Polyaspartic acid

Polyaspartic acid
Names
Other names
PASP
Identifiers
25608-40-6 (poly-L-aspartic acid)
Properties
(C4H5NO3)n
Molar mass variable
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Polyaspartic acid (PASA) is a biodegradable, water-soluble polyaminoacid with potential to replace many non-biodegradable polymers. It is used as a pure homopolymer and in various copolymers.[1] In nature, PASA has been found in as fragments of larger proteins with length up to 50 amino acids,[2] but as of 2004 had not been isolated as a pure homo polymeric material from any natural source.[3] The first isolation of synthetic oligomeric sodium polyaspartate, obtained by thermal polycondensation of aspartic acid, was done by Hugo Schiff in late 19th century.[4] Later it was proposed that thermal polymerization process leads through polysuccinimide intermediate.[5][6] Polyaspartic acid is currently produced on the industrial scale and is available as commercial product in forms of acid and sodium polyaspartate.

Properties and structure

PASA is a yellow liquid miscible with water. Due to presence of carboxylic groups it is polyelectrolyte with anionic character. Naturally occurring PASA fragments consists of α,-linked L-aspartatic acid.[2] In contrast, the repeating unit of synthetic polyaspartic acid may exist in four different isomeric forms depending on the stereochemistry of starting material (D- and L-aspartic acid) and synthetic procedure leading to α and β links.

Synthesis

Isomers of PASA repeating unit

There are currently many different synthetic protocols available leading to PASA. In the simplest[7] and the oldest approach[3] aspartic acid is heated to high temperature resulting in water release and the formation of polysuccinimide. In the subsequent step this polymer is reacted with sodium hydroxide in water which yields partial cleavage of the succinimide ring. In this process sodium-DL-(α,β)-poly(aspartate) with 30% α-linkages and 70% β-linkages[8] randomly distributed along the polymer chain,[9] and racemized chiral center of aspartic acid is produced.[10] There were many catalysts reported for improving thermal polymerization method. Main benefits from their application is increasing of the conversion rate and higher molecular weight of the product.[11][12] Polyaspartic acid can also be synthesized by polymerization of maleic anhydride in presence of ammonium hydroxide.[1][13] High control over repeating unit isomers can be achieved by polymerization of N-carboxyanhydrides (NCA) derivatives,[14] by polymerization of aspartic acid esters[15] or by application of enzyme catalyzed reaction.[16] Pure homopolymers, D- or L- PASA with α- or β-links only, can be synthesized using those methods.

Applications

Polyaspartic acid and its derivatives are environmentally friendly, biodegradable alternative to traditional polyanionic materials, in particular as replacement for polyacrylic acid.[17] PASA has ability to inhibit deposition of calcium carbonate, calcium sulfate, barium sulfate and calcium phosphate salts and can be used as an antiscalining agent in cooling water systems, water desalination processes, and waste water treatment operations.[18] In addition and due to its ability to chelate metal ions it provides corrosion inhibition.[8] It can act as a super-swelling material in diaper/feminine-hygiene products and food packaging.[19] It can also be used as biodegradable detergent and dispersant for various applications.[20] There is a broad interest in this material from biomedical and material research community.

