PERIODATE OXIDATION OF PEG–600, AN ESSENTIAL PHARMACEUTICAL POLYMER
Keywords:PEG-600, Alkaline medium, Periodate, Oxidation, Kinetics
Objective: To study the kinetics of periodate oxidation of polyethylene glycol-600 (PEG-600), a familiar non-toxic polymer used in pharmaceutical and other fields of industry.
Methods: Reactions were carried out in alkaline medium and measured the kinetics by iodometry. One oxygen atom loss or two electrons transfer was observed per each molecule of periodate i.e., the rate of reaction was measured periodate converts to iodate because the formed iodate species is unable to oxidize the substrate molecules.
Results: Based on log (a-x) versus t plots, order w. r. t. oxidant (periodate) is unity. Reactions were found to be independent of substrate (PEG-600) concentration. A decrease in rate with an increase in alkali concentration [OH–] was found and order was inverse fractional. Temperature dependence of reaction rate was studied and then calculated the corresponding Arrhenius parameters.
Conclusion: An appropriate rate law was proposed by considering the above experimental results.
D’souza AA, Shegokar R. Polyethylene glycol (PEG): a versatile polymer for pharmaceutical applications. Expert Opin Drug Delivery 2016;13:1257-75.
Kolate A, Baradia D, Patil S, Vhora I, Kore G, Misra A. PEG-a versatile conjugating ligand for drugs and drug delivery systems. J Controlled Release 2014;192:67-81.
Thomas A, Müller SS, Frey H. Beyond poly (ethylene glycol): Linear polyglycerol as a multifunctional polyether for biomedical and pharmaceutical applications. Biomacromolecules 2014;15:1935-54.
Cartotto RC, Peters WJ, Neligan PC, Douglas LG, Beeston J. Chemical burns. Can J Surg 1996;39:205.
Chen J, Spear SK, Huddleston JG, Rogers RD. Polyethylene glycol and solutions of polyethylene glycol as green reaction media. Green Chem 2005;7:64-82.
Venkateswarlu M, Balaji V, Susmitha M, Suresh D. Study on durability characteristics of conventional concrete with PEG-600 as self curing compound. Eur J Adv Eng Technol 2015;2:47-52.
Lidiya, Preethi M. Mechanical properties of self curing concrete incorporating polyethylene glycol-600. Int Res J Eng Technol 2018;5:584-9.
Kinahan IM, Smyth MR. High-performance liquid chromatographic determination of PEG 600 in human urine. J Chromatogr B: Biomed Sci Appl 1991;565:297-307.
Cerqueira DA, Rodrigues Filho G, de Assuncao RM, da Silva Meireles C, Toledo LC, Zeni M, Mello K, et al. Characterization of cellulose triacetate membranes, produced from sugarcane bagasse, using PEG 600 as additive. Polym Bull 2008;60:397-404.
Liang M, Zhou H, Huang Q, Hu S, Li W. Synergistic effect of polyethylene glycol 600 and polysorbate 20 on corrosion inhibition of zinc anode in alkaline batteries. J Appl Electrochem 2011;41:991-7.
Chattopadhyay DP, Sharma JK, Patra AK. Effect of crosslinking in presence of PEG 600 on dyeability of cotton. Indian J Fibre Text Res 1997;22:124-9.
Laidler KJ. Text book of chemical kinetics. 3rd Ed. Pearson Education Company, Singapore; 2004.
Venkata Nadh R, Syama Sundar B, Radhakrishnamurti PS. Kinetics of ruthenium (III) catalyzed and uncatalyzed oxidation of monoethanolamine by N-bromosuccinimide. Russ J Phys Chem A 2016;90:1760-5.
Nadh RV, Sundar BS, Radhakrishnamurti PS. Kinetics and mechanism of ruthenium (III) catalysed and uncatalysed oxidation of ethylamine and benzylamine by N-bromosuccinimide. Oxid Commun 2005;28:81-9.
Kumar YL, Nadh RV, Radhakrishnamurti PS. Shift of reaction pathway by added chloride ions in the oxidation of aromatic ketones by dichloroisocyanuric acid-a kinetic study. Russ J Phys Chem A 2016;90:552-9.
Kumar YL, Nadh RV, Radhakrishnamurti PS. Ruthenium (III) catalyzed oxidation of sugar alcohols by dichloroisocyanuric acid-a kinetic study. Russ J Phys Chem A 2016;90:300-7.
Kumar YL, Nadh RV, Radhakrishnamurti PS. Role of added chloride ions in alteration of reaction pathway in the oxidation of cyclic ketones by dichloroisocyanuric acid-a kinetic study. Russ J Phys Chem A 2015;89:376-83.
Kumar YL, Nadh RV, Radhakrishnamurti PS. Reactions of enolisable ketones with dichloroisocyanuric acid in absence and presence of added chloride ions–a kinetic study. Bull Chem Soc Ethiop 2015;29:129-36.
Venkata Nadh R, Syama Sundar B, Radhakrishnamurti PS. Kinetics of oxidation of aniline, p-aminobenzoic acid, and p-nitroaniline by 2, 6-dichloroquinone-4-chloro-imide. Russ J Phys Chem A 2001;75:174-8.
Neeraja V, Venakata Nadh R, Syama Sundar B, Radhakrishnamurti PS. Kinetic studies of thiocyanate and iodide oxidation with 2, 6-dichloroquinone-4-chloro-imide: A novel and a new oxidizing agent. Oxid Commun 1998;21:369-75.
