By combining the unique characteristics of molecular bottlebrushes (MBBs) and the properties of stimuli‐responsive polymers, we show that MBBs with randomly grafted poly(
- NSF-PAR ID:
- 10173073
- Date Published:
- Journal Name:
- Materials Chemistry Frontiers
- Volume:
- 2
- Issue:
- 12
- ISSN:
- 2052-1537
- Page Range / eLocation ID:
- 2230 to 2238
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract n ‐butyl acrylate) and pH‐responsive poly(2‐(N ,N ‐diethylamino)ethyl methacrylate) (PDEAEMA) side chains are efficient and robust pH‐responsive emulsifiers. Water‐in‐toluene emulsions were formed at pH 4.0 and disrupted by increasing the pH to 10.0. The emulsion generation and disruption was reversible over the ten cycles investigated, and the bottlebrushes remained intact. The exceptional emulsion stability stemmed from the high interfacial binding energy of MBBs, imparted by their large molecular size and Janus architecture at the interface, as evidenced by the interfacial jamming and wrinkling of the assemblies upon reducing the interfacial area. At pH 10.0, PDEAEMA became water‐insoluble, and the MBBs desorbed from the interface, causing de‐emulsification. Consequently, we have shown that the judicious design of MBBs can generate properties of particle emulsifiers from their large size, while the responsiveness of the MBBs enables more potential applications. -
more » « less
Abstract By combining the unique characteristics of molecular bottlebrushes (MBBs) and the properties of stimuli‐responsive polymers, we show that MBBs with randomly grafted poly(
n ‐butyl acrylate) and pH‐responsive poly(2‐(N ,N ‐diethylamino)ethyl methacrylate) (PDEAEMA) side chains are efficient and robust pH‐responsive emulsifiers. Water‐in‐toluene emulsions were formed at pH 4.0 and disrupted by increasing the pH to 10.0. The emulsion generation and disruption was reversible over the ten cycles investigated, and the bottlebrushes remained intact. The exceptional emulsion stability stemmed from the high interfacial binding energy of MBBs, imparted by their large molecular size and Janus architecture at the interface, as evidenced by the interfacial jamming and wrinkling of the assemblies upon reducing the interfacial area. At pH 10.0, PDEAEMA became water‐insoluble, and the MBBs desorbed from the interface, causing de‐emulsification. Consequently, we have shown that the judicious design of MBBs can generate properties of particle emulsifiers from their large size, while the responsiveness of the MBBs enables more potential applications. -
more » « less
Abstract Known for their adaptability to surroundings, capability of transport control of molecules, or the ability of converting one type of energy to another as a result of external or internal stimuli, responsive polymers play a significant role in advancing scientific discoveries that may lead to an array of diverge applications. This review outlines recent advances in the developments of selected commodity polymers equipped with stimuli‐responsiveness to temperature, pH, ionic strength, enzyme or glucose levels, carbon dioxide, water, redox agents, electromagnetic radiation, or electric and magnetic fields. Utilized diverse applications ranging from drug delivery to biosensing, dynamic structural components to color‐changing coatings, this review focuses on commodity acrylics, epoxies, esters, carbonates, urethanes, and siloxane‐based polymers containing responsive elements built into their architecture. In the context of stimuli‐responsive chemistries, current technological advances as well as a critical outline of future opportunities and applications are also tackled.
-
In this work, we designed and fabricated a nanoscopic sugar-based magnetic hybrid material that is capable of tackling environmental pollution posed by marine oil spills, while minimizing potential secondary problems that may occur from microplastic contamination. These readily-defined magnetic nanocomposites were constructed through co-assembly of magnetic iron oxide nanoparticles (MIONs) and a degradable amphiphilic polymer, poly(ethylene glycol)- b -dopamine-functionalized poly(ethyl propargyl glucose carbonate)- b -poly(ethyl glucose carbonate), PEG- b -PGC[(EPC-MPA)- co -(EPC-DOPA)]- b -PGC(EC), driven by supramolecular co-assembly in water with enhanced interactions provided via complexation between dopamine and MIONs. The composite nanoscopic assemblies possessed a pseudo -micellar structure, with MIONs trapped within the polymer framework. The triblock terpolymer was synthesized by sequential ring-opening polymerizations (ROPs) of two glucose-derived carbonate monomers, initiated by a PEG macroinitiator. Dopamine anchoring groups were subsequently installed by first introducing carboxylic acid groups using a thiol–yne click reaction, followed by amidation with dopamine. The resulting amphiphilic triblock terpolymers and MIONs were co-assembled to afford hybrid nanocomposites using solvent exchange processes from organic solvent to water. In combination with hydrophobic interactions, the linkage between dopamine and iron oxide stabilized the overall nanoscopic structure to allow for the establishment of a uniform globular morphology, whereas attempts at co-assembly with the triblock terpolymer precursor, lacking dopamine side chains, failed to afford well-defined nanostructures. The magnetic hybrid nanoparticles demonstrated high oil sorption capacities, ca. 8 times their initial dry weight, attributed, in part, to large surface areas leading to effective contact between the nanomaterials and hydrocarbon pollutants. Moreover, the naturally-derived polymer framework undergoes hydrolytic degradation to break down into byproducts that include glucose, ethanol and dopamine if not recovered after deployment, alleviating concerns of potential microplastic generation and persistence.more » « less
-
more » « less
Abstract Clinical application of injectable, thermoresponsive hydrogels is hindered by lack of degradability and controlled drug release. To overcome these challenges, a family of thermoresponsive, ABC triblock polymer‐based hydrogels has been engineered to degrade and release drug cargo through either oxidative or hydrolytic/enzymatic mechanisms dictated by the “A” block composition. Three ABC triblock copolymers are synthesized with varying “A” blocks, including oxidation‐sensitive poly(propylene sulfide), slow hydrolytically/enzymatically degradable poly(ε‐caprolactone), and fast hydrolytically/enzymatically degradable poly(
d ,l ‐lactide‐co ‐glycolide), forming the respective formulations PPS135‐b ‐PDMA152‐b ‐PNIPAAM225(PDN), PCL85‐b ‐PDMA150‐b ‐PNIPAAM150(CDN), and PLGA60‐b ‐PDMA148‐b ‐PNIPAAM152(LGDN). For all three polymers, hydrophilic poly(N ,N ‐dimethylacrylamide) and thermally responsive poly(N ‐isopropylacrylamide) comprise the “B” and “C” blocks, respectively. These copolymers form micelles in aqueous solutions at ambient temperature that can be preloaded with small molecule drugs. These solutions quickly transition into hydrogels upon heating to 37 °C, forming a supra‐assembly of physically crosslinked, drug‐loaded micelles. PDN hydrogels are selectively degraded under oxidative conditions while CDN and LGDN hydrogels are inert to oxidation but show differential rates of hydrolytic/enzymatic decomposition. All three hydrogels are cytocompatible in vitro and in vivo, and drug‐loaded hydrogels demonstrate differential release kinetics in vivo corresponding with their specific degradation mechanism. These collective data highlight the potential cell and drug delivery use of this tunable class of ABC triblock polymer thermogels.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C8QM00353J
