Dynamic Covalent Polymer Networks: A Molecular Platform for Designing Functions beyond Chemical Recycling and Self-Healing

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(3), P. 1716 - 1745

Published: Jan. 4, 2021

Dynamic covalent polymer networks (DCPN) have historically attracted attention for their unique roles in chemical recycling and self-healing, which are both relevant sustainable societal development. Efforts these directions intensified the past decade with notable progress newly discovered dynamic chemistry, fundamental material concepts, extension toward emerging applications including energy electronic devices. Beyond that, values of DCPN discovering/designing functional properties not offered by classical thermoplastic thermoset polymers recently gained traction. In particular, bond exchangeability has shown unparalleled design versatility various areas shape-shifting materials/devices, artificial muscles, microfabrication. Going beyond this basic exchangeability, molecular mechanisms to manipulate network topologies (topological transformation) led opportunities program polymers, concepts such as living topological isomerization. review, we provide an overview above particular focuses on strategies exploitation properties. Based this, point out remaining issues offer perspectives how class materials can shape future ways that complementary polymers.

Language: Английский

---

Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals

Science, Journal Year: 2021, Volume and Issue: 373(6556), P. 783 - 789

Published: Aug. 12, 2021

Identifying plastics capable of chemical recycling to monomer (CRM) is the foremost challenge in creating a sustainable circular plastic economy. Polyacetals are promising candidates for CRM but lack useful tensile strengths owing low molecular weights produced using current uncontrolled cationic ring-opening polymerization (CROP) methods. Here, we present reversible-deactivation CROP cyclic acetals commercial halomethyl ether initiator and an indium(III) bromide catalyst. Using this method, synthesize poly(1,3-dioxolane) (PDXL), which demonstrates strength comparable some commodity polyolefins. Depolymerization PDXL strong acid catalysts returns near-quantitative yield even proceeds from waste mixture. Our efficient method affords tough thermoplastic that can undergo selective depolymerization monomer.

Language: Английский

---

Disulfide-Mediated Reversible Polymerization toward Intrinsically Dynamic Smart Materials

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2022 - 2033

Published: Jan. 6, 2022

The development of a dynamic chemistry toolbox to endow materials behavior has been key the rational design future smart materials. rise supramolecular and covalent offers many approaches construction polymers that can adapt, respond, repair, recycle. Within this toolbox, building blocks based on 1,2-dithiolanes have become an important scaffold, featuring their reversible polymerization mediated by disulfide bonds, which enables unique class at intersection adaptable networks. This Perspective aims explore as versatile structural unit for summarizing state art well providing overview fundamental challenges involved in research area its potential directions.

Language: Английский

---

100th Anniversary of Macromolecular Science Viewpoint: Toward Catalytic Chemical Recycling of Waste (and Future) Plastics

ACS Macro Letters, Journal Year: 2020, Volume and Issue: 9(11), P. 1494 - 1506

Published: Oct. 12, 2020

The current global materials economy has long been inefficient due to unproductive reuse and recycling efforts. Within the wider portfolio, plastics have revolutionary many industries but they treated as disposable commodities leading their increasing accumulation in environment waste. field of chemistry had significant bearing ushering industry will undoubtedly a hand transforming it become more sustainable. Existing approaches include development synthetic biodegradable turning renewable raw order produce similar our petrol-based or create new polymers. Additionally, chemists are confronting environmental crisis by developing alternative methods deal with legacy plastic Important emergent technologies, such catalytic chemical upcycling, potential alleviate numerous issues related future refuse and, doing so, help pivot from linearity circularity.

Language: Английский

---

Polymeric Nanoparticles for Drug Delivery

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 5505 - 5616

Published: April 16, 2024

The recent emergence of nanomedicine has revolutionized the therapeutic landscape and necessitated creation more sophisticated drug delivery systems. Polymeric nanoparticles sit at forefront numerous promising designs, due to their unmatched control over physiochemical properties such as size, shape, architecture, charge, surface functionality. Furthermore, polymeric have ability navigate various biological barriers precisely target specific sites within body, encapsulate a diverse range cargo efficiently release this in response internal external stimuli. However, despite these remarkable advantages, presence wider clinical application is minimal. This review will provide comprehensive understanding vehicles. affecting be outlined first, followed by description nanoparticle designs preparation methods, beginning with polymers on which they are based. meticulously explore current performance against myriad diseases including cancer, viral bacterial infections, before finally evaluating advantages crucial challenges that determine potential decades come.

