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. 2017 Aug 30;9(9):403.
doi: 10.3390/polym9090403.

Polyol Structure and Ionic Moieties Influence the Hydrolytic Stability and Enzymatic Hydrolysis of Bio-Based 2,5-Furandicarboxylic Acid (FDCA) Copolyesters

Karolina Haernvall  1 , Sabine Zitzenbacher  2 , Motonori Yamamoto  3 , Michael Bernhard Schick  4 , Doris Ribitsch  5 , Georg M Guebitz  6   7
Affiliations

Polyol Structure and Ionic Moieties Influence the Hydrolytic Stability and Enzymatic Hydrolysis of Bio-Based 2,5-Furandicarboxylic Acid (FDCA) Copolyesters

Karolina Haernvall et al. Polymers (Basel). .

Abstract

A series of copolyesters based on furanic acid and sulfonated isophthalic acid with various polyols were synthetized and their susceptibility to enzymatic hydrolysis by cutinase 1 from Thermobifida cellulosilytica (Thc_Cut1) investigated. All copolyesters consisted of 30 mol % 5-sulfoisophthalate units (NaSIP) and 70 mol % 2,5-furandicarboxylic acid (FDCA), while the polyol component was varied, including 1,2-ethanediol, 1,4-butanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, or tetraethylene glycol. The composition of the copolyesters was confirmed by ¹H-NMR and the number average molecular weight (Mn) was determined by GPC to range from 2630 to 8030 g/mol. A DSC analysis revealed glass-transition temperatures (Tg) from 84 to 6 °C, which were decreasing with increasing diol chain length. The crystallinity was below 1% for all polyesters. The hydrolytic stability increased with the chain length of the alkyl diol unit, while it was generally higher for the ether diol units. Thc_Cut1 was able to hydrolyze all of the copolyesters containing alkyl diols ranging from two to eight carbon chain lengths, while the highest activities were detected for the shorter chain lengths with an amount of 13.6 ± 0.7 mM FDCA released after 72 h of incubation at 50 °C. Faster hydrolysis was observed when replacing an alkyl diol by ether diols, as indicated, e.g., by a fivefold higher release of FDCA for triethylene glycol when compared to 1,8-octanediol. A positive influence of introducing ionic phthalic acid was observed while the enzyme preferentially cleaved ester bonds associated to the non-charged building blocks.

Keywords: Thermobifida cellulosilytica; bio-based; cutinase; poly(2,5-furan dicarboxylate); sulfonated isophthalic acid.

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Conflict of interest statement

The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

Figures

Figure 1
Figure 1
(A) Chemical structure of copolyesters based on 5-sulfoisophthalic acid and 2,5-furandicarboxylic acid with altering alkyl and ether diols, with altering alkyl diol (green diamond) and ether diol (pink rectangle), where n is 2, 4, or 8, and m is 2, 3, or 4. (B) Chemical structure of polyesters based on 2,5-furandicarboxylic acid with altering alkyl diol (yellow diamond) and ether diol (blue rectangle), where n is 3, 5, 6, 8, 9 or 12.
Figure 2
Figure 2
1H-NMR spectrum of (A) PBFSI, (B) POFSI, (C) PDEFSI, (D) PTEFSI and (E) PTeEFSI.
Figure 2
Figure 2
1H-NMR spectrum of (A) PBFSI, (B) POFSI, (C) PDEFSI, (D) PTEFSI and (E) PTeEFSI.
Figure 3
Figure 3
DSC thermographs for the glass-transition temperatures of the melted polymer with a cooling rate of 20 K/min for (A) PEFSI, (B) PBFSI, (C) POFSI, (D) PDEFSI, (E) PTEFSI and (F) PTeEFSI in dimethyl sulfoxide.
Figure 4
Figure 4
FTIR spectrum of copolyesters based on 5-sulfoisophthalic acid and 2,5-furandicarboxylic acid with altering alkyl (A) and ether (B) with altering polyols, where the codes represent the different alkyl and ether diols in the copolyesters and where PEFSI is 1,2-ethanediol, PBFSI is 1,4-butanediol, POFSI is 1,8-octanediol, PDEFSI is diethylene glycol, PTEFSI is triethylene glycol, and PTeEFSI is tetraethylene glycol.
Figure 5
Figure 5
Hydrolytic degradation of copolyesters based on 5-sulfoisophthalic acid and 2,5-furandicarboxylic acid with (A) altering alkyl and (B) ether diols in 100 mM phosphate buffer of pH 7 and 50 °C after 24, 48, and 72 h represented by the amount of released 2,5-furandicarboxylic acid (FDCA). Each bar represents the average of three independent samples; error bars indicate the standard deviation.
Figure 6
Figure 6
Enzymatic hydrolysis of copolyesters based on 5-sulfoisophthalic acid and 2,5-furandicarboxylic acid with altering (A) alkyl diols and (B) ether diols by cutinase 1 from Thermobifida cellulosilytica after 24, 48, and 72 h at 50 °C represented by the amount of released 2,5-furandicarboxylic acid (FDCA). Each bar represents the average of three independent samples; error bars indicate the standard deviation.
Figure 7
Figure 7
Enzymatic hydrolysis of polyesters based on 2,5-furandicarboxylic acid and copolyesters based on 5-sulfoisophthalic acid and 2,5-furandicarboxylic acid with (A) alkyl diol 1,8-octanediol and (B) ether diol diethylene glycol by cutinase 1 from Thermobifida cellulosilytica after 24, 48 and 72 h at 50 °C represented by the amount of released 2,5-furandicarboxylic acid (FDCA). Each bar represents the average of three independent samples; error bars indicate the standard deviation.
Figure 8
Figure 8
Enzymatic hydrolysis of copolyesters consisting of 5-sulfoisophthalic acid and 2,5-furandicarboxylic acid with altering ether diols by cutinase 1 from Thermobifida cellulosilytica after 72 h at 50 °C represented by the amount of released FDCA. Each circle represents the average of three independent samples; error bars indicate the standard deviation.
Figure 9
Figure 9
Enzymatic hydrolysis of polyesters consisting of 2,5-furandicarboxylic acid with altering alkyl diols by cutinase 1 from Thermobifida cellulosilytica after 72 h at 50 °C represented by the amount of released FDCA. Each circle represents the average of three independent samples; error bars indicate the standard deviation.
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