Autoxidation of Polysorbates

Donbrow, M.; Azaz, E.; Pillersdorf, A.

doi:10.1002/jps.2600671211

Cited by 157 publications

(169 citation statements)

References 13 publications

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“…Aqueous solutions of polysorbates undergo autoxidation, which occurs along the polyoxyethylene moieties and in unsaturated fatty acids (CIR, 1984;Donbrow et al, 1978;Kerwin, 2008;Yao et al, 2009). In an initiation step, an alkyl radical is formed, followed by reaction with oxygen to peroxyl radicals, which propagate the radical-chain reaction.…”

Section: Reaction and Fate In Foodmentioning

confidence: 99%

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Scientific Opinion on the re‐evaluation of polyoxyethylene sorbitan monolaurate (E 432), polyoxyethylene sorbitan monooleate (E 433), polyoxyethylene sorbitan monopalmitate (E 434), polyoxyethylene sorbitan monostearate (E 435) and polyoxyethylene sorbitan tristearate (E 436) as food additives

Panel¹

2015

EFS2

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The Panel on Food Additives and Nutrient Sources added to Food (ANS) re-evaluated the safety of polysorbate 20 (E 432), polysorbate 80 (E 433), polysorbate 40 (E 434), polysorbate 60 (E 435) and polysorbate 65 (E 436) as food additives. The Joint Food and Agriculture Organization of the United Nations (FAO)/World Health Organization (WHO) Expert Committee on Food Additives (JECFA) derived an Acceptable Daily Intake (ADI) of 25 mg/kg body weight (bw)/day (group ADI for polysorbates 20, 40, 60, 65 and 80) and the Scientific Committee on Food (SCF) derived a group ADI of 10 mg/kg bw/day. Small amounts of polyoxyethylene sorbitans are absorbed. Similar toxicokinetics would be expected for all polysorbates based on their similarities in structure and metabolic fate. The acute toxicity is very low. There is no concern regarding genotoxicity, carcinogenicity or developmental toxicity. From a limited number of studies, there is no indication of reproductive toxicity. The Panel considered the long-term carcinogenicity study in rats with a No Observed Adverse Effect Level (NOAEL) equivalent to 2 500 mg/kg bw/day -consistent with the NOAEL defined in subchronic studies -as the key study and allocated a group ADI of 25 mg/kg bw/day using an uncertainty factor of 100. The estimated exposure of toddlers at the highest level in non-brand loyal scenario remains very close to the ADI (24.5 mg/kg bw/day). The Panel is aware that for three food categories no reported uses have been obtained and that other dietary sources of exposure to polysorbates could not been considered in this opinion and therefore more data (usage and analytical data) are needed to decrease uncertainties in the refined exposure assessment scenario used. 20, 40, 60, 65 and 80 (SCF, 1985). The basis was a No Observed Effect Level (NOEL) equivalent to 1 460 mg/kg bw/day in the diet in the 90-day study in rats with polyoxyethylene sorbitan monostearate (polysorbate 60) (BIBRA, 1981; cited in SCF, 1985). A higher group ADI value of 0-25 mg/kg bw/day was allocated by the Joint Food and Agriculture Organization of the United Nations (FAO)/World Health Organization (WHO) Expert Committee on Food Additives (JECFA, 1974a, b).The Panel was not provided with a newly submitted dossier and based its evaluation on previous evaluations and reviews, additional literature that has become available since then and data available following a public call for data. The Panel noted that not all original studies on which previous evaluations were based were available for re-evaluation by the Panel. Specifications for the polysorbates have been defined in Commission Regulation (EU) No 231/2012 and by JECFA (JECFA, 2006a).The Panel considered the evaluation of polysorbates (E 432-E 436) as a group in one opinion because of their similarities in structure and metabolic fate. These additives are hydrolysed to oxyethylene sorbitans and the relevant fatty acids, the latter being normal constituents of the diet. From the toxicological data as described in this opinion, there is ...

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Section: Reaction and Fate In Foodmentioning

confidence: 99%

“…Storing the polysorbate solutions away from light, in the presence of nitrogen and at lower temperatures helps prevent degradation. Degradation can also be prevented by the addition of low concentrations of the antioxidant butylated hydroxytoluene (Donbrow et al, 1978;Kerwin, 2008). …”

Section: Reaction and Fate In Foodmentioning

confidence: 99%

Scientific Opinion on the re‐evaluation of polyoxyethylene sorbitan monolaurate (E 432), polyoxyethylene sorbitan monooleate (E 433), polyoxyethylene sorbitan monopalmitate (E 434), polyoxyethylene sorbitan monostearate (E 435) and polyoxyethylene sorbitan tristearate (E 436) as food additives