Language: Английский

---

Dual closed-loop chemical recycling of synthetic polymers by intrinsically reconfigurable poly(disulfides)

Matter, Journal Year: 2021, Volume and Issue: 4(4), P. 1352 - 1364

Published: Feb. 6, 2021

Language: Английский

---

Covalent Adaptable Liquid Crystal Networks Enabled by Reversible Ring-Opening Cascades of Cyclic Disulfides

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(32), P. 12543 - 12551

Published: July 19, 2021

The development of covalent adaptable liquid crystal networks (LCNs) enabled by introducing dynamic bonds has endowed actuators with self-healing properties and reversible shape programmability, broadening their applications in diverse soft robotic devices. However, the finite molecular design strategy limits recyclability architectural diversity these materials. Here, a is first reported for fabricating photoresponsive polydisulfide-based LCNs ring-opening polymerization cyclic dithiolane groups. Based on disulfide metathesis, resulting materials are self-healable, reshapable, reprogrammable. Importantly, equilibrium between polymer backbones dithiolane-functionalized monomers enables catalytic depolymerization to recycle monomers, which could significantly weaken disadvantage subtractive manufacturing photomechanical This work rooted chemistry would provide an economical environmentally friendly fabrication functional robotics excellent programmability renewability beyond.

Language: Английский

---

Thiol-Mediated Uptake

JACS Au, Journal Year: 2021, Volume and Issue: 1(6), P. 710 - 728

Published: May 3, 2021

This Perspective focuses on thiol-mediated uptake, that is, the entry of substrates into cells enabled by oligochalcogenides or mimics, often disulfides, and inhibited thiol-reactive agents. A short chronology from initial observations in 1990 until today is followed a summary cell-penetrating poly(disulfide)s (CPDs) cyclic (COCs) as privileged scaffolds uptake inhibitors potential antivirals. In spirit Perspective, main part brings together topics possibly could help to explain how really works. Extreme sulfur chemistry mostly related COCs their thiosulfinates/-onates, diselenolanes, benzopolysulfanes, but also arsenics Michael acceptors, viewed context acidity, ring tension, exchange cascades, adaptive networks, affinity columns, molecular walkers, ring-opening polymerizations, templated polymerizations. Micellar pores (or lipid ion channels) are considered, peptides natural antibiotics voltage sensors, concise gallery membrane proteins, possible targets provided, including CLIC1, chloride channel; TMEM16F, Ca-activated scramblase; EGFR, epithelial growth factor receptor; protein-disulfide isomerase, known HIV transferrin receptor, top hit proteomics recently identified cellular SARS-CoV-2.

Language: Английский

---

Self-healing, reprocessable, degradable, thermadapt shape memory multifunctional polymers based on dynamic imine bonds and their application in nondestructively recyclable carbon fiber composites

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 454, P. 139992 - 139992

Published: Oct. 27, 2022

Language: Английский

---

Closed-loop chemical recycling of cross-linked polymeric materials based on reversible amidation chemistry

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Dec. 9, 2022

Abstract Closed-loop chemical recycling provides a solution to the end-of-use problem of synthetic polymers. However, it remains major challenge design dynamic bonds, capable effective bonding and reversible cleaving, for preparing chemically recyclable cross-linked Herein, we report maleic acid tertiary amide bond based upon amidation reaction between anhydrides secondary amines. This allows construction polymer networks with tailorable robust mechanical properties, covering strong elastomers tensile strength 22.3 MPa rigid plastics yield 38.3 MPa. Impressively, these polymeric materials can be completely depolymerized in an acidic aqueous at ambient temperature, leading efficient monomer recovery >94% separation yields. Meanwhile, recovered monomers used remanufacture without losing their original performance. work unveils general approach tunable performance closed-loop recyclability, which will open new avenue sustainable materials.

Language: Английский

---