Sorption of aspartic and glutamic aminoacids on calcined hydrotalcite
© Silvério et al.; licensee Springer. 2013
Received: 18 October 2012
Accepted: 4 May 2013
Published: 8 May 2013
Sorption of aspartic and glutamic aminoacids by regeneration of calcined hydrotalcite is reported. Hydrotalcite was synthesized by coprecipitation and calcined at 773 K. Sorption experiments were performed at 298 K and 310 K, and the results reveal that at low aminoacids equilibrium concentrations, intercalation of hydroxyl anions takes place while at high equilibrium concentrations, the sorption process occur by means re-hydration and aminoacids intercalation of hydrotalcite. The results also suggested that Asp and Glu sorption is a temperature dependent process. The amount of sorbed amino acid decreases as the temperature increase. The effect is more pronounced for Glu sorption probably due to its higher hydrophobic character, which makes the sorption more difficult in comparison with sorption of Asp at higher temperature.
KeywordsHydrotalcite Layered double hydroxides Aminoacids Adsorption Sorption
Hydrotalcite-like compounds, also known as Layered Double Hydroxides (LDH) have received considerable attention due to their properties and applications (Costantino et al. 2008; Takehira & Shishido 2007; Darder et al. 2007; Evans & Xue 2006; Velu et al. 2005; Anbarasan et al. 2005; Zhu et al. 2005; Tronto et al. 2004). Their structure consists of sheets disposed in a layered array formed by octahedral sharing their edges, with bi and trivalent cations on the centers of octahedral hexacoordinated with hydroxyl anions. Layers of LDH are residual positive charge neutralized by anions located in the interlayer domain.
Hydrotalcite can be used to remove anions from aqueous solution by three different processes: adsorption, anion exchange and regeneration of a calcined precursor (Zhu et al. 2005; Takehira et al. 2005; Aisawa et al. 2004). Mg-Al and Zn-Al LDH systems present the specific property known “memory effect” that consists in the capacity of calcined LDH regenerate its lamellar structure by incorporation of anions when it is put in contact with an intercalating anion in aqueous solution (Kooli et al. 1997). Taking advantage of the “memory effect”, different molecules such as polyorganic anions, benzoate, tereftalate and surfactants, have been sorbed onto LDH (Cardoso et al. 2003; Cardoso et al. 2004; Crepaldi et al. 2002).
Aspartic (Asp) and glutamic (Glu) aminoacids are used in pharmaceutical and food industry, where industrial wastewater treatment is not often practiced (Ohtsubo et al. 2005; Shih & Van 2001). These aminoacids differ due to an extra CH2 group in the Glu aliphatic chain and both have a carboxylic group. This work is focused on evaluation of sorption process of Asp and Glu aminoacids by regeneration of calcined MgAl-LDH in order to verify the efficiency of its adsorbent for wastewaters treatment.
Materials and methods
Layered double hydroxide – the sorbent
The LDH was prepared by coprecipitation at variable pH as proposed by Reichle (Reichle et al. 1986). All reactants were of analytical grade and were used without further purification. Magnesium Nitrate (>99%), Aluminum Nitrate (>98%), Sodium Hydroxide (>98%) and Sodium Carbonate (>99%) were purchased from Merck. All solids were characterized by Powder X-Ray Diffraction (PXRD), using a Siemens D5005 X-ray Diffractometer, with a graphite monochromator selecting the Cu-Kα1 radiation (0.15406 nm) in an angular 2θ range of 2-70° and step rate of 0.02° s-1; Fourier Transform Infra-Red Spectroscopy (FT-IR), with an ABB Bomem MB 100 spectrometer over the range 400–4000 cm-1 with 32 scans and a 4 cm-1 resolution, using pressed KBr pellets at 2% (w/w) of sample; Thermogravimetric and Differential Thermal Analysis (TGA/DTA), using a TA Instruments SDT 2960 in synthetic air atmosphere at a heating rate of 10 K min-1; Scanning Electron Microscopy (SEM) using a Zeiss DSM 960-Digital Scanning Microscope; and Specific Surface Area (SSA) performed on Quanta Chrome Nova 1200 equipment.
