Degradation in Order: Simple and Versatile One‐Pot Combination of Two Macromolecular Concepts to Encode Diverse and Spatially Regulated Degradability Functions

Abstract

The clever one-pot combination of two macromolecular concepts,r ing-opening polymerization (ROP) and step-growthp olymerization (SGP), is demonstrated to be as imple,y et powerful tool to design al ibrary of sequencecontrolled polymers with diverse and spatially regulated degradability functions.R OP and SGP occur sequentially at room temperature when the organocatalytic conditions are switched from basic to acidic,and each allows the encoding of specific degradable bonds.R OP controls the sequence length and position of the degradability functions,while SGP between the complementary vinyl ether and hydroxyl chain-ends enables the formation of acetal bonds and high-molar-mass copolymers.The result is the rational combination of cleavable bonds prone to either bulk or surface erosion within the same macromolecule.T he strategy is versatile and offers higher chemical diversity and level of control over the primary structure than current aliphatic polyesters or polycarbonates, while being simple,effective,and atom-economical and having potential for scalability.

Ring opening copolymerization of δ-valerolactone with 2-methyl-1,3-dioxane-4-one towards poly(3-hydroxypropionate-co-5-hydroxyvalerate) copolyesters

“…Recently, multiple measures have been taken to develop poly(acetal-ester)s and polyacetals. [24][25][26][27][28][29][30][31] 2-Methyl-1,3-dioxane-4one (MDO) as a kind of cycloacetal ester has both an ester group and an acetal bond, [32][33][34][35][36] and showed an unprecedented result during its Et 2 Zn catalyzed ROP, where poly(hemiacetal ester) (PMDO) was obtained at a low ratio of catalyst/initiator (low [Zn]) and the polyester (P3HP) was obtained at a high ratio of catalyst/initiator (high [Zn]). MDO as an alternative β-PL is accessible for the synthesis of P3HP.…”

Introducing SuFEx click chemistry into aliphatic polycarbonates: a novel toolbox/platform for post-modification as biomaterials

“…As a guanidine Lewis base, 1,5,7-triazabicyclo[4,4,0]dec-5ene (TBD) has recently attracted interest in terms of catalysis of a wide range of chemical reactions, including SuFEx click chemistry [32][33][34] and ROP. [35][36][37][38] With the versatility of TBD as an organocatalyst, it is inspiring to explore the design of an APC system where ROP and PPM via SuFEx can be achieved synchronously and simultaneously without constraining or antagonizing each other. Therefore, in this work, we innovatively propose to incorporate SuFEx click chemistry into APCs for the synthesis of carbonates, as well as ROP and biofunctionalization.…”

Organocatalytic orthogonal ATRP and ring-opening polymerization using a single dual-function photocatalyst

“…9–17 Accordingly, the development of effective orthogonal polymerization systems has attracted considerable research interest in the past few years, which are highly desirable in both academia and industry. 18–22…”

“…[9][10][11][12][13][14][15][16][17] Accordingly, the development of effective orthogonal polymerization systems has attracted considerable research interest in the past few years, which are highly desirable in both academia and industry. [18][19][20][21][22] The reversible-deactivation radical polymerization (RDRP) method represents a powerful tool for the precise construction of macromolecules with a predictable molecular mass, low dispersity, high end-group fidelity, and advanced complex structures [23][24][25][26][27][28][29][30] and could serve as a useful and versatile component in orthogonal polymerization. [15][16][17][18][19][26][27][28][29][30][31][32][33][34] For example, as early as 1998, Jérôme, Hedrick and co-workers 31 demonstrated the one-pot preparation of block and graft copolymers by combining nitroxide-mediated living free-radical polymerization (NMP) and ring-opening polymerization (ROP) with the help of Sn and Al metal complexes, but high polydispersity indices were observed even with this dual-living polymerization strategy.…”

“…[18][19][20][21][22] The reversible-deactivation radical polymerization (RDRP) method represents a powerful tool for the precise construction of macromolecules with a predictable molecular mass, low dispersity, high end-group fidelity, and advanced complex structures [23][24][25][26][27][28][29][30] and could serve as a useful and versatile component in orthogonal polymerization. [15][16][17][18][19][26][27][28][29][30][31][32][33][34] For example, as early as 1998, Jérôme, Hedrick and co-workers 31 demonstrated the one-pot preparation of block and graft copolymers by combining nitroxide-mediated living free-radical polymerization (NMP) and ring-opening polymerization (ROP) with the help of Sn and Al metal complexes, but high polydispersity indices were observed even with this dual-living polymerization strategy. In 2005, the Howdle group disclosed a successful combination of conventional metal-based atom transfer radical polymerization (ATRP) and enzymatic ROP using supercritical carbon dioxide as a solvent.…”