Panel¹

2015

EFS2

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“…The rate of hydrolysis can be mitigated by storage under cold conditions and protection from light and oxygen (Gilardi-Lorenz, 2006). Degradation should be expected to reduce the ability of polysorbate solutions to act as surfactants (e.g., Donbrow et al, 1978) while also contaminating them with products of the breakdown reactions that may produce a false-positive organic detection. This may be a particular problem for surfactants that closely resemble organic and biological species, such as the polysorbates.…”

Section: Surfactants For Extraterrestrial Organic Extractionmentioning

confidence: 99%

Searching for Life on Mars: Degradation of Surfactant Solutions Used in Organic Extraction Experiments

et al. 2014

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Life-detection instruments on future Mars missions may use surfactant solutions to extract organic matter from samples of martian rocks. The thermal and radiation environments of space and Mars are capable of degrading these solutions, thereby reducing their ability to dissolve organic species. Successful extraction and detection of biosignatures on Mars requires an understanding of how degradation in extraterrestrial environments can affect surfactant performance. We exposed solutions of the surfactants polysorbate 80 (PS80), Zonyl FS-300, and poly[dimethylsiloxane-co-[3-(2-(2-hydroxyethoxy)ethoxy)propyl]methylsiloxane] (PDMSHEPMS) to elevated radiation and heat levels, combined with prolonged storage. Degradation was investigated by measuring changes in pH and electrical conductivity and by using the degraded solutions to extract a suite of organic compounds spiked onto grains of the martian soil simulant JSC Mars-1. Results indicate that the proton fluences expected during a mission to Mars do not cause significant degradation of surfactant compounds. Solutions of PS80 or PDMSHEPMS stored at -20°C are able to extract the spiked standards with acceptable recovery efficiencies. Extraction efficiencies for spiked standards decrease progressively with increasing temperature, and prolonged storage at 60°C renders the surfactant solutions ineffective. Neither the presence of ascorbic acid nor the choice of solvent unequivocally alters the efficiency of extraction of the spiked standards. Since degradation of polysorbates has the potential to produce organic compounds that could be mistaken for indigenous martian organic matter, the polysiloxane PDMSHEPMS may be a superior choice of surfactant for the exploration of Mars.

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“…21 These peroxide species can catalyze oxidation of protein formulations. 22 A process of removing peroxides from polyethylene glycol solutions was discussed recently.…”

Section: Introductionmentioning

confidence: 99%

The effect of neighboring amino acid residues and solution environment on the oxidative stability of tyrosine in small peptides

Zhang

Kalonia

2007

AAPS PharmSciTech

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The effects of neighboring residues and formulation variables on tyrosine oxidation were investigated in model dipeptides (glysyl tyrosine, N-acetyl tyrosine, glutamyl tyrosine, and tyrosyl arginine) and tripeptide (lysyl tyrosyl lysine). The tyrosyl peptides were oxidized by light under alkaline conditions by a zero-order reaction. The rate of the photoreaction was dependent on tyrosyl pK a , which was perturbed by the presence of neighboring charged amino acid residues. The strength of light exposure, oxygen headspace, and the presence of cationic surfactant, cetyltrimethylammonia chloride had a significant effect on the kinetics of tyrosyl photooxidation. Tyrosine and model tyrosyl peptides were also oxidized by hydrogen peroxide/metal ions at neutral pH. Metal-catalyzed oxidation followed first-order kinetics. Adjacent negatively charged amino acids accelerated tyrosine oxidation owing to affinity of the negative charges to metalions, whereas positively charged amino acid residues disfavored the reaction. The oxidation of tyrosine in peptides was greatly affected by the presence of adjacent charged residues, and the extent of the effect depended on the solution environment.

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Autoxidation of Polysorbates

Cited by 157 publications

References 13 publications

Scientific Opinion on the re‐evaluation of polyoxyethylene sorbitan monolaurate (E 432), polyoxyethylene sorbitan monooleate (E 433), polyoxyethylene sorbitan monopalmitate (E 434), polyoxyethylene sorbitan monostearate (E 435) and polyoxyethylene sorbitan tristearate (E 436) as food additives

Scientific Opinion on the re‐evaluation of polyoxyethylene sorbitan monolaurate (E 432), polyoxyethylene sorbitan monooleate (E 433), polyoxyethylene sorbitan monopalmitate (E 434), polyoxyethylene sorbitan monostearate (E 435) and polyoxyethylene sorbitan tristearate (E 436) as food additives

Searching for Life on Mars: Degradation of Surfactant Solutions Used in Organic Extraction Experiments

The effect of neighboring amino acid residues and solution environment on the oxidative stability of tyrosine in small peptides

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