Understanding Potentials and Restrictions of Solvent‐Free Enzymatic Polycondensation of Itaconic Acid: An Experimental and Computational Analysis

Abstract

Itaconic acid is ac hemically versatile unsaturated diacid that can be produced by fermentation and potentially it can replace petrol-based monomers such as maleic and fumarica cids in the production of curable polyesters or new biocompatible functionalized materials.U nfortunately,d ue to the presence of the unsaturated C=Cb ond, polycondensation of itaconica cid is hampered by cross reactivity and isomerization. Therefore,e nzymatic polycondensations wouldr espondt ot he need of mild and selective synthetic routes for the production of novelb io-based polymers.T he present work analyses the feasibility of enzymatic polycondensation of diethyli taconate and, for the first time,p rovidesc omprehensives olutions embracing botht he formulation of the biocata-lyst, the reaction conditions and the choice of the comonomers.C omputational docking was used to disclose the structural factorsresponsible for the low reactivity of dimethyl itaconate and to identify possible solutions.S urprisingly,e xperimentala nd computational analyses revealed that 1,4-butanediol is an unsuitable co-monomer for the polycondensation of dimethyli taconate whereast he cyclica nd rigid 1,4-cyclohexanedimethanol promotes the elongation of the oligomers.

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“…The reaction is highly specific, cleaving the C 2 -C 3 bond of glucose molecules and converting the hydroxyl groups into aldehyde groups. These observations indicate that further optimization studies should pursue the direction of preparing CaLB formulations with lower loadings, with the consequent economic advantages 19 . Secondly, the oxidized RH was also reacted with a diamino spacer, and the latter was then activated with glutaraldehyde ( Figure 3b) The enzyme was finally anchored on the aldehyde groups via the Lys residues.…”

“…(tpG) and the invertase from Saccharomyces cerevisiae (ISc) 17 . Overall, lipases have a wide industrial impact in the food, pharma and cosmetic sectors but their catalytic potential is far from being fully exploited for the production of commodities or biodiesel [19][20][21] . CaLB (3.1.1.3) is widely employed in the production of fine chemicals for its selectivity but also in the production of esters for body care sector.…”

“…Recently we demonstrated that the covalent immobilization of enzymes on appropriate robust carriers is the pre-requisite for carrying out enzymatic polycondensations while preventing the detachment of the enzyme protein from the support 19,20,37 .…”

“…As an alternative solution, it was demonstrated that distributing the catalyst on the widest carrier surface facilitates the enzyme-substrate approach and promotes the polycondensation 19 . As an alternative solution, it was demonstrated that distributing the catalyst on the widest carrier surface facilitates the enzyme-substrate approach and promotes the polycondensation 19 .…”

“…Such solution is necessarily related to the possibility of using inexpensive, widely available and possibly renewable carriers. 19, 20 Therefore, the RH-CaLB formulation has been tested in solvent free polycondensation of dimethyl adipate with 1,4-butanediol.…”