An official website of the United States government
Abstract We report the thermoresponsive assembly and rheology of an amphiphilic thermosensitive graft copolymer, poly(ethylene glycol)-graft-(poly(vinyl caprolactam)- co -poly(vinyl acetate)) (commercial name Soluplus ® ), which has been investigated for potential biomedical applications. It has received attention due to is ability to solubilize hydrophobic drugs and for its thickening behavior close to body temperature. Through use of the synchrotron at Brookhaven National Lab, and collaboration with the department of energy, the nanoscale structure and properties can be probed in greater detail. Soluplus ® undergoes two structural changes as temperature is increased; the first, a concentration independent change where samples become turbid at 32 °C. Increasing the temperature further causes the formation of physically associated hydrogels. This sol-gel transition is concentration dependent and occurs at 32 °C for 40 wt% samples, and increases to 42 °C for 10 wt% samples. From variable temperature SAXS characterization micelles of 20–25 nm in radius can be seen and maintain their size and packing below 32 °C. A gradual increase in the aggregation of micelles corresponding to a thickening of the material is also observed. Close to and above the gelation temperature, micelles collapse and form a physically associated 3D network. A model is proposed to explain these physical effects, where the poly(vinyl caprolactam) group transitions from the hydrophilic corona at room temperature to the hydrophobic core as temperature is increased.
more »
« less
Thermally Induced Gelling Systems Based on Patchy Polymeric Micelles
Abstract Thermogels that exhibit a sol‐gel transition at body temperature represent a promising class of injectable biomaterials for biomedical applications. Thermogels reported thus far are generally composed of amphiphilic block copolymer micelles with an isotropic thermosensitive surface that induces intermicellar aggregation upon heating. Despite the promise, these hydrogels exhibit low mechanical strengths due to their uncontrollable aggregation resulting in void formation. To gain better control over intermicellar assembly, herein a novel thermogel design concept is presented based on patchy polymeric micelles bearing multiple thermosensitive surface domains. These domains serve as “patches” to bridge the micelles to form a percolated network structure. Patchy micelles are prepared from a binary mixture of amphiphilic block copolymers: Poly(N‐acryloylmorpholine)‐b‐poly(N‐benzylacrylamide) (PAM‐PBzAM) and poly (N‐isopropyl acrylamide)‐b‐poly(N‐benzylacrylamide) (PNIPAM‐PBzAM), where PBzAM, PAM and PNIPAM are the hydrophobic, hydrophilic and thermosensitive blocks, respectively. At 25 °C, the polymers self‐assembled into mixed shell micelles having a phase‐separated shell with PAM‐ and PNIPAM‐rich domains. At 37 °C, the PNIPAM domains undergo a hydrophilic‐to‐hydrophobic transition to induce intermicellar assembly into entangled worm‐like structures resulting in hydrogel formation. Patchy micelles form a homogeneous network structure without voids. The micelle design significantly affects the inter‐micellar assembly, the thermogelling behavior, and the mechanical properties of the hydrogels.
