Synthesis, self-assembly and (absence of) protein interactions of poly(glycerol methacrylate)-silicone macro-amphiphiles

The present study focuses on the synthesis of amphiphilic block copolymers containing poly(glycerol monomethacrylate) (PGMMA), showing the advantages of a protection/deprotection strategy based on silyl groups. PGMMA blocks were synthesized via ATRP started by a double functional poly(dimethyl siloxane) (PDMS) macroinitiator of molecular weight ≈7000 g mol-1. The resulting triblock copolymers were characterized by low polydispersity (generally ≤1.1) and their aggregation concentration in water was essentially dominated by the PDMS block length (critical aggregation concentration substantially invariant for GMMA degree of polymerization ≥30). For GMMA blocks with DP > 50, the self-assembly in water produced 35-50 nm spherical micelles, while shorter hydrophilic chains produced larger aggregates apparently displaying worm-like morphologies. Block copolymers with long GMMA chains (DP ≈ 200) produced particularly stable micellar aggregates, which were then selected for a preliminary assessment of the possibility of adsorption of plasma proteins (albumin and fibrinogen); using diffusion NMR as an analytical technique, no significant adsorption was recorded both on micelles and on soluble PGMMA employed as a control, indicating the possibility of a "stealth" behaviour. This journal is © 2013 The Royal Society of Chemistry.

Synthesis and self-assembly behaviour of poly(Nα-Boc-l-tryptophan)-block-poly(ethylene glycol)-block-poly(Nα-Boc-l-tryptophan)

We report for the first time the use of Nα-Boc-l-tryptophan for the synthesis of amphiphilic BAB triblock copolymers for potential drug delivery applications. A library of poly(Nα-Boc-l-tryptophan)-block-poly(ethylene glycol)-block-poly(Nα-Boc-l-tryptophan) (PBoclTrp-b-PEG-b-PBoclTrp) amphiphilic copolymers were synthesized through the ring opening polymerization of Nα-Boc-l-tryptophan Nα-carboxy anhydride as initiated by diamino-terminated PEG of fixed molecular weight (Mn 3350). The influence of the hydrophobic block length over self-assembly was investigated for 4 of the BAB copolymers of molecular weights varying between Mn 5000 and Mn 17000. It was found that an increase in hydrophobic block length led to an increase in hydrodynamic size of aggregates in solution, as well as a decrease in critical micelle concentration. TEM analysis showed the formation of spherical micelles with the largest of the copolymers forming interconnected networks of spherical micelles. The influence of hydrophobic block length over the formation of secondary structure was analyzed using circular dichroism and infrared spectroscopy. Collectively we found that the presence of t-Boc protected l-tryptophan leads to the preferential formation of α-helix secondary structure through hydrogen bonding, which, in a drug delivery vehicle context, could help in controlling drug release. Also, it is believed that the use of novel Nα-Boc-l-tryptophan could improve drug stabilization in the hydrophobic core via π-π interactions between indole rings.

The influence of variant PE-b-PEO segments on physical properties of LLDPE graft copolymers

A method was adopted to fix a series of polymers of PE-b-PEO with different PEO/PE segments on the chains of LLDPE. Maleic anhydride (MA) reacting with hydroxyl group of PE-b-PEO (mPE-b-PEO) was used as the intermediate. The structures of intermediates and graft copolymers were approved by H-1 NMR and FTIR. XPS analysis revealed a great amount of oxygen on the surface of grafted copolymers although the end group of PEO was fixed on the LLDPE chains through MA. Thermal properties of the graft copolymers as determined by differential scanning calorimetry (DSC) showed that PE segments in the grafted monomers could promote the heterogeneous nucleation of the polymer, increase T., and crystal growth rate.

Nonisothermal crystallization kinetics of PEO in ethylene terephthalate-ethylene oxide segmented copolymers

The nonisothermal crystallization behavior of Ethylene Terephthalate-Ethylene Oxide (ET-EO) segmented copolymers has been studied with the use of differential scanning calorimetry (DSC). The kinetics of PEO in ET-EO segmented copolymer under nonisothermal crystallization conditions has been analyzed with the Ozawa equation. The results show that there is no agreement with Ozawa's theoretical predictions in the whole crystallization process owing to the constraint of ET segments imposed on the EO segments. A distinct two-crystallization process has been investigated by using the Avrami equation modified by Jeziorny to deal with the nonisothermal crystallization data. The value of the Avrami exponent n is independent of the length of soft segments. However, the crystallization rate is sensitive to the length of soft segments. The longer the soft segments, the faster the crystallization will be.

