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Colloids and Surfaces A: Physicochem. Eng.

Aspects 296 (2007) 230237

Cation enhanced hydrophilic character of textured alginate gel beads


Philippe Trens , Romain Valentin, Franc oise Quignard
Laboratoire de Mat eriaux Catalytiques et Catalyse en Chimie Organique, UMR 5618, ENSCM-UM1-CNRS, FR 1878 F ed eration Gerhardt, 8, Rue de lEcole Normale, 34296 Montpellier Cedex 5, France Received 10 June 2006; received in revised form 31 August 2006; accepted 29 September 2006 Available online 5 October 2006

Abstract The hydrophilic character of modied polysaccharides has been studied by means of water adsorption at 303 and 323 K. Modication of the initial material results from either the introduction of cationic species in the organic framework of polysaccharides (Ca or Co, up to 15%, w/w) or the drying stage of the nal materials leading to aerogels or xerogels. The hydrophilic character of the nal materials has been discussed in terms of water adsorption or absorption capacities. A strong enhancement of this property is evidenced when using aerogel textured materials as compared to xerogels regardless of the nature of the cation introduced in the organic framework. Water absorption capacities are also further strongly enhanced when cobalt is used as complexing species. This difference between calcium and cobalt species towards adsorption has been discussed in terms of hydration spheres, whereas water absorption has been interpreted in terms of cationic-mediated organic framework expansion. 2006 Elsevier B.V. All rights reserved.
Keywords: Absorption; Adsorption; Polysaccharides; Transition metal; Water

1. Introduction Alginates are abundant polysaccharides produced by brown algae, and apart from being a structural polysaccharide and providing rigidity to the algae it also helps to prevent the desiccation of those plants exposed to air at low tide. Alginates are mainly constituted of (1 to >4) linked -d-mannuronic (M) and -lguluronic (G) residues, according to three kinds of sequences (M)m , (G)n and (M,G)x . These natural polyelectrolytes are able to gelify water when added in tiny amounts. Hydrogels containing 12% polymer and 9899% water can be shaped as self-standing spheres or lms with good mechanical stability. Gelling of alginates occurs when divalent cations take part in the interchain binding between G blocks leading to a three-dimensional network. Alginates form ionotropic gels when divalent or trivalent cations coordinate to two carboxylic groups of the macromolecule. The properties of alginate gels are inuenced by the ratio and sequencing of the uronic monomers [1,2], the concentration of the cation in the maturation bath and the time of maturation [3,4].

Corresponding author. Fax: +33 467 163 470. E-mail address: philippe.trens@enscm.fr (P. Trens).

Those properties are at the basis both of their natural function as water-storage agents for living organisms as well as of their main application. Alginates are extensively used for the entrapment of biologically active materials for applications as different as the controlled release of drug or cosmetics, biological catalysis and the transport of enzymes for detergency [511]. In fact, the use of alginates as immobilizing agents in different applications lies in their ability to form heat-stable strong gels. In all these applications, alginate is maintained in an aqueous media. Evaporative drying methods bring about the collapse of the gel structure and do not allow to preserve the accessibility of the functional groups. On the contrary, the technique of supercritical drying allows to avoid shrinking of the gels and has already brought to several breakthroughs in other elds of the materials science. When dried under CO2 supercritical conditions, the hydrogels transform into dispersed aerogels with surface areas as high as 500 m2 g1 [12]. These differences in the textural properties of the material, according to the drying procedure, allows to consider different elds of applications such as catalysis, depollution, gases separation and so on. Whatever the drying process, alginates are meant to preserve at least a part of their natural water adsorption property. As a consequence, it could be possible to take advantage of this specic property but it could be a drawback as well, depending on the desired applications.

0927-7757/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.colsurfa.2006.09.049

