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Tuning Net Charge in Aliphatic Polycarbonates Alters Solubility and Protein Complexation Behavior.

ABSTRACT: A synthetic strategy yielded polyelectrolytes and polyampholytes with tunable net charge for complexation and protein binding. Organocatalytic ring-opening polymerizations yielded aliphatic polycarbonates that were functionalized with both carboxylate and ammonium side chains in a post-polymerization, radical-mediated thiol-ene reaction. Incorporating net charge into the polymer architecture altered the chain dimensions in phosphate buffered solution in a manner consistent with self-complexation and complexation behavior with model proteins. A net cationic polyampholyte with 5% of carboxylate side chains formed large clusters rather than small complexes with bovine serum albumin, while 50% carboxylate polyampholyte was insoluble. Overall, the aliphatic polycarbonates with varying net charge exhibited different macrophase solution behaviors when mixed with protein, where self-complexation appears to compete with protein binding and larger-scale complexation.

SUBMITTER: Posey ND

PROVIDER: S-EPMC8427630 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Tuning Net Charge in Aliphatic Polycarbonates Alters Solubility and Protein Complexation Behavior.

Posey Nicholas D ND Ma Yuanchi Y Lueckheide Michael M Danischewski Julia J Fagan Jeffrey A JA Prabhu Vivek M VM

ACS omega 20210826 35

A synthetic strategy yielded polyelectrolytes and polyampholytes with tunable net charge for complexation and protein binding. Organocatalytic ring-opening polymerizations yielded aliphatic polycarbonates that were functionalized with both carboxylate and ammonium side chains in a post-polymerization, radical-mediated thiol-ene reaction. Incorporating net charge into the polymer architecture altered the chain dimensions in phosphate buffered solution in a manner consistent with self-complexation ...[more]

PMID: 34514231

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Project description:Herein, N-heterocyclic olefins (NHOs) are utilized as catalysts for the ring-opening polymerization (ROP) of functional aliphatic carbonates. This emerging class of catalysts provides high reactivity and rapid conversion. Aiming for the polymerization of monomers with high side chain functionality, six-membered carbonates derived from 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) served as model compounds. Tuning the reactivity of NHO from predominant side chain transesterification at room temperature toward ring-opening at lowered temperatures (-40 °C) enables controlled ROP. These refined conditions give narrowly distributed polymers of the hydrophobic carbonate 5-methyl-5-benzyloxycarbonyl-1,3-dioxan-2-one (MTC-OBn) (Đ < 1.30) at (pseudo)first-order kinetic polymerization progression. End group definition of these polymers demonstrated by mass spectrometry underlines the absence of side reactions. For the active ester monomer 5-methyl-5-pentafluorophenyloxycarbonyl-1,3-dioxane-2-one (MTC-PFP) with elevated side chain reactivity, a cocatalysis system consisting of NHO and the Lewis acid magnesium iodide is required to retune the reactivity from side chains toward controlled ROP. Excellent definition of the products (Đ < 1.30) and mass spectrometry data demonstrate the feasibility of this cocatalyst approach, since MTC-PFP has thus far only been polymerized successfully using acidic catalysts with moderate control. The broad feasibility of our findings was further demonstrated by the synthesis of block copolymers for bioapplications and their successful nanoparticular assembly. High tolerability of NHO in vitro with concentrations ranging up to 400 μM (equivalent to 0.056 mg/mL) further emphasize the suitability as a catalyst for the synthesis of bioapplicable materials. The polycarbonate block copolymer mPEG44-b-poly(MTC-OBn) enables physical entrapment of hydrophobic dyes in sub-20 nm micelles, whereas the active ester block copolymer mPEG44-b-poly(MTC-PFP) is postfunctionalizable by covalent dye attachment. Both block copolymers thereby serve as platforms for physical or covalent modification of nanocarriers for drug delivery.

Dataset Information

Tuning Net Charge in Aliphatic Polycarbonates Alters Solubility and Protein Complexation Behavior.

Publications

Tuning Net Charge in Aliphatic Polycarbonates Alters Solubility and Protein Complexation Behavior.

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