Synthesis and mechanistic insights of macromolecular assemblies from ABA triblock copolymer blends

Macromolecular assembly of block copolymers into numerous nanostructures resembles self-organization of proteins and cellular components found in nature. In order to mimic nature’s assemblies either to cure a disease or construct functional devices, the organization principles underpinning the emergence of complex shapes need to be understood. In the same vein, this study aimed at understanding morphology evolution in a triblock copolymer blend in aqueous solution. An ABA type amphiphilic triblock copolymer (polystyrene-b-polyethylene oxide-b-polystyrene, PS-b-PEO-b-PS) was synthesized at different compositions via atom transfer radical polymerization (ATRP) and self-assembly behavior of a binary mixture in aqueous solution was studied. Block copolymers that form worms and vesicles in its pristine state was shown to form complex morphologies such as fused rings, “jellyfish”, toroid vesicles, large compound vesicles and large lamellae after blending. The tendency of vesicle-forming block copolymer to form bilayers may be responsible for triggering complex morphologies when mixed with a worm or micelle-forming polymer. In other words, the interplay between curvature effects produced by two distinct polymers with different hydrophobic block lengths results in complex morphologies due to chain segregation within the nanostructure.

Crystallization and morphology of poly(ethylene oxide-b-lactide) crystalline-crystalline diblock copolymers

The crystallization behaviors and morphology of asymmetric crystalline-crystalline diblock copolymers poly(ethylene oxide-lactide) (PEO-b-PLLA) were investigated using differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and microscopic techniques (polarized optical microscopy (POM) and atomic force microscopy (AFM)). Both blocks of PEO5-b-PLLA(16) can be crystallized, which was confirmed by WAXD, while PEO block in PEO5-b-PLLA(30) is difficult to crystallize because of the confinement induced by the high glass transition temperature and crystallization of PLLA block with the microphase separation of the block copolymer.

Molecular weight dependence of phase Behavior of PEO/P(EO-b-DMS) blends: Application of Sanchez-Lacombe lattice fluid theory

Molecular weight dependence of phase separation behavior of the Poly (ethylene oxide) (PEO)/Poly(ethylene oxide-block-dimethylsiloxane) (P(EO-b-DMS)) blends was investigated by both experimental and theoretical methods. The cloud point curves of PEO/P(EO-b-DMS) blends were obtained by turbidity method. Based on Sanchez-Lacombe lattice fluid theory (SLLFT), the adjustable parameter, epsilon*(12)/k (quantifying the interaction energy between different components), was evaluated by fitting the experimental data in phase diagrams. To calculate the spinodals, binodals, and the volume changes of mixing for these blends, three modified combining rules of the scaling parameters for the block copolymer were introduced.

Effect of binary block-selective solvents on self-assembly of ABA triblock copolymer in dilute solution

We have studied the self-assembly of the ABA triblock copolymer (P4VP-b-PS-b-P4VP) in dilute solution by using binary block-selective solvents, that is, water and methanol. The triblock copolymer was first dissolved in dioxane to form a homogeneous solution. Subsequently, a given volume of selective solvent was added slowly to the solution to induce self-assembly of the copolymer. It was found that the copolymer (P4VP(43)-b-PS366-b-P4VP(43)) tended to form spherical aggregate or bilayer structure when we used methanol or water as the single selective solvent, respectively.

Polymer Crystallization Influenced by Initial Orientation of Cylindrical Diblock Copolymers in Thin Films

The effect of the initial states (disordered perpendicular cylinder structure vs. parallel cylinder structure) on the crystallization of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) thin films during cyclohexane annealing was investigated. The cylindrical domains perpendicular or parallel to the surface were obtained by controlling the film thickness. During solvent annealing, for the film with the perpendicular cylinders, the ordering degree of cylinders was increased.