See also

Sodium polyaspartate

References

  1. 1 2 Roweton, S.; Huang, S. J.; Swift, G. (1997). "Poly(aspartic acid): Synthesis, biodegradation, and current applications". Journal of environmental polymer degradation 5 (3): 175–181. doi:10.1007/BF02763661.
  2. 1 2 Rusenko, Kirt W.; Donachy, Julie E.; Wheeler, A. P. (1991). "Purification And Characterization Of A Shell Matrix Phosphoprotein From The American Oyster". In Sikes, C. Steven; Wheeler, A. P. Surface Reactive Peptides and Polymers. ACS Symposium Series 444. ACS. pp. 107–124. doi:10.1021/bk-1991-0444.ch008. ISBN 9780841218864.
  3. 1 2 Joentgen, Winfried; Müller, Nikolaus; Mitschker, Alfred; Schmidt, Holger (2004). "Polyaspartic acids". In Fahnestock, Stephen; Steinbüchel, Alexander. Polyamides and Complex Proteinaceous Materials I. Biopolymers 7. Wiley-VCH. pp. 175–179. ISBN 9783527302222.
  4. ↑ Schiff, Hugo (1897). "Ueber Polyaspartsäuren". Ber. Dtsch. Chem. Ges. (in German) 30 (3): 2449–2459. doi:10.1002/cber.18970300316.
  5. ↑ Kovács, J.; Könyves, I.; Pusztai, Á. (1953). "Darstellung von Polyasparaginsäuren (Polyaspartsäuren) aus dem thermischen Autokondensationsprodukt der Asparaginsäure". Experientia (in German) 9 (12): 459–460. doi:10.1007/BF02165821.
  6. ↑ Kovács, J.; Könyves, I. (1954). "Uber DL-α,β-Polyasparaginsaure". Naturwissenschaften (in German) 41 (14): 333. Bibcode:1954NW.....41..333K. doi:10.1007/BF00644501.
  7. ↑ Bennett, G. D. (2005). "A Green Polymerization of Aspartic Acid for the Undergraduate Organic Laboratory". Journal of Chemical Education 82 (9): 1380–1381. Bibcode:2005JChEd..82.1380B. doi:10.1021/ed082p1380.
  8. 1 2 Low, Kim C.; Wheeler, A. P.; Koskan, Larry P. (1996). "6: Commercial Poly(aspartic acid) and Its Uses". In Glass, J. Edward. Hydrophilic Polymers. Advances in Chemistry 248. ACS. pp. 99 –111. doi:10.1021/ba-1996-0248.ch006. ISBN 9780841231337.
  9. ↑ Pivcova, H.; Saudek, V.; Drobnik, J.; Vlasak, J. (1981). "NMR Study of Poly(aspartic acid). I. α-and β -Peptide Bonds in Poly( aspartic acid) Prepared by Thermal Polycondensation". Biopolymers 20 (8): 1605–1614. doi:10.1002/bip.1981.360200804.
  10. ↑ Kokufuta, Etso; Suzuki, Shinnichiro; Harad, Kaoru (1978). "Temperature Effect on the Molecular Weight and the Optical Purity of Anhydropolyaspartic Acid Prepared by Thermal Polycondensation". Bulletin of the Chemical Society of Japan 51 (5): 1555–1556. doi:10.1246/bcsj.51.1555.
  11. ↑ Nakato, Takeshi; Kusuno, Atsushi; Kakuchi, Toyoji (2000). "Synthesis of poly(succinimide) by bulk polycondensation of L-aspartic acid with an acid catalyst". Journal of Polymer Science Part A: Polymer Chemistry 38 (1): 117–122. doi:10.1002/(SICI)1099-0518(20000101)38:1<117::AID-POLA15>3.0.CO;2-F.
  12. ↑ Wang, Yaquan; Hou, Yongjiang; Ruan, Gang; Pan, Ming; Liu, Tengfei (2003). "Study on the polymerization of aspartic acid catalyzed by phosphoric acid". Journal of Macromolecular Science-Pure and Applied Chemistry A40 (3): 293–307. doi:10.1081/MA-120018116.
  13. ↑ US patent 5468838, Boehmke, Gunter & Schmitz, Gerd, "Polysuccinimide, polyaspartic acid and their salts are prepared by reaction of maleic anhydride and ammonia, polycondensation of the resulting product in the presence of a solubilizing agent and, if appropriate, hydrolysis.", published 1995-11-21, assigned to Bayer AG
  14. ↑ Rao, Vanga S.; Lapointe, Philippe; McGregor, Donald N. (1993). "Temperature Effect on the Molecular Weight and the Optical Purity of Anhydropolyaspartic Acid Prepared by Thermal Polycondensation". Makromolekulare Chemie-Macromolecular Chemistry and Physics 194 (4): 1095–1104. doi:10.1002/macp.1993.021940405.
  15. ↑ Saudek,, V.; Pivcova, H.; Drobnik, J. (1981). "NMR Study of Poly(aspartic acid). II. a- and p-Peptide Bonds in Poly(aspartic acid) Prepared by Common Methods". Biopolymers 20 (8): 1615–1623. doi:10.1002/bip.1981.360200805.
  16. ↑ Soeda, Yasuyuki; Toshima, Kazunobu; Matsuma, Shuichi (2003). "Sustainable enzymatic preparation of polyaspartate using a bacterial protease". Biomacromolecules 4 (2): 193–203. doi:10.1021/bm0200534.
  17. ↑ Gross, Richard A.; Kalra, Bhanu (2002). "Biodegradable Polymers for the Environment". Science 297 (5582): 803–807. Bibcode:2002Sci...297..803G. doi:10.1126/science.297.5582.803. PMID 12161646.
  18. ↑ Hasson, David; Shemer, Hilla; Sher, Alexander (2011). "State of the Art of Friendly "Green" Scale Control Inhibitors: A Review Article". Industrial & Engineering Chemistry Research 50 (12): 7601–7607. doi:10.1021/ie200370v.
  19. ↑ Zahuriaan-Mehr, M. J.; Pourjavadi, A.; Salimi, H.; Kurdtabar, M. (2009). "Protein- and homo poly(amino acid)-based hydrogels with super-swelling properties". Polymers for Advanced Technologies 20 (8): 655–671. doi:10.1002/pat.1395.
  20. ↑ Thombre, Sunita M.; Sarwade, Bhimaro D. (2005). "Synthesis and Biodegradability of Polyaspartic Acid: A Critical Review" (PDF). Journal of Macromolecular Science, Part A 42 (9): 1299–1315. doi:10.1080/10601320500189604.
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