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When adsorbing water vapour, it is possible to probe the surface sites of the materials as well as determining the adsorption (or absorption) capabilities at a specic temperature. It is also possible to derive the enthalpy of adsorption accompanying the adsorption phenomenon. The afnity between adsorptive and adsorbent can be directly determined by microcalorimetry, but it can also be deduced from adsorption isotherms and the use of models like the BET model through its CBET parameter [13]. It is not a usual procedure to derive that CBET parameter from adsorption isotherms of vapours like water even though it has already been proven useful in the past in order to determine the hydrophobic/lipophilic balance of silica surfaces [14]. A recent example is the comparison of nitrogen and n-hexane towards adsorption onto mineral surfaces, employed to have a precise picture of the adsorptive/adsorbent interaction [15]. Adsorption isotherms comparison methods such as t-plot or s can also give information about the porous system detected by the probe molecule used, allowing to discuss the porosity in terms of kinetic diameter/pore diameter ratio [16]. In this work, the differences towards water adsorption of dried forms of alginate were studied in order to correlate the textural properties as well as the nature of exchanged cationic species to the hydrophilic character of the prepared materials. 2. Experimental 2.1. Methods 2.1.1. Water adsorption experiments Water adsorption experiments have been performed by using a home made apparatus widely described elsewhere. Deionised water has been outgassed by liquidthaw cycles using liquid nitrogen. The adsorbents have been activated at 323 K for 8 h under primary vacuum prior to water adsorption. These thermal treatments led to an average weight loss of 15% regardless of the nature of the material, which already gives an indication of the water absorption capabilities of the different samples at room temperature and under an ambient partial pressure of water of ca. 20 Torr. Pristine samples of each material have been employed for each single experiment to avoid any ageing that could occur after adsorption desorption cycles. 2.1.2. Textural characterization Nitrogen adsorption at 77 K has been performed by using a micromeritics 2010 apparatus. Prior to the analysis, alginate samples were outgassed at 323 K until a stable static vacuum of 3 103 Torr was reached. Water losses could be estimated for the different materials by thermal analysis (NETZSCH, TG 209 C), using a 5 K min1 ramp under air ow. Scanning electron microscopy on the dried microspheres has been done with a Hitachi S 4500 microscope with an accelerating eld of 20 kV after platinum metallization. 2.1.3. Elemental analyses Cation content of the different materials was determined by ICP (plasma with inductive coupling). The solid is attacked by

a mixture of aqua regia and HF, then after maximum evaporation, the residue is dissolved in HCl (1.2N) and the solution is analyzed. The metal content of the organic solutions is given after drying by evaporation of the solutions. These analyses were carried out with the Service Central dAnalyse of CNRS in Solaize. The results were as followsCo: 10.5%, Na: 0.007% in Co based materials, Ca: 7.9%, Na: 0.01% in Ca based materials, residual Na coming from the original Na-alginate. 2.2. Materials Calcium is already widely employed to precipitate alginate and is also food compatible. It is not the case of cobalt which is a striking example of cation able to precipitate alginate but having different specic properties in terms of hydration spheres and related physicochemical properties. These two cations were compared for their water sorption capabilities. 2.2.1. Preparation 2.2.1.1. Hydrogel spheres formation. Sodium alginate (Sigma Aldrich from Macrocystis Pyrifera, 3600 cP viscosity of a 2% solution, mannuronic/guluronic ratio 1.82 by IR spectroscopic evaluation) was dissolved in distilled water at a concentration of 1% (w/w) [17]. The polymer solution was added dropwise at room temperature to the stirred 0.24 molar M2+ solution (M2+ = Ca2+ , Co2+ ) using a syringe with a 0.8 mm diameter needle. The microspheres were cured in the gelation solution for 15 h and washed with distilled water. 2.2.2. Drying 2.2.2.1. Xerogel and aerogel spheres formation. Two different procedures were followed in order to dry the microspheres. Xerogels were formed by room temperature drying of the hydrogel spheres. The aerogels were formed by CO2 supercritical drying. This method consists in the extraction of the solvent above the critical point. Supercritical CO2 was chosen because of its low critical point of 31.5 C, at 70 bar. The hydrogel microspheres were dehydrated by immersion in a series of successive ethanolwater baths of increasing alcohol concentration (10, 30, 50, 70, 90, 100%) during 15 min each [18]. Ethanol was later replaced by liquid CO2 and the spheres were later dried under CO2 supercritical conditions (74 bar, 31.5 C) in a Polaron 3100 apparatus. The strength and porosity of the beads could also be somewhat controlled by choosing alginate with a specic composition. As already demonstrated, the higher the lguluronic acid content, the stronger the gel. On the other hand, if a higher composition of d-mannuronic acid is chosen for immobilization, beads with larger internal pore sizes are produced [19]. Samples with Ca and Co were prepared and labeled M-Aero or M-Xero according to the drying process and the nature of the cation. The inuence of the drying procedure on the morphology of the microspheres is illustrated in Fig. 1. At the macroscopic scale it is clear that an important shrinkage occurred for the xerogel (Fig. 1c) while the aerogel retained the original size of the beads (Fig. 1b).

