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Amino acid complexes with tin as a new class of catalysts with high reactivity and low toxicity towards biocompatible aliphatic polyesters

Polymer Journal volume 52, pages 567–574 (2020)Cite this article

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Abstract

A series of complexes consisting of natural amino acids and tin (Sn(AA)2) prepared by conventional neutralization reactions were tested as a new class of cost-effective catalysts with high reactivity and low toxicity towards some biocompatible aliphatic polyesters. In our system, by using a simple catalyst and a benzyl alcohol (BnOH) initiator, biocompatible, and biodegradable aliphatic polyesters, such as poly(l-lactide), poly(ε-caprolactone), and poly(trimethylene carbonate), were well prepared. The results demonstrated that Sn(AA)2 catalysts, especially the phenylalanine-tin complex (Sn(L-Phe)2) (Mn, up to 194 kg/mol), were suitable for the synthesis of moderate and high-molecular weight poly(l-lactide), which exhibited good biocompatibility. Analysis of the backbone structure and end groups of low-molar-mass polymers by using MALDI-TOF mass spectra and 1H NMR spectroscopy suggested that the reaction proceeds by a dual activation mechanism. Given their low cost, simple preparation, high reactivity, and low toxicity, complexes consisting of natural amino acids and tin are promising for industrial-scale production of biocompatible aliphatic polyesters.

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References

  1. Arcy R, Burke J, Tirelli N. Branched polyesters: preparative strategies and applications. Adv drug Deliv Rev. 2016;107:60–81.

    Article  Google Scholar 

  2. Yu I, Acosta-Ramírez A, Mehrkhodavandi P. Mechanism of living lactide polymerization by dinuclear indium catalysts and its impact on isoselectivity. J Am Chem Soc. 2012;134:12758–73.

    Article  CAS  Google Scholar 

  3. Hu T, Yang C, Lin S, Yu Q, Wang G. Biodegradable stents for coronary artery disease treatment: recent advances and future perspectives. Mater Sci Eng C. 2018;91:163–78.

    Article  CAS  Google Scholar 

  4. Nottelet B, Darcos V, Coudane J. Aliphatic polyesters for medical imaging and theranostic applications. Eur J Pharm Biopharm. 2015;97:350–70.

    Article  CAS  Google Scholar 

  5. Jérôme C, Lecomte P. Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization. Adv Drug Deliv Rev. 2008;60:1056–76.

    Article  Google Scholar 

  6. Stjerndahl A, Wistrand AF, Albertsson AC. Industrial utilization of tin-initiated resorbable polymers: synthesis on a large scale with a low amount of initiator residue. Biomacromolecules. 2007;8:937–40.

    Article  CAS  Google Scholar 

  7. Platel RH, Hodgson LM, Williams CK. Biocompatible initiators for lactide polymerization. Polym Rev. 2008;48:11–63.

    Article  CAS  Google Scholar 

  8. Dusselier M, Van Wouwe P, Dewaele A, Jacobs PA, Sels BF. Shape-selective zeolite catalysis for bioplastics production. Science. 2015;349:78–80.

    Article  CAS  Google Scholar 

  9. Bagh B, Broere DLJ, Sinha V, Kuijpers PF, Leest NPV, Bruin BD, et al. Catalytic synthesis of N-heterocycles via direct C(sp3)-H amination using an air-stable iron (III) species with a redox-active ligand. J Am Chem Soc. 2017;139:5117–24.

    Article  CAS  Google Scholar 

  10. Nachtergael A, Coulembier O, Dubois P, Helvenstein M, Mespouille L. Organocatalysis paradigm revisited: are metal-free catalysts really harmless. Biomacromolecules. 2015;16:507–14.

    Article  CAS  Google Scholar 

  11. Kricheldorf HR, Weidner SM. High molar mass cyclic poly(L-lactide) via ring-expansion polymerization with cyclic dibutyltin bisphenoxides. Eur Polym J. 2018;105:158–66.

    Article  CAS  Google Scholar 

  12. Kricheldorf HR, Weidner SM. SnOct2-catalyzed syntheses of cyclic poly(l-lactide)s with catechol as low-toxic co-catalyst. J Polym Environ. 2019;27:2697–706.

    Article  CAS  Google Scholar 

  13. Liang Y, Sui M, He M, Wei Z, Zhang W. A strategy of in situ catalysis and nucleation of biocompatible zinc salts of amino acids towards poly (l-lactide) with enhanced crystallization rate. Polymers. 2019;11:No.790.

    Article  Google Scholar 

  14. Zhou ZH, Hou SY, Wan HL. Peroxomolybdate (VI)-citrate and-malate complex interconversions by pH-dependence. synthetic, structural and spectroscopic studies. Dalton Trans. 2004;9:1393–9.