Nadh RV, Sundar BS, Radhakrishnamurti PS. Kinetics of oxidation of ethylamine, monoethanolamine and benzylamine by chloramine-T. Oxid Commun 2000;23:102-11.
Nadh RV, Sundar BS, Radhakrishnamurti PS. Kinetics of oxidation of iodide Ion by Ce (IV). Asian J Chem 1997;9:515-21.
Venkata Nadh R, Syama Sundar B, Radhakrishnamurti PS. Kinetics of oxidation of iodide by vanadium (V). J Indian Chem Soc 1999;76:75-8.
Szymanski JK, Temprano Coleto F, Perez Mercader J. Unusual kinetics of poly (ethylene glycol) oxidation with cerium (IV) ions in sulfuric acid medium and implications for copolymer synthesis. Phys Chem Chem Phys 2015;17:6713-7.
Nagarajan S, Srinivasan KS, Rao KV. Kinetic and mechanistic studies on the oxidation of poly (ethylene glycol) by ceric sulphate in sulphuric acid medium. Polym J 1994;26:851-7.
Chen X, Gao LJ, Gu F. Fenton oxidation of different molecular weights polyethylene glycols in wastewater. Adv Mater Res 2014;1033:382-6.
Prousek J, Duriskova I. Oxidative degradation of poly (ethylene glycol) s (PEG) by the fenton and photo-fenton reactions. Chemickelisty 1998;92:218-20.
Luo W, Zhu L, Wang N, Tang H, Cao M, She Y. Efficient removal of organic pollutants with magnetic nanoscaled BiFeO3 as a reusable heterogeneous fenton-like catalyst. Environ Sci Technol 2010;44:1786-91.
Imamura S, Nakamura M, Kawabata N, Yoshida J, Ishida S. Wet oxidation of poly (ethylene glycol) catalyzed by manganese-cerium composite oxide. Ind Eng Chem Prod Res Dev 1986;25:34-7.
Lele BS, Kulkarni MG. Single step room temperature oxidation of poly (ethylene glycol) to poly (oxyethylene)‐dicarboxylic acid. J Appl Polym Sci 1998;170:883-90.
Hassan R, Ibrahim S, Sayed S. Kinetics and mechanistic aspects on electron‐transfer process for permanganate oxidation of poly (ethylene glycol) in aqueous acidic solutions in the presence and absence of Ru (III) catalyst. Int J Chem Kinet 2018;50:775-83.
Kumar YL, Nadh RV, Radhakrishnamurti PS. Kinetics of oxidation of myo-inositol by potassium periodate in alkaline medium. Asian J Chem 2012;24:5869-72.
Kumar YL, Nadh RV, Radhakrishnamurti PS. Substrate inhibition: oxidation of d-sorbitol and d-mannitol by potassium periodate in alkaline medium. Russ J Phys Chem A 2014;88:774-8.
Aveston J. Hydrolysis of potassium periodate: ultracentrifugation, potentiometric titration, and Raman spectra. J Chem Soc A 1969:273-5. Doi: 10.1039/j19690000273
Crouthamel CE, Hayes AM, Martin DS. Ionization and hydration equilibria of periodic acid. J Am Chem Soc 1951;173:82-7.
Tuwar SM, Nandibewoor ST, Raju JR. Oxidation of allyl alcohol by diperiodatonickelate (IV) in aqueous alkaline medium. J Indian Chem Soc 1992;69:651-3.
Shan JH, Li SM, Huo SY, Shen SG, Sun HW. Kinetics and mechanism of the oxidation of β-alanine by dihydroxydiperiodatoargentate (III) in an alkaline medium. J Iran Chem Soc 2005;2:226-31.
Kulkarni SD, Nandibewoor ST. A kinetic and 1 study on oxidation of Isoniazid drug by alkaline diperiodatocuprate (III)–A free radical intervention. Transition Met Chem 2006;31:1034-9.
Shan H, Wang HY, Song CY, Wang F. Kinetics and mechanism of oxidation of 2-Aminoethanol and 3-Amino-1-propanol by diperiodatoargentate (III) in alkaline medium. J Iran Chem Soc 2009;6:393-8.
Wynne Jones WF, Eyring H. The absolute rate of reactions in condensed phases. J Chem Phys 1935;5:492-502.
http://msdssearch.dow.com/PublishedLiteratureDOWCOM/dh_0887/0901b80380887904.pdf [Last accessed on 10 May 2019]
Feigl F. Spot tests in organic analysis, elsevier publishing co., New York; 1956. p. 208.
Henning T. Polyethylene glycols (PEGs), the pharmaceutical industry. SOFW-J 2001;127:28-32.
Shanmugam AN, Subhapradha NA, Suman S, Ramasamy P, Saravanan R, Shanmugam V, et al. Characterization of biopolymer “chitosan” from the shell of donacid clam donax scortum (linnaeus, 1758) and its antioxidant activity. Int J Pharm Pharm Sci 2012;4:460-5.
Sailaja AK, Amareshwar P, Chakravarty P. Different techniques used for the preparation of nanoparticles using natural polymers and their application. Int J Pharm Pharm Sci 2011;3:45-50.
Mishra RK, Banthia AK, Majeed AB. Pectin based formulations for biomedical applications: a review. Asian J Pharm Clin Res 2012;5:1-7.