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Fig. 1. Pictures of Ca exchanged materials before (a) and after drying (b and c).

3. Results 3.1. Nitrogen adsorption Adsorption isotherms of nitrogen at 77 K over Ca-Aero and Co-Aero are shown in Fig. 2. The adsorption isotherms of the Maerogels are of type IV at the borderline with type II in the IUPAC classication indicating the presence of large mesopores with a pore size distribution continuing into the macropore domain [20].

The monolayermultilayer adsorption process (0.05 < p/p < 0.35) allows evaluating the surface area of the sample using the method rst developed by Brunauer Emmett and Teller described in Section 1 [13]. The cross sectional area of nitrogen was taken as 0.162 nm2 . The presence of micropores was excluded by using the s method with a non-porous silica taken as a reference (Aerosil 200, not shown here) [16]. High surface areas close to 400 m2 g1 were obtained; the values are reported in Table 1. The corresponding xerogels exhibit no signicant specic surface area (<2 m2 g1 ). It can be noticed that nitrogen adsorption over Ca-Aero is greater that that observed with Co-Aero (monolayer capacities Vm ) which is consistent with previous results already published [21]. It was concluded that that non-buffered gelation by transition-metal cations is a mixed ionotropic-acid process,
Table 1 Textural properties of the aerogel form of the different materials estimated from nitrogen adsorption at 77 K Material Ca-Aero Co-Aero Vm (cm3 g1 ) 116.1 74.0 CBET 131 144 SBET (m2 g1 ) 508 324

Fig. 2. Adsorption isotherms of nitrogen at 77 K.

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Fig. 3. Water uptake on Na-alginate vs. water relative pressure.

leading to a reticulation of the polymer chains, thus limiting swelling possibility [21]. CBET values are pretty similar indicating the same kind of interaction of the materials surfaces towards nitrogen molecules. Keeping in mind that values over 100 correspond to microporous materials when probing with nitrogen, those values are high as compared to those obtained from the adsorption of nitrogen over mineral oxides, especially because those prepared materials are not microporous. The gures presented in Table 1 can therefore be interpreted as high afnity systems in which strong interaction exist between nitrogen species and polysaccharides surface, regardless of the nature of the exchanged metal. 3.2. Water adsorption 3.2.1. Na-alginate Water adsorption on commercial powder Na-alginate at 303 or 323 K is shown on Fig. 3. Two temperatures were studied in order to distinguish between adsorption, which is essentially an exothermic phenomenon so that an increase of temperature should result in a decrease of adsorbed amount, and absorption

which should increase when polymeric chains are made exible by an increase of temperature. The water uptake strongly increases when temperature is raised by 20 K, which indicates that absorption is the main uptake process, at least for intermediate relative pressures up to saturation (0.2 < p/p < 1). The curvature of the curves at low relative pressure indicates the afnity of water species towards surface sites, typically cationic species and alcohol functions. The ill-dened knees obtained on these adsorption isotherms would rather indicate a mild afnity of water for these surface sites conrmed by the values of CBET derived from the BET model applied on these adsorption isotherms (see later). The shape of the curves at higher relative pressure is rather linear which is consistent with a Henrys law absorption process, in which the uptake is simply directly proportional to the equilibrium relative pressure. This suggests that the inuence of surface towards uptake processes is only visible at very low equilibrium relative pressure. This is precisely the difference between absorption and adsorption which is only evoked when surface is involved in uptake processes. Na-alginate has been exchanged using Ca or Co cationic species and textured as described above. 3.2.2. Ca-exchanged materials Water vapour adsorption over Ca-Aero and Ca-Xero samples at 303 and 323 K is shown in Fig. 4. The overall shape of the curves is quite similar to that obtained with Na-alginate which conrms that cationic exchange does change the overall properties of the material, provided that the cationic species exhibit similar chemical properties. Increasing the temperature results in an increase of adsorbed water. The Ca-Xero leads to adsorbed amounts close to those found with Na-alginate whereas larger amounts of water vapour are adsorbed with Ca-Aero which is consistent with nitrogen adsorption results. This point again stresses the advantage of using CO2 supercritical drying as compared to classical thermal dry-

Fig. 4. Water uptake on Ca-Xero and Ca-Aero vs. water relative pressure.

