CO₂‐Fueled Transient Breathing Nanogels that Couple Nonequilibrium Catalytic Polymerization

Abstract

Here we present a “breathing” nanogel that is fueled by CO2 gas to perform temporally programmable catalytic polymerization. The nanogel is composed of common frustrated Lewis pair polymers (FLPs). Dynamic CO2‐FLP gas‐bridging bonds endow the nanogel with a transient volume contraction, and the resulting proximal effect of bound FLPs unlocks its catalytic capacity toward CO2. Reverse gas depletion via a CO2‐participated polymerization can induce a reverse nanogel expansion, which shuts down the catalytic activity. Control of external factors (fuel level, temperature or additives) can regulate the breathing period, amplitude and lifecycle, so as to affect the catalytic polymerization. Moreover, editing the nanogel breathing procedure can sequentially evoke the copolymerization of CO2 with different epoxide monomers preloaded therein, which allows to obtain block‐tunable copolycarbonates that are unachievable by other methods. This synthetic dissipative system would be function as a prototype of gas‐driven nanosynthesizer.

Light-Induced Polymeric Frustrated Radical Pairs as Building Blocks for Materials and Photocatalysts

“…No CO 2 activation by Poly-1 / Poly-2 or Poly-1/Poly-3 to form free-standing gels occurred; no visual or NMR evidence of direct carbon capture was observed up to 2 bar of CO 2 pressures and temperatures from 0 to 80 °C (Figure b). This is not surprising as no CO 2 activation under mild conditions by small-molecular PMes 3 /B­(C 6 F 5 ) 3 has ever been reported, despite published polymeric systems with similar Lewis acidity and basicity suggesting strong binding. ,, We have not been able to reproduce these findings and note that CO 2 capture in polymeric FLPs should be more challenging than that for analogous small molecules due to the relative entropic penalties in both cases.…”

“…The work has inspired other poly­(FLP) systems including masked polystyrene-based FLPs for catalytic C–H borylation and three-dimensional phosphine networks with exogenous tris­(pentafluorophenyl)­borane (B­(C 6 F 5 ) 3 ) for dihydrogen cleavage . Transformations of CO 2 /H 2 by polymer-supported FLPs have also been documented. − …”

Is aromatic plants environmental health engineering (APEHE) a leverage point of the earth system?

“…Meanwhile, on the premise of meeting indoor needs, redundant BVOCs can be considered by some methods of enrichment and transformation and the recovery of MAPs [ 74 ], research and development of new fuels [ 75 ] or hybrid fuels [ 76 ] and applications in other fields, such as gas-powered nanosynthesizers for automatic production of polymers on demand [ 77 ].…”

Dynamic supramolecular hydrogels mediated by chemical reactions

“…In the past decades, a number of out-of-equilibrium supramolecular hydrogel systems were designed and created by orchestrating inverse chemical reaction networks such as enzymatic reactions, 77–79 pH feedback loops, 70,73,121–124 redox reactions, 124 oscillatory reactions, 125 and transient chemical signals dictated by reaction-diffusion. 92,126,127 Amongst them, a pH-dependent reversible condensation/hydrolysis reaction of boric acid and diols has been reported by Liu and co-workers.…”

“…The group of van Eelkema and van Esch pioneered the development of out-of-equilibrium supramolecular hydrogels using methylation reagents as the fuels. 22,53 After that, various beautiful examples of out-of-equilibrium supramolecular assemblies powered by different chemical fuels, including carbodiimide, 57–62 ATP, 55,63–69 pH regulators, 70–75 enzymatic reactions, 15,66,76–78 carbon dioxide, 79,80 and others, 81–84 have been carefully developed. The resultant supramolecular hydrogels show high dynamics, tunable lifetime and stiffness, and a regenerative capability.…”