    Article  Google Scholar 

  15. Che P, Fang D, Zhang D, Feng J, Wang J, Hu N, et al. Hydrothermal synthesis and crystal structure of a new two-dimensional zinc citrate complex. J Coord Chem. 2005;58:1581–8.

    Article  CAS  Google Scholar 

  16. Song P, Chen G, Wei Z, Chang Y, Zhang W, Liang J. Rapid crystallization of poly (L-lactic acid) induced by a nanoscaled zinc citrate complex as nucleating agent. Polymer. 2012;53:4300–9.

    Article  CAS  Google Scholar 

  17. Wu Y, Chen W, Meng F, Wu Y, Chen W, Meng F, et al. Core-crosslinked pH-sensitive degradable micelles: a promising approach to resolve the extracellular stability versus intracellular drug release dilemma. J Controlled Release. 2012;164:338–45.

    Article  CAS  Google Scholar 

  18. Jaiswal AK, Kadam SS, Soni VP, Bellare JR. Improved functionalization of electrospun PLLA/gelatin scaffold by alternate soaking method for bone tissue engineering. Appl Surf Sci. 2013;268:477–88.

    Article  CAS  Google Scholar 

  19. Sheng SJ, Hu X, Wang F, Ma Y, Gu M. Mechanical and thermal property characterization of poly-L-lactide (PLLA) scaffold developed using pressure-controllable green foaming technology. Mater Sci Eng C. 2015;49:612–22.

    Article  CAS  Google Scholar 

  20. Liu C, Liu C, Gao Y, Cheng F, Xiao G, Wang J, et al. Apatite formation on poly(aryl ether sulfone ketone) Surfaces by means of polydopamine layers functionalized with phosphonate groups. Adv Mater Interfaces. 2018;5:1800003.

    Article  Google Scholar 

  21. Tang J, Kong B, Wu H, Xu M, Wang Y, Wang Y, et al. Carbon nanodots featuring efficient FRET for real-time monitoring of drug delivery and two-photon imaging. Adv Mater. 2013;25:6569–74.

    Article  CAS  Google Scholar 

  22. Pascual A, Sardon H, Veloso A, Ruiperez F, Mecerreyes D. Organocatalyzed synthesis of aliphatic polyesters from ethylene brassylate: a cheap and renewable macrolactone. ACS Macro Lett. 2014;3:849–53.

    Article  CAS  Google Scholar 

  23. Kremer AB, Mehrkhodavandi P. Dinuclear catalysts for the ring opening polymerization of lactide. Coord Chem Rev. 2019;380:35–57.

    Article  CAS  Google Scholar 

  24. Saito T, Aizawa Y, Yamamoto T, Tajima K, Isono T, Satoh T. Alkali metal carboxylate as an efficient and simple catalyst for ring-opening polymerization of cyclic esters. Macromolecules. 2018;51:689–96.

    Article  CAS  Google Scholar 

  25. Chisholm MH, Patmore NJ, Zhou Z. Concerning the relative importance of enantiomorphic site vs. chain end control in the stereoselective polymerization of lactides: reactions of (R, R-salen)-and (S, S-salen)-aluminium alkoxides LAlOCH2 R complexes (R=CH3 and S-CHMeCl). Chem Commun. 2005;127–9.

  26. Xu FJ, Wang ZH, Yang WT. Surface functionalization of polycaprolactone films via surface-initiated atom transfer radical polymerization for covalently coupling cell-adhesive biomolecules. Biomaterials. 2010;31:3139–47.

    Article  CAS  Google Scholar 

  27. Li J, Zhang X, Zhao M, Wu L, Luo K, Pu Y, et al. Tumor-pH-sensitive PLLA-based microsphere with acid cleavable acetal bonds on the backbone for efficient localized chemotherapy. Biomacromolecules. 2018;19:3140–8.

    Article  CAS  Google Scholar 

  28. Bian Y, Wei Z, Wang Z, Tu Z, Zheng L, Wang W, et al. Development of biodegradable polyesters based on a hydroxylated coumarin initiator towards fluorescent visible paclitaxel-loaded microspheres. J Mater Chem B. 2019;7:2261–76.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the Fundamental Research Funds for the Central Universities (No. DUT19LAB27).

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Authors and Affiliations

  1. State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory of Polymer Science and Engineering, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, China

    Maomao He, Yi Cheng, Mingze Xia, Xuefei Leng, Yanshai Wang, Zhiyong Wei & Yang Li

  2. School of Materials Science and Engineering, Jilin University, Changchun, 110022, China

    Yuan Liang & Wanxi Zhang

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  1. Maomao He
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Correspondence to Zhiyong Wei or Yang Li.

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He, M., Cheng, Y., Liang, Y. et al. Amino acid complexes with tin as a new class of catalysts with high reactivity and low toxicity towards biocompatible aliphatic polyesters. Polym J 52, 567–574 (2020). https://doi.org/10.1038/s41428-020-0314-0

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