Publication: Effect of pH and temperature on the aggregation behaviour of dirhamnolipid biosurfactant. An experimental and molecular dynamics study
Authors
Ortiz, Julia ; Oliva, Alfonso ; Teruel Puche, José Antonio ; Aranda Martínez, Francisco José ; Ortiz López, Antonio
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Publisher
Elsevier
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DOI
https://doi.org/10.1016/j.jcis.2021.03.177
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info:eu-repo/semantics/article
Description
Abstract
Hypothesis: Pseudomonas aeruginosa dirhamnolipid (diRL) has been shown to form aggregates of different size and structure, under various conditions. Due to the presence of a carboxyl group in the molecule, it is expected that pH would strongly affect this aggregation behaviour. In addition, preliminary observations of temperature-induced changes in the states of aggregation of diRL supported the need of further investigation.
Experiments: A systematic experimental study, using differential scanning calorimetry (DSC), small-angle Xray diffraction (SAXD), and Fourier-transform infrared pectroscopy (FTIR), has been carried out to charac terize pH and temperature driven changes in the aggregation behavior of diRL biosurfactant. Molecular dynamics (MD) simulations, supported by the experimental results, allowed depicting molecular details on formation of diRL membranes and other aggregated structures under various physicochemical conditions.
Findings: DiRL could adopt fairly organizedmultilayered structures (membranes) at low pH and temperature, which became highly disordered upon increasing either of these parameters. The effect of pH on the gauche/ all-trans conformer ratio of the diRL acyl chains was not of significance, whereas temperature-induced effects were observed. For the first time it is described that diRL underwent an endothermic thermotropic transition with Tc = 34 C as observed by DSC, at pH 4.5 (protonated diRL), but not at pH 7.4 (unprotonated diRL). FTIR confirmed these findings, showing a significant additional disordering of the all-trans acyl chains upon increasing temperature around that same value in the protonated form, an effect not observed for the disso ciated form of the biosurfactant. In addition, at pH 7.4, changing temperature did not modify the hydration state of the polar moiety of diRL, whereas at pH 4.5 a significant decrease in the hydration state around 34 C took place. SAXD data showed that protonated diRL formed multilayered structures at 20 C, which con verted into poorly correlated layers at 50 C. MD simulations supported these findings, showing that the membrane-like structures formed by protonated diRL at 20 C became unstable at higher temperatures, tend ing to form other structures, which could be micelles or other type of layered structures, whereas the nega tively charged form of diRL organized in micelle-type aggregates in the whole range of temperature under study.
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Citation
Journal of Colloid and Interface Science, 597 (2021) 160-170
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