Effect of molecular exchange on water droplet size analysis as determined by diffusion NMR: The W/O/W double emulsion case

Lien Vermeir; Paolo Sabatino; Mathieu Balcaen; Arnout Declerck; Koen Dewettinck; José C Martins; Gisela Guthausen; Paul Van der Meeren

doi:10.1016/j.jcis.2016.04.029

Effect of molecular exchange on water droplet size analysis as determined by diffusion NMR: The W/O/W double emulsion case

J Colloid Interface Sci. 2016 Aug 1:475:57-65. doi: 10.1016/j.jcis.2016.04.029. Epub 2016 Apr 20.

Authors

Lien Vermeir¹, Paolo Sabatino², Mathieu Balcaen³, Arnout Declerck⁴, Koen Dewettinck⁵, José C Martins⁶, Gisela Guthausen⁷, Paul Van der Meeren⁸

Affiliations

¹ Particle and Interfacial Technology Group, Department of Applied Analytical and Physical Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium. Electronic address: Lien.Vermeir@UGent.be.
² Particle and Interfacial Technology Group, Department of Applied Analytical and Physical Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium; NMR and Structure Analysis Unit, Department of Organic Chemistry, Faculty of Sciences, Ghent University, Krijgslaan 281 S4, B-9000 Ghent, Belgium. Electronic address: P.Sabatino@yahoo.it.
³ Particle and Interfacial Technology Group, Department of Applied Analytical and Physical Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium. Electronic address: Mathieu.Balcaen@UGent.be.
⁴ Particle and Interfacial Technology Group, Department of Applied Analytical and Physical Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium. Electronic address: Arnout.Declerck@UGent.be.
⁵ Laboratory of Food Technology and Engineering, Department of Food Safety and Food Quality, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium. Electronic address: Koen.Dewettinck@UGent.be.
⁶ NMR and Structure Analysis Unit, Department of Organic Chemistry, Faculty of Sciences, Ghent University, Krijgslaan 281 S4, B-9000 Ghent, Belgium. Electronic address: Jose.Martins@UGent.be.
⁷ Pro(2)NMR, MVM and IBG-4, Karlsruher Institut für Technologie, Adenauerring 20b, DE-76131 Karlsruhe, Germany. Electronic address: Gisela.Guthausen@kit.edu.
⁸ Particle and Interfacial Technology Group, Department of Applied Analytical and Physical Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium. Electronic address: Paul.VanderMeeren@UGent.be.

PMID: 27153218
DOI: 10.1016/j.jcis.2016.04.029

Abstract

Hypothesis: The accuracy of the inner water droplet size determination of W/O/W emulsions upon water diffusion measurement by diffusion NMR was evaluated. The resulting droplet size data were compared to the results acquired from the diffusion measurement of a highly water soluble marker compound with low permeability in the oil layer of a W/O/W emulsion, which provide a closer representation of the actual droplet size. Differences in droplet size data obtained from water and the marker were ascribed to extra-droplet water diffusion.

Experiments: The diffusion data of the tetramethylammonium cation marker were measured using high-resolution pulsed field gradient NMR, whereas the water diffusion was measured using both low-resolution and high-resolution NMR. Different data analysis procedures were evaluated to correct for the effect of extra-droplet water diffusion on the accuracy of water droplet size analysis.

Findings: Using the water diffusion data, the use of a low measurement temperature and diffusion delay Δ could reduce the droplet size overestimation resulting from extra-droplet water diffusion, but this undesirable effect was inevitable. Detailed analysis of the diffusion data revealed that the extra-droplet diffusion effect was due to an exchange between the inner water phase and the oil phase, rather than by exchange between the internal and external aqueous phase. A promising data analysis procedure for retrieving reliable size data consisted of the application of Einstein's diffusion law to the experimentally determined diffusion distances. This simple procedure allowed determining the inner water droplet size of W/O/W emulsions upon measurement of water diffusion by low-resolution NMR at or even above room temperature.

Keywords: Diffusion NMR (Nuclear Magnetic Resonance); High-resolution NMR; Low-resolution NMR; Molecular exchange; Tetramethylammonium chloride; W/O/W emulsion (water-in-oil-in-water); Water droplet size analysis; Water exchange; pfg-NMR diffusometry (pulsed field gradient).

MeSH terms

Diffusion
Emulsions / chemistry
Magnetic Resonance Spectroscopy
Particle Size
Quaternary Ammonium Compounds / chemistry*
Surface Properties
Water / analysis*

Substances

Emulsions
Quaternary Ammonium Compounds
Water
tetramethylammonium