Effect of Hofmeister Ions on Transport Properties of Aqueous Solutions of Sodium Hyaluronate
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International Journal of Molecular Sciences Article Effect of Hofmeister Ions on Transport Properties of Aqueous Solutions of Sodium Hyaluronate Lenka Musilová 1,2, Aleš Mráˇcek 1,2,* , VˇeraKašpárková 2,3, Antonín Minaˇrík 1,2, Artur J. M. Valente 4,*, Eduarda F. G. Azevedo 4, Luis M. P. Veríssimo 4, M. Melia Rodrigo 4, Miguel A. Esteso 5,6 and Ana C. F. Ribeiro 4 1 Department of Physics and Materials Engineering, Faculty of Technology, Tomas Bata University in Zlín, Vavreˇckova275, 760 01 Zlín, Czech Republic; [email protected] (L.M.); [email protected] (A.M.) 2 Centre of Polymer Systems, Tomas Bata University in Zlín, tˇr.Tomáše Bati 5678, 760 01 Zlín, Czech Republic; [email protected] 3 Department of Fat, Surfactant and Cosmetics Technology, Faculty of Technology, Tomas Bata University in Zlín, Vavreˇckova275, 762 72 Zlín, Czech Republic 4 Department of Chemistry, University of Coimbra, CQC, 3004-535 Coimbra, Portugal; [email protected] (E.F.G.A.); [email protected] (L.M.P.V.); [email protected] (M.M.R.); [email protected] (A.C.F.R.) 5 U.D. Química Física, Universidad de Alcalá, 28871 Alcalá de Henares, Spain; [email protected] 6 Universidad Católica Santa Teresa de Jesús de Ávila, Calle los Canteros s/n, 05005 Ávila, Spain * Correspondence: [email protected] (A.M.); [email protected] (A.J.M.V.); Tel.: +420-608-707-577 (A.M.); +351-239-854-459 (A.J.M.V.) ◦ Abstract: Tracer diffusion coefficients obtained from the Taylor dispersion technique at 25.0 C were measured to study the influence of sodium, ammonium and magnesium salts at 0.01 and 0.1 mol Citation: Musilová, L.; Mráˇcek,A.; dm−3 on the transport behavior of sodium hyaluronate (NaHy, 0.1%). The selection of these salts Kašpárková, V.; Minaˇrík,A.; Valente, was based on their position in Hofmeister series, which describe the specific influence of different A.J.M.; Azevedo, E.F.G.; Veríssimo, ions (cations and anions) on some physicochemical properties of a system that can be interpreted L.M.P.; Rodrigo, M.M.; Esteso, M.A.; as a salting-in or salting-out effect. In our case, in general, an increase in the ionic strength (i.e., Ribeiro, A.C.F. Effect of Hofmeister −3 Ions on Transport Properties of concentrations at 0.01 mol dm ) led to a significant decrease in the limiting diffusion coefficient of Aqueous Solutions of Sodium the NaHy 0.1%, indicating, in those circumstances, the presence of salting-in effects. However, the Hyaluronate. Int. J. Mol. Sci. 2021, 22, opposite effect (salting-out) was verified with the increase in concentration of some salts, mainly for −3 1932. https://doi.org/10.3390/ NH4SCN at 0.1 mol dm . In this particular salt, the cation is weakly hydrated and, consequently, ijms22041932 its presence does not favor interactions between NaHy and water molecules, promoting, in those circumstances, less resistance to the movement of NaHy and thus to the increase of its diffusion (19%). Academic Editor: These data, complemented by viscosity measurements, permit us to have a better understanding Alexander B. Doktorov about the effect of these salts on the transport behaviour of NaHy. Received: 24 January 2021 Accepted: 11 February 2021 Keywords: sodium hyaluronate; transport properties; viscosity; Hofmeister series Published: 16 February 2021 Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in 1. Introduction published maps and institutional affil- iations. Hyaluronan (sodium salt of hyaluronic acid, NaHy), was firstly obtained by Meyer et al. [1] from the vitreous humor of cattle eyes. It consists of a disaccharide repeating sequence of D-glucuronic acid and N-acetyl-D-glucosamine, linked via alternating β-(1!4) and β-(1!3) glycosidic bonds (Figure1)[ 2]. Hyaluronic acid (HyA) is a natural linear polysaccharide, being naturally present and abundant in all biologic fluids of some bacteria Copyright: © 2021 by the authors. and all vertebrates [2–4]. Due to its biocompatibility, biodegradability and presence in the Licensee MDPI, Basel, Switzerland. This article is an open access article native extracellular matrix of tissues [5], HyA has been extensively applied for medical [6,7] distributed under the terms and and biomedical applications [8,9], including drug delivery [10–12], bioprinting [13] and conditions of the Creative Commons tissue engineering [14], cosmetics [15] and wastewater treatment [16]. Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). Int. J. Mol. Sci. 2021, 22, 1932. https://doi.org/10.3390/ijms22041932 https://www.mdpi.com/journal/ijms Int.Int. J.J. Mol.Mol. Sci. 2021,, 22,, 1932x FOR PEER REVIEW 22 of of 1314 Figure 1. Molecular structure of the disaccharide repeating unitunit inin hyaluronichyaluronic acidacid salt.salt. For most of thesethese applications,applications, knowledge of the transporttransport properties of HyAHyA inin aqueous solutions plays a key role.role. ForFor example,example, whilstwhilst forfor electrospinningelectrospinning thethe solutionsolution viscosity is relevant, for drugdrug deliverydelivery thethe understandingunderstanding of massmass transporttransport byby diffusiondiffusion is essentialessential as aa limitinglimiting kinetickinetic constant.constant. DespiteDespite this,this, onlyonly fewfew articlesarticles describedescribe thethe behaviour ofof hyaluronichyaluronic acid acid solutions solutions in in terms terms of transportof transport properties. properties. Verissimo Verissimo et al. et [17 al.] reported[17] reported mutual mutual diffusion diffusion coefficients coefficients of sodium of sodium hyaluronate hyaluronate in the in concentration the concentration range −3 ◦ 0.50range to 0.50 50 gto dm 50 g ,dm at 25−3, atC, 25 allowing °C, allowing the estimation the estimation of different of different parameters parameters such such as the as diffusionthe diffusion coefficient coefficient at infinitesimal at infinitesimal concentration, concentration, the limitingthe limiting ionic ionic conductivity conductivity and and the tracerthe tracer diffusion diffusion coefficient coefficient of hyaluronate of hyaluronate ion. ion. Later, Later, these these studies studies were were complemented complemented by viscosityby viscosity data, data, and itsand influence its influence on the on diffusion the diffusion coefficients coefficients were discussed were discussed [18]. However, [18]. onlyHowever, few data only have few showndata have the shown effect of the the effect ionic of strength the ionic on strength the HyA on behavior the HyA in behavior aqueous solution.in aqueous By solution. using optical By using techniques, optical techniques, Wik and Comper Wik and studied Comper the studied effect the of the effect ionic of strengththe ionic on strength the mutual on diffusionthe mutual coefficient diffusion of hyaluronate.coefficient of However, hyaluronate. the obtained However, results the mustobtained be consideredresults must as be approximate considered accordingas approximate to the according authors [19 to]. the Some authors of us [19]. [20] Some have reportedof us [20] dynamic have reported light-scattering dynamic (DLS), light-sca viscosityttering and (DLS), surface viscosity tension (SFT)and surface measurements tension to characterize the influence of the following salts: Na2SO4, (NH4)2SO4, NaSCN, NH4SCN (SFT) measurements to characterize the influence of the following salts: Na2SO4, and NaCl, on the behavior of hyaluronan in diluted solutions at a temperature range (NH4)2SO4, NaSCN, NH4SCN and NaCl, on the behavior of hyaluronan in diluted of 15–45 ◦C. In the sequence of this work, we intend to extend these studies measuring solutions at a temperature range of 15–45 °C. In the sequence of this work, we intend to viscosities for the same aqueous systems but using other NaHy with lower molecular extend these studies measuring viscosities for the same aqueous systems but using other mass (Mw = 124 kDa), and also characterise the influence of these particular salts on the NaHy with lower molecular mass (Mw = 124 kDa), and also characterise the influence of diffusion of NaHy using the same samples of this compound (i.e., Mw = 1.8–2.1 MDa these particular salts on the diffusion of NaHy using the same samples of this compound and Mw = 124 kDa). The selection of these salts was based on the ordering of Hofmeister (i.e., Mw = 1.8–2.1 MDa and Mw = 124 kDa). The selection of these salts was based on the series [21] and its related properties (viscosity or surface energy and entropies of ion ordering of Hofmeister series [21] and its related properties (viscosity or surface energy solvation) [22], this classification being proposed in accordance with the abilities of these and entropies of ion solvation) [22], this classification being proposed in accordance with ions to induce the water structuring or breaking (Figure2). The ions on the left side are the abilities of these ions to induce the water structuring or breaking (Figure 2). The ions called kosmotropes (“water structure makers”), while on the right side are chaotropes on the left side are called kosmotropes (“water structure makers”), while on the right side (“water structure breakers”) [21]. It is known that Hofmeister or specific ion effects affect someare chaotropes physicochemical (“water propertiesstructure breakers”) of aqueous [21] [23,.24 It] is and known nonaqueous that Ho [fmeister25,26] systems. or specific As anion example, effects affect there some are studies physicochemical made by Mr ápropˇceketerties al. [27of] aqueous about the [23,24] influence and of nonaqueous Hofmeister series[25,26] ions systems. on HyA As behaviouran example, and there HyA are film-swelling. studies made Additionally by Mráček diffusion et al. [27] coefficients about the ofinfluence water on of the Hofmeister swelling process series of filmsions ofon sodium HyA hyaluronatebehaviour and theirHyA hydrophobically film-swelling. modifiedAdditionally derivatives diffusion have coefficients also been of studiedwater on [28 the,29 ].swelling Mráˇceket process al. [29 of] alsofilms showed, of sodium by usinghyaluronate viscosity and measurements, their hydrophobically that the presencemodified of derivatives specific ions have such also as sulphatebeen studied and thiocyanate[28,29]. Mráč anions,ek et al.