Novel temperature- and pH-responsive graft copolymers composed of poly(L-glutamic acid) and poly(N-isopropylacrylamide)

A series of novel temperature- and pH-responsive graft copolymers, poly(L-glutamic acid)-g-poly(N-isopropylacrylamide), were synthesized by coupling amino-semitelechelic poly(N-isopropylacrylamide) with N-hydroxysuccinimide-activated poly(L-glutamic acid). The graft copolymers and their precursors were characterized, by ESI-FTICR Mass Spectrum, intrinsic viscosity measurements and proton nuclear magnetic resonance (H-1 NMR). The phase-transition and aggregation behaviors of the graft copolymers in aqueous solutions were investigated by the turbidity measurements and dynamic laser scattering.

"Sandglass"-shaped self-assembly of coil-rod-coil triblock copolymer containing rigid aniline-pentamer

The amphiphilic PEG1 500-b-EM AP-b-PEG1 500 (EM PAP) triblock copolymer of poly(ethylene glycol) (PEG) and emeraldine aniline-pentamer (EM AP) in its concentrated solution can self-assemble into a special shape like "sandglass", as observed by transmission electron microscopy (TEM), field emission scanning electron microscopy (ESEM) and atomic force microscopy (AFM). This "sandglass"- shaped assembly is composed of several "rods" aggregated in the middle, with every "rod" being about 8 VLrn in length and 300 nm in diameter.

Order-Order Transition of C -> sdG -> sL -> S in ABC Triblock Copolymer Thin Film Induced by Solvent Vapor

The morphology transition of polystyrene-block-poly(butadiene)-block-poly(2-vinylpyridine) (SBV) triblock thin film induced in benzene vapor showing weak selectivity for PS is investigated. The order-order transitions (OOT) in the sequence of core-shell cylinders (C), sphere in 'diblock gyroid' (sdG), sphere in lamella (sL) and sphere (S) are observed. The projection along (111) direction in Gyroid phase (sdG(111)) is found to epitaxially grow from C(001) in the film.

Study of morphology and phase diagram of the H-shaped (AC)B(CA) ternary block copolymers using self-consistent field theory

By using a combinatorial screening method based on the self-consistent field theory (SCFT) for polymer systems, the micro-phase morphologies of the H-shaped (AC)B(CA) ternary block copolymer system are studied in three-dimensional (3D) space. By systematically varying the volume fractions of the components A, B, and C, six triangle phase diagrams of this H-shaped (AC)B(CA) ternary block copolymer system with equal interaction energies among the three components are constructed from the weaker segregation regime to the strong segregation regime, In this study, thirteen 3D micro-phase morphologies for this H-shaped ternary block copolymer system are identified to be stable and seven 3D microphase morphologies are found to be metastable.

Bump-Surface Multicompartment Micelles from a Linear ABC Triblock Copolymer: A Combination Study by Experiment and Computer Simulation

Novel bump-surface multicompartment micelles formed by a linear amphiphilic ABC triblock copolymer via self-assembly in selective solvent were successfully observed both in simulation and experiment. The results revealed that the block A forms the most inner core, and the blocks B and C form the inner and outer layers, respectively, and the bumps were formed by block A and more likely to be born on curving surfaces. Moreover, the micelle shape could be controlled by changing the solvent selectivity of the blocks A and B. Spherical, cylindrical, and discoidal micelles with bumpy surfaces were obtained both in experiment and simulation.

Effect of Shear Flow on the Formation of Ring-Shaped ABA Amphiphilic Triblock Copolymer Micelles

We have investigated the effect of Shear flow on the formation of rill.-shaped ABA triblock copolymer (P4VP(43)-b-PS260-b-P4VP(43)) micelles. The results reveal that Shear flow Plays an important role in the formation of the rings Both ring size and its, distribution are found to be dependent sensitively on the stirring rate. Sizable rings are more likely to be formed at moderate stirring rate, Interestingly, the ring formation mechanism is also dependent oil the Shear flow. Copolymers are likely to form rings via end-to-end cylinder connection at low stirring rates, whereas they tend to form rings via the pathway of the rod-sphere-vesicle-ring it high stirring rates.