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Fig. 5. Pictures of Co-Aero before outgassing at 323 K (a), after outgassing at 323 K (b), after 5 min back in static air (c).

ing since it is possible to favour a particular behaviour towards water sorption. 3.2.3. Co-exchanged materials The inuence of water on the colour of Co-Aero sample is shown in Fig. 5. From this gure, it is clear that in the case of CoAero, the activation process changed the coordination number of cobalt from VI in the starting material down to IV, as the color of the beads changes from pink to blue. After water adsorption, the color of the microspheres goes back to pink which implies that sorption of water occurs on the cations as well as on the polysaccharide network. This does not happen on the Co-Xero sample.

Water vapour adsorption over Co-Aero and Co-Xero samples at 303 and 323 K is shown in Fig. 6. In the case of Co-exchanged materials, small amounts of water are adsorbed onto the Xero form of the material whereas large amounts of water are adsorbed onto the Aero form of the material. The Co-exchanged material seems to be very dependent on its texture to adsorb water. Temperature has little effect on the Xero form of the material, however, the adsorbed amount are already very small so that an increase of 20 K probably cannot make any sensible difference.

Fig. 6. Water uptake on Co-Xero and Co-Aero vs. water relative pressure.

Fig. 7. Thermal analyses of Ca-Aero and Co-Aero obtained in air ow.

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4. Discussion As mentioned above, water losses could be estimated for the different materials by thermal analysis, and yielded the following water contents: Ca-Aero: 22%, Ca-Xero: 12%, Co-Aero: 23%, Co Xero: 8% (Fig. 7). This is consistent with the results shown above (i) Aero forms of the materials absorb higher amounts of water, (ii) Xero-forms of the materials favour CaXero towards water adsorption. It is somehow surprising that both Ca-Aero and Co-Aero release similar amounts of water upon heating, while the sorption isotherms clearly favour CoAero towards water sorption. Thermogravimetric experiments are realized on samples stored without particular care, and this amount could reect the difference on the humidity level in the atmosphere. On the other hand, the hydration spheres of calcium and cobalt are not identical, neither in number, nor in strength. The 2223% of water evolved from the materials are probably weakly bound to the polymeric chains, but this amount clearly does not represent the whole sorbed water content. Considering the thermal analyses of Ca-Aero and Ca-Xero materials, it can be noticed that water removal is strictly identical for the two materials up to 440 K from which temperature the degradation of the materials starts. It can be noticed that this phenomenon occurs at a temperature slightly lower in the case of Co-Aero which suggests that calcium stabilizes Ca-Aero particles while cobalt does not (or less). This phenomenon compares with the fact that some metals, such as nickel which allows hydrogenolysis, could even catalyse their polymethacrylic acid salts thermal degradation [22]. In the case of Co-Aero, the drastic change in slope during the degradation process could be due to a temperature from which this catalytic degradation begins. On the Ca-Aero trace, there is a clear step occurring at a temperature of 860 K which can be attributed to the thermal transformation of calcite CaCO3 into calcium oxide. These thermal analyses do not allow to distinguish the dehydration process of the cationic species due to the degradation of the materials, nevertheless, these conrm the occurrence of absorption regardless of the nature of the complexing cations. 4.1. Inuence of texture over sorption capabilities Texture clearly inuences the water uptakes. On Fig. 4, it can be seen that the inuence of texture between Ca-Aero and Ca-Xero leads to an enhancement of the absorption capacity as a function of the relative pressure but this effect is not so effective (10% at p/p = 0.5), considering the difference of texture shown by nitrogen adsorption (Table 1). The specic surface area of Ca-Aero is huge as compared to that of Ca-Xero (508 and <2 m2 g1 , respectively), but this does not induce any effective water absorption enhancement. However, this inuence is more striking when considering Co-Aero, as the enhancement of water uptake as compared to that obtained with Co-Xero is 600%. There is clear difference between the Aero forms of the nal materials towards water sorption which will be further discussed later in the paper. As mentioned, the extent of enhancement in the case of Ca-Aero is rather modest as compared to Ca-Xero, especially