From TGA/DTA and elemental analysis the formula of the LDH precursor was obtained as , which corresponds to a Mg/Al ratio of 2.3/1. This information is extremely important because the anionic exchange by regeneration depends on of this ratio. Immediately before use in adsorption, the LDH precursor was calcined at 773 K for 4 hours under O2 (White Martins) flow giving rise a Mg-Al mixed oxy-hydroxide – the adsorbent.
Aspartic and glutamic acids – the sorbates
The aminoacids (Asp and Glu) were acquired from Merck (>99.5% assay), and used without further purification. All aminoacids solutions were prepared with deionized water (MilliQ®), and the pH was adjusted to 10 with NaOH.
Sorption experiments of Asp and Glu were carried out in bath method with 100 mg of the calcined precursor into 25 cm3 of amino acid solutions at different concentrations (concentration ranging from 0.001 to 0.04 mol.dm-3 for Asp, and from 0.001 to 0.06 mol.dm-3 for Glu) at pH 10. The obtained suspension was ultra-sonicated for 10 minutes to homogenize particle size, before adsorption. The isotherms were obtained at 298 K and 310 K.
Closed samples were place in a thermostatic bath with orbital shaking, for 70 hours, to ensure that the sorption equilibrium would be reached. After that, each sample was divided into two parts: one was centrifuged at 10,000 G for 20 minutes and the supernatant was used to quantifier the amount of amino acid, using a UV–vis 8453 Hewlett Packard spectrophotometer, and the solid was dried and characterized by PXRD and FTIR; the other part of the sample was kept in aqueous suspension, during 10 minutes, until largest particles were decanted, and after that, it was used for determination of electrokinetical (zeta) potential. The measurement of electrokinetical potential was carried out in triplicate at the same temperature of sorption experiments.
Results and discussion
The lower amount of amino acid removed obtained at 310 K can be explained considering that with at higher temperature of the system, the higher is the importance of entropy for the system’s Gibb’s free energy (ΔG = ΔH – TΔS), thus the role of enthalpy is reduced. Thus, organization of compact aggregates with a larger number of amino acid molecules at the LDH should become more difficult. Moreover, as the experiments were performed in aqueous medium, the interlayer section of the LDH provides an environment energetically most suitable to host hydrophobic molecules. At 298 K this effect is intensified in favor of Glu intercalation due to its higher hydrophobic character than Asp. Therefore, the more hydrophobic is the amino acid, the more it will be sorbed at the same equilibrium concentration at 298 K while the opposite trend occurs at 310 K.
At lower aminoacids concentrations, the sorption process does not seem to be influenced by temperature and the amounts of aminoacids removed are approximately the same for all conditions. The LDH reconstruction with both aminoacids seems to be very similar. The regeneration at low aminoacids concentrations occurs predominantly via intercalation of OH- anions from aqueous solution (pH 10). As the amino acid concentration increases, a competition between OH- and amino acid takes place with amino acid intercalation. At lower amino acid concentrations, approximately 99% of Asp or Glu are removed; whereas, at higher amino acid concentration, near the limit of solubility, the extraction rate is approximately 20%. The electrokinetical potential curves related to each isotherm are also very similar. Positives values at low equilibrium concentrations decrease, reaching values as negative as −6 mV, while the aminoacids concentration increase. The profiles of electrokinetical potential curves are in agreement with the respective isotherm profile.
The amount of charge available for removal of anionic species by the calcined LDH was calculated taking into account the amount of Al3+, and it was found 5.36 × 10-3 mol of charge (+1) per g of calcined LDH. Then, 2.68 × 10-3 mol of Asp or Glu could be removed by anionic exchange. The maximum amount remove (after isotherms) is about 2.7 × 10-3 mol Glu per g of LDH at 298 K. The other values in the corresponding isotherms are lower.
