(acrylic acid)-co-poly(acrylate-POSS). It was found that POSS is a powerful hydrophobic unit. With very low POSS concentration in the copolymers, i.e., one POSS unit per 40 to 110 acrylic acid repeat units, the obtained amphiphilic hybrid copolymers could self-assemble in aqueous solution to form nanoaggregates, as revealed by the laser light scattering and fluorescence studies on the aqueous solutions of the obtained copolymers. The formation of hydrophobic core in the self-assembled aggregates is verified by the solubilization of pyrene (used as probe in fluorescence measurements) in aqueous solution of the copolymers. In addition to pH-dependent self-assembly behavior, it is also demonstrated that the particle size and aggregation number of the aggregates can be tuned simply by varying the composition of the copolymer, i.e., by changing the molar ratio of poly(acrylic acid) to poly(acrylate-POSS) in the copolymer. Finally, preliminary results on the influence of salt (NaCl) on the self-assembly of poly(acrylic acid)-co-poly(acrylate-POSS) in aqueous solution are also presented.

Direct nanoimprinting of metal oxides by in situ thermal co-polymerization of their methacrylates

The use of polymerization to solidify, strengthen and imprint liquid organic materials is the basis of ultraviolet (UV) nanoimprint lithography. In spite of these advantages, the use of polymerization to pattern materials in thermal nanoimprint lithography is almost non-existent. In this study, we demonstrate a facile and general method to directly imprint a host of unary metal oxides (Fe2O3, ZrO2, TiO2, Nb2O5 and Ta2O5) at a very high resolution viain situ thermal free radical co-polymerization of various metal methacrylates in the presence of cross-linker ethylene glycol dimethacrylate using a silicon mold. Polymerization during nanoimprinting rigidly shapes the patterns, traps the metal atoms, reduces the surface energy and strengthens the structures, thereby giving ∼100% yield after demolding. It was found that the higher oxidation state of metal resulted in excessive cracking of imprinted structures. This could be due to a higher degree of cross-linking of the precursor leading to shrinkage-related stress. Optimization of the resin composition by partially replacing ethylene glycol dimethacrylate with methyl methacrylate alleviated this problem. Heat-treatment of the imprinted structures resulted in the loss of organics, their subsequent shrinkage and converted the patterns to their corresponding metal oxides with line-widths as small as 25 nm.