more »
« less
- PAR ID:
- 10641323
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 35
- Issue:
- 12
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The effect of vortex‐induced mechanical stresses on the fluorescent properties of dye‐containing poly(ethylene glycol)‐block‐poly(lactic acid) (PEG‐b‐PLA) block copolymer micelles has been investigated. PEG‐b‐PLA block copolymer micelles containing fluorescent dyes, 3,3′‐dioctadecyloxacarbocyanine perchlorate (DiO) and/or 1,1′‐dioctadecyl‐3,3,3′,3′‐tetramethylindocarbocyanine perchlorate (DiI), are prepared by a simple one‐step procedure that involves the self‐assembly of block copolymers and spontaneous incorporation of hydrophobic dyes into the core of the micelles. Upon vortexing, the micelle dispersion samples showed a decrease in fluorescence intensity in a rotational speed‐ and time‐dependent manner. The results demonstrated that the vortexing can alter the fluorescent properties of the dye‐containing PEG‐b‐PLA block copolymer micelle dispersion samples, suggesting the potential utility of block copolymer micelles as a mechanical stress‐responsive nanomaterial.more » « less
-
null (Ed.)Recent developments in the field of polymer vesicles, i.e. polymersomes, have demonstrated that disrupting the equilibrium conditions of the milieu could lead to shape transformation into stable non-spherical morphologies, bringing on-demand shape control to reality and bearing great promise for cell mimicry and a variety of biomedical applications. Here, we studied the self-assembly behavior of glassy amphiphilic triblock copolymers, poly(ethylene glycol)- block -polystyrene- stat -poly(coumarin methacrylate)- block -poly(ethylene glycol) (PEG- b -P(S- stat -CMA)- b -PEG), and their response to various stimuli. By changing the respective molecular weights of both the hydrophobic P(S- stat -CMA) and the hydrophilic PEG blocks, we varied the hydrophobic volume fraction thereby accessing a range of morphologies from spherical and worm-like micelles, as well as polymersomes. For the latter, we observed that slow osmotic pressure changes induced by dialysis led to a decrease in size while rapid osmotic pressure changes by addition of a PEG fusogen led to morphological transformations into rod-like and tubular polymersomes. We also found out that chemically crosslinking the vesicles before inducing osmotic pressure changes led to the vesicles exhibiting hypotonic shock, atypical for glassy polymersomes. We believe that this approach combining the robustness of triblock copolymers and light-based transformations will help expand the toolbox to design ever more complex biomimetic constructs.more » « less
-
Abstract The self‐assembly of amphiphilic bottlebrush block copolymers (BCPs), featuring backbones densely grafted with two types of side chains, is less well understood compared to linear BCPs. In particular, the solution self‐assembly of tapered bottlebrush BCPs—cone‐shaped BCPs with hydrophilic or hydrophobic tips—remains unexplored. This study investigates eight tapered and four cylindrical bottlebrush BCPs with varied ratios of hydrophobic polystyrene (PS) and hydrophilic poly(acrylic acid) (PAA) side chains, synthesized via sequential addition of macromonomers using ring‐opening metathesis polymerization (SAM‐ROMP). Self‐assembled nanostructures formed in water were analyzed using cryogenic transmission electron microscopy, small‐angle neutron scattering, and dynamic light scattering. Most BCPs generated multiple nanostructures with surface protrusions, including spherical micelles, cylindrical micelles, and vesicles, alongside transitional forms like ellipsoids and semi‐vesicles. Coarse‐grained molecular dynamics simulations supported the experimental findings, which revealed two distinct self‐assembly pathways. The first involved micelle fusion, producing elliptical and cylindrical aggregates, sometimes forming Y‐junctions. The second pathway featured micelle maturation into semivesicles, which developed into vesicles or large compound vesicles. This work provides the first experimental evidence of vesicle formation via semivesicles in bottlebrush BCPs and demonstrates the significant influence of cone directionality on self‐assembly behavior in these cone‐shaped polymeric amphiphiles.more » « less
-
ABSTRACT Carbohydrates are the fundamental building blocks of many natural polymers, their wide bioavailability, high chemical functionality, and stereochemical diversity make them attractive starting materials for the development of new synthetic polymers. In this work, one such carbohydrate,d‐glucopyranoside, was utilized to produce a hydrophobic five‐membered cyclic carbonate monomer to afford sugar‐based amphiphilic copolymers and block copolymers via organocatalyzed ring‐opening polymerizations with 4‐methylbenzyl alcohol and methoxy poly(ethylene glycol) as initiator and macroinitiator, respectively. To modulate the amphiphilicities of these polymers acidic benzylidene cleavage reactions were performed to deprotect the sugar repeat units and present hydrophilic hydroxyl side chain groups. Assembly of the polymers under aqueous conditions revealed interesting morphological differences, based on the polymer molar mass and repeat unit composition. The initial polymers, prior to the removal of the benzylidenes, underwent a morphological change from micelles to vesicles as the sugar block length was increased, causing a decrease in the hydrophilic–hydrophobic ratio. Deprotection of the sugar block increased the hydrophilicity and gave micellar morphologies. This tunable polymeric platform holds promise for the production of advanced materials for implementation in a diverse range of applications. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem.2019,57, 432–440more » « less