General parameters observed for the material sorbed with Asp and Glu at 298 K and 310 K
Medium particle size (Å)
Pore total volume (cm3.g-1)
Average pore diameter (Å)
Regenerated with OH
Initial area (Asp-298 K)
Initial area (Glu-298 K)
Last point (Asp-298 K)
Last point (Asp-310 K)
Last point (Glu-298 K)
Last point (Glu-310 K)
The results showed that Asp and Glu intercalation by sorption is a process that dependent on the amino acid concentration. At low amino acid concentrations, the LDH is regenerated predominantly with intercalated hydroxyl anions. As the amino acid concentration increases, a competition between the hydroxyl anions and the amino acid for intercalation in the interlayer domain takes place with amino acid dislocating the equilibrium in favor of Asp or Glu intercalation. The results also suggested that Asp and Glu sorption is a temperature dependent process, with a decrease in the amount of sorbed amino acid with increasing temperature. This effect is more pronounced in the case of Glu, probably due to its higher hydrophobic character, which makes the sorption more difficult in comparison with sorption of Asp at higher temperature. Thus, aminoacids hydrophobicity contributes to sorption: the more hydrophobic is the amino acid, the more it will be sorbed at the same equilibrium concentration at 298 K, while the opposite trend occurs at 310 K.
The authors thank the Brazilian agencies CAPES and CNPq for financial support.
- Aisawa S, Hirahara H, Uchiyama H, Takahashi S, Narita E, Solid State J: Chem. 2002, 167: 152-159.
- Aisawa S, Kudo H, Hoshi T, Takahashi S, Hirahara H, Umetsu Y, Narita E, Solid State J: Chem. 2004, 177: 3987-3994.
- Anbarasan R, Lee WD, Im SS: Bull Mater Sci. 2005, 28: 145-149. 10.1007/BF02704234View Article
- Cardoso LP, Tronto J, Crepaldi EL, Valim JB: Mol Cryst Liq Cryst. 2003, 390: 49-56.View Article
- Cardoso LP, Valim JB, Phys J: Chem Solids. 2004, 65: 481-485. 10.1016/j.jpcs.2003.08.034View Article
- Costantino U, Ambrogi V, Nocchetti M, Perioli ML: Microporous Mesoporous Mater. 2008, 107: 149-160. 10.1016/j.micromeso.2007.02.005View Article
- Crepaldi EL, Tronto J, Cardoso LP, Valim JB: Colloids Surf A. 2002, 211: 103-114. 10.1016/S0927-7757(02)00233-9View Article
- Darder M, Aranda P, Ruiz-Hitzky E: Adv Mater. 2007, 19: 1309-1319. 10.1002/adma.200602328View Article
- Evans DG, Xue DA: Chem Comm. 2006, 5: 485-496.View Article
- Fudala A, Palinko I, Kiricsi I: J Mol Struct. 1999, 483: 33-37.View Article
- Kooli F, Depège C, Ennaqadi A: A de Roy and J. P. Besse. Clays Clay Miner 1997, 45: 92-98. 10.1346/CCMN.1997.0450111View Article
- Ohtsubo K, Suzuki K, Yasui Y, Kasumi T, Food Comp J: Anal. 2005, 18: 303-316.
- Reichle WT, Kang SY, Everhardt DS: J Catal. 1986, 101: 352. 10.1016/0021-9517(86)90262-9View Article
- Shih IL, Van YT: Bioresour Technol. 2001, 79: 207-225. 10.1016/S0960-8524(01)00074-8View Article
- Takehira K, Shishido T: Catal Surv Asia. 2007, 11: 1-30. 10.1007/s10563-007-9016-2View Article
- Takehira K, Kawabata T, Shishido S, Murakami K, Ohi T, Shoro D, Honda M, Takaki K: J Catal. 2005, 231: 92-104. 10.1016/j.jcat.2005.01.025View Article
- Tronto J, Cardoso LP, Valim JB, Marchetti JM, Bentley MVB: Mol Crist Liq Crist. 2003, 390: 79-89. Part 2View Article
- Tronto J, dos Reis MJ, Silverio F, Balbo VR, Marchetti JM, Valim JB, Phys J: Chem Solids. 2004, 65: 475-480. 10.1016/j.jpcs.2003.09.019View Article
- Velu S, Suzuki K, Vijayaraj M, Barman S, Gopinath CS: Appl Catal B. 2005, 55: 287-299. 10.1016/j.apcatb.2004.09.007View Article
- West AR: Solide State Chemistry and its Applications. Chichester: J. Wiley; 1987.
- Whilton NT, Vickers PJ, Mann S: J Mater Chem. 1997, 7: 1623-1629. 10.1039/a701237cView Article
- Zhu MX, Li YP, Xie M, Xin HZ: J Hazard Mater. 2005, 120: 163-171. 10.1016/j.jhazmat.2004.12.029View Article
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