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Surfactant Behaviour of Sodium Dodecylsulfate In Subscriber access provided by CMU Libraries - http://library.cmich.edu Article Surfactant Behaviour of Sodium Dodecylsulfate in the Deep Eutectic Solvent Choline Chloride: Urea Thomas Arnold, Andrew J Jackson, Adrian Sanchez- Fernandez, Daniel Magnone, Ann E. Terry, and Karen J. Edler Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.5b02596 • Publication Date (Web): 05 Nov 2015 Downloaded from http://pubs.acs.org on November 7, 2015 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts. Langmuir is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties. Page 1 of 35 Langmuir 1 2 3 4 5 6 7 8 Surfactant Behaviour of Sodium Dodecylsulfate in 9 10 11 12 the Deep Eutectic Solvent Choline Chloride: Urea 13 14 15 16 1* 2,3 3,4 1† 5 17 T. Arnold , A.J. Jackson , A. Sanchez-Fernandez , D. Magnone , A.E. Terry and K.J. 18 19 Edler 4 20 21 22 1 Diamond Light Source, Harwell Campus, Didcot, OX11 ODE, UK 23 24 25 2 26 European Spallation Source, Lund, Sweden 27 28 29 3 Department of Physical Chemistry, Lund University, SE-221 00, Lund, Sweden 30 31 32 4 33 Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK 34 35 36 5 ISIS Spallation Neutron Source, Harwell Campus, Didcot, OX11 ODE, UK 37 38 39 KEYWORDS: Deep Eutectic Solvent, Sodium Dodecylsulfate (SDS), Choline Chloride, Urea, 40 41 42 Micelle, Surfactant, Self-assembly, Small angle scattering, X-ray reflectometry 43 44 45 46 Deep Eutectic Solvents (DES) resemble ionic liquids but are formed from an ionic mixture 47 48 instead of being a single ionic compound. Here we present some results that demonstrate that the 49 50 surfactant sodium dodecylsulfate (SDS) remains surface active and shows self-assembly 51 52 53 phenomena in the most commonly studied DES, choline chloride/Urea. X-ray reflectivity (XRR) 54 55 and Small Angle Neutron Scattering (SANS) suggests the behaviour is significantly different 56 57 58 from that in water. Our SANS data supports our determination of the critical micelle 59 60 ACS Paragon Plus Environment 1 Langmuir Page 2 of 35 1 2 3 concentration using surface-tension measurements and suggests that the micelles formed in DES 4 5 6 do not have the same shape and size as those seen in water. Reflectivity measurements have also 7 8 demonstrated that the surfactants remain surface active below this concentration. 9 10 11 12 13 14 Introduction 15 16 17 The discovery of new solvents for amphiphile self-assembly aids in understanding the 18 19 important solvent properties which enable this self-aggregation, allows the systems to be tuned 20 21 22 for particular applications (via control of polarity, surface tension, viscosity, conductivity, 23 24 refractive index and thermal properties) and improves our understanding of the ‘‘solvophobic 25 26 effect’’ to allow further development of useful self-organised materials. Micellization, 27 28 29 particularly of non-ionic surfactants in protic ionic liquids, has been the subject of several studies 30 31 beginning in the 1980s 1 but with a recent upsurge of interest 2-7. At least 37 protic ionic liquids 32 33 have been identified as solvents where micellization can occur 6. However the hygroscopic nature 34 35 36 of ionic liquids, and the frequent extremes of pH found in these solvents are not conducive to 37 38 long term stability of surfactants in these media and their expense and toxicity prevents their use 39 40 in many applications. 41 42 43 Deep Eutectic Solvents (DES) are an alternative to ionic liquids with several potential 44 45 advantages. In particular they are easily prepared from cheap, non-toxic molecules and can be 46 47 48 formed from biodegradable and biocompatible neutral species. DES resemble ionic liquids but 49 50 are formed from an ionic mixture instead of being a single ionic compound. In deep eutectic 51 52 solvents, formation of a liquid at ambient temperatures relies on a large depression in freezing 53 54 55 point coming from a favourable hydrogen bonding interaction between the constituents. The 56 57 freezing point depression is largest at the eutectic point and can be as much as 270 °C. 8 DES 58 59 60 ACS Paragon Plus Environment 2 Page 3 of 35 Langmuir 1 2 3 share with ionic liquids properties which make them highly desirable as “green solvents”; they 4 5 6 have very low volatility, are generally non-flammable and have a wider liquid temperature range 7 8 than molecular solvents. DES in general have been shown to be good solvents for a range of 9 10 9 10 11 11 inorganic salts and have been studied most in the electroplating of metals such as zinc, silver 12 12 13 13 and aluminium. DES can also be used to create alloys, and metal nanoparticles as well as in 14 15 the processing of metal oxides. 14 DES have also been investigated for use in pharmaceutical 16 17 15 18 applications and also for selective extractions of, for example, high value species from 19 20 biomass 16 and glycerol from biodiesel. 17 21 22 In general most DES are composed of a quaternary ammonium halide salt mixed with metal 23 24 25 salts or a “hydrogen-bond donor”. The strong interaction of this donor with the halide ions 26 27 stabilises the liquid and results in the large depression of freezing point at the eutectic 28 29 composition. The most studied series of DES are those prepared using choline chloride which is 30 31 32 a food additive (choline is an essential nutrient, usually grouped with the B vitamins) with one of 33 34 many other species, including urea 18 or M 2+ ions such as Zn 2+ .19 A wide range of other DES have 35 36 37 also been identified and their synthesis and properties have recently been reviewed by Zhang et 38 20 39 al. This review summarises what is known about the freezing points, density, viscosity, 40 41 polarity, acidity, ionic conductivity, and surface tension for a range of different DES. 42 43 44 Importantly one of the most noticeable properties of many DES is high viscosity. This may result 45 46 from many factors including the presence of an extensive hydrogen-bonding network, relatively 47 48 large ion sizes and electrostatic forces within the liquid. 49 50 51 Very recently it has been suggested that sodium dodecyl sulfate (SDS) shows some self- 52 53 assembly phenomena in choline chloride / urea DES containing either water or cyclohexane 21 . 54 55 These authors presented surface tension and dynamic light scattering (DLS) measurements for a 56 57 58 59 60 ACS Paragon Plus Environment 3 Langmuir Page 4 of 35 1 2 3 series of choline chloride / urea solutions containing both SDS and water. Crucially they did not 4 5 6 report any results for SDS in the pure DES, so we cannot be sure that the observed structures are 7 8 micelles nor that similar behavior would be observed in the absence of water. The DLS results 9 10 11 presented indicate that the self-assembled structures are substantially larger than those observed 12 13 in water, which is an interesting result. For most polar, but non-aqueous solvents, SDS is found 14 15 to form smaller micelles are found than for the same surfactant in water 22, 23 . This result, in itself 16 17 18 merits further investigation, but disappointingly these authors did not present any additional 19 20 experimental evidence to refine the details of the observed structures. Typically DLS does not 21 22 give information on particle shape, since the calculations based on diffusion rates assume 23 24 25 spherical objects. They did however present some data (surface tension, DLS, fluorescence 26 27 spectroscopy and small angle x-ray scattering (SAXS)) on micro-emulsions formed by 28 29 cyclohexane and the DES in the presence of SDS. They used this data to conclude that the 30 31 32 solubility of cyclohexane in this DES was improved by the presence of SDS. This was explained 33 34 by the formation of a micro-emulsion, a conclusion that is consistent with the data presented.
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