with respect to the difference in specic surface areas between Ca-Xero and Ca-Aero, determined by nitrogen adsorption at 77 K. Since Ca-Xero has a very small surface area (<2 m2 g1 ), this behaviour towards water uptake suggests a strong swelling of the Ca-Xero which corresponds to an absorption mechanism. From water adsorption onto this material, it can be concluded that the gelication mechanism leads to exible materials able to swell under water uptake. Further, the difference between nitrogen adsorption and water sorption over the different materials can be explained by the fact that the organic frameworks are essentially rigid at 77 K, so that nitrogen molecules can only probe accessible surface sites while both diffusion and swelling of the organic frameworks should be rather limited. These results are somehow conrmed by water sorption on Co-exchanged materials even though there is a strong difference with Na-alginate towards water sorption. Co-Xero exhibits a very limited sorption capability towards water suggesting that swelling is not possible to a large extent, whereas Co-Aero presents very high water sorption capacity, in line with the difference between specic surface areas of the two materials. 4.2. Inuence of cationic species over sorption capabilities The enthalpies of hydration of Co2+ and Ca2+ are 2036 and 1602 kJ mol1 , respectively. These data are very high as compared to typical water adsorption enthalpies over polymers [23]. This strongly suggests that hydration of all the cations occurs at the very beginning of the water sorption on the materials. This is conrmed by the fast change in colour of the materials during the initial stages of the adsorption process. The same features are displayed on the water sorption isotherms over Ca and Co exchanged materials with respect to temperature. The water uptakes are very close to one another (for the different temperatures studied), which suggests that Ca and Na as cationic species do play a similar role towards absorption. The traces at low relative pressure (p/p < 0.1) are also very similar indicating that Na and Ca cations exhibit similar interaction with water molecules. On the other hand, there is a striking difference with Coexchanged materials which can be discussed: the traces are linear, especially at low relative pressure which suggests an important difference between Co and Ca based materials towards adsorption. The inexion in the absorption trace is an indication of the afnity between water vapour and the materials surfaces. As mentioned in Section 1, the use of the Brunauer Emmett Teller (BET) model allows deriving a parameter, CBET , indicator of this afnity. It is dened as CBET exp(E1 EL )/RT which relates the interaction strength of the rst adsorbed monolayer as compared to the interaction of any other adsorbed layer with the surface, taken as the liquefaction enthalpy. Two examples of curves of BET transforms are shown in Fig. 8. These curves are linear in a rather narrow relative pressure range, suggesting that the BET model may not be ideal to describe the adsorptionabsorption processes but can never-

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Fig. 8. BET transform of the sorption isotherm of water over Ca-Aero and Co-Aero vs. water relative pressure.

Table 2 Interaction water vapour/substrates estimated from the BET model CBET 303 K Ca-Aero Ca-Xero Co-Aero Co-Xero Na-alginate 9.2 5.0 4.0 9.5 323 K 12.7 11.7 5.2 9.9

theless be employed in that particular relative pressure domain. The values obtained for the CBET parameters are summarized in Table 2 in the case of the nal materials as well as the original Na-alginate. The results shown in Table 2 conrm the traces of the sorption isotherms at low relative pressure. In the case of Caexchanged materials, higher values are found as compared to Co-exchanged materials so that the BET method can give qualitative information related to surface/sorbate interaction even in such non-ideal systems. Temperature plays an important role in decreasing the strength of the polymeric beads. When this occurs, water molecules are able to penetrate the whole particles, leading to higher CBET values which explains that the difference between Ca-Xero and Ca-Aero is not so large at 323 K. Na-alginate exhibits a behaviour somewhere in between that of Ca-Xero and Ca-Aero, even though its texture should look like Ca-Xero. This conrms that the cationic exchange that Na-alginate has undergone modied its polymeric structure. 5. Conclusion The hydrophilic character of modied polysaccharides has been studied by means of water adsorption at 303 and 323 K. Modication of the initial material results from either the introduction of cationic species in the organic framework of polysaccharides (Ca or Co, up to 15%, w/w) or the drying stage of the

nal materials leading to aerogels or xerogels. This hydrophilic character has been discussed in terms of water adsorption or absorption capacities. A strong enhancement of this specic property is evidenced when using aerogel textured materials as compared to xerogels regardless of the nature of the cation introduced in the organic framework. Water absorption capacities are also further strongly modied when cobalt is used as complexing cation. Water sorption capacity is strongly limited with Co-Xero but dramatically enhanced with Co-Aero which could give interesting applications, not necessarily in food science, but more likely in sensors technology. This difference between calcium and cobalt species towards adsorption has been discussed in terms of hydration spheres, whereas water absorption has been interpreted in terms of cationic-mediated organic framework expansion induced by reticulation of the polysaccharides only occurring when cobalt is used to exchange sodium from Naalginate. The differences observed in the hydrophilic character of the materials according to the nature of the cation suggest that it could be possible to take advantage of this specic property, although chemical composition need to be adjusted depending on the desired application. References
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