Mesoporous silicas with covalently immobilized β-cyclodextrin moieties: synthesis, structure, and sorption properties
- 255 Downloads
Mesoporous silicas with chemically attached macrocyclic moieties were successfully prepared by sol-gel condensation of tetraethyl orthosilicate and β-cyclodextrin-silane in the presence of a structure-directing agent. Introduction of β-cyclodextrin groups into the silica framework was confirmed by the results of IR spectral, thermogravimetric, and quantitative chemical analysis of surface compounds. The porous structure of the obtained materials was characterized by nitrogen adsorption-desorption measurements, powder X-ray diffraction, transmission electron microscopy, and dynamic light scattering. It was found that the composition of the reaction mixture used in β-cyclodextrin-silane synthesis significantly affects the structural parameters of the resulting silicas. The increase in (3-aminopropyl)triethoxysilane as well as the coupling agent content in relation to β-cyclodextrin leads ultimately to the lowering or complete loss of hexagonal arrangement of pore channels in the synthesized materials. Formation of hexagonally ordered mesoporous structure was observed at molar composition of the mixture 0.049 TEOS:0.001 β-CD-silane:0.007 CTMAB:0.27 NH4OH:7.2 H2O and equimolar ratio of components in β-CD-silane synthesis. The sorption of alizarin yellow on starting silica and synthesized materials with chemically attached β-cyclodextrin moieties was studied in phosphate buffer solutions with pH 7.0. Experimental results of the dye equilibrium sorption were analyzed using Langmuir, Freundlich, and Redlich-Peterson isotherm models. It was proved that the Redlich-Peterson isotherm model is the most appropriate for fitting the equilibrium sorption of alizarin yellow on parent silica with hexagonally arranged mesoporous structure as well as on modified one with chemically immobilized β-cyclodextrin groups.
KeywordsMesoporous silica β-Cyclodextrin Chemical immobilization Alizarin yellow Sorption Environmental applications
We received no funding for this study.
Compliance with ethical standards
The authors declare that they have no competing interests.
- Agrawal R, Gupta V (2012) Cyclodextrins—a review on pharmaceutical application for drug delivery. Intern J Pharm Frontier Res 2:95–112Google Scholar
- Alahmadi SM, Mohamad S, Maan MJ (2014) Organic-inorganic hybrid materials based on mesoporous silica MCM-41 with β-cyclodextrin and its applications. Asian J Chem 26:4323–4329Google Scholar
- Chen L, Zhang L-F, Ching C-B, Ng S-C (2002) Synthesis and chromatographic properties of a novel chiral stationary phase derived from heptakis(6-azido-6-deoxy-2,3-di-O-phenylcarbamoylated)-β-cyclodextrin immobilized onto aminofunctionalized silica gel via multiple urea linkages. J Chromatogr A 950:65–74CrossRefGoogle Scholar
- Fujimura K, Ueda T, Ando T (1983) Retention behavior of some aromatic compounds on chemically bonded cyclodextrin silica stationary phase in liquid chromatography. Am Chem Soc 55:446–450Google Scholar
- Grun M, Unger KK, Matsumoto A, Tsutsumi K (1997) Ordered mesoporous MCM-41 adsorbents: novel routes in synthesis, product characterization and specification. In: McEnaney B, Mays JT, Rouquerol J, Rodriguez-Reynoso J, KSW S, Unger KK (eds) Characterisation of porous solids IV. The Royal Society of Chemistry, London, pp 81–89Google Scholar
- Helfferich FG (1995) Ion exchange. Dover, New YorkGoogle Scholar
- Katz E, Eksteen R, Schoenmakers P, Miller N (eds) (1998) Handbook of HPLC—chromatographic science series. Marcel Dekker Inc., New YorkGoogle Scholar
- Kawaguchi Y, Tanaka M, Nakae M, Funazo K, Shono T (1983) Chemically bonded cyclodextrin stationary phases for liquid chromatographic separation of aromatic compounds. Am Chem Soc 55:1852–1857Google Scholar
- Korenman IM (1970) Photometric analysis. Methods of determination of organic compounds. Khimia, Moscow (in Russian) Google Scholar
- Lala R, Thorat A, Cargote CS (2011) Current trends in β-cyclodextrin based drug delivery systems. IJRAP 2:1520–1526Google Scholar
- Larkin P (2011) Infrared and Raman spectroscopy: principles and spectral interpretation. Elsevier, OxfordGoogle Scholar
- Mondjinou YA, McCauliff LA, Kulkarni A, Paul L, Hyun S-H, Zhang Z, Wu Z, Wirth M, Storch J, Thompson DH (2013) Synthesis of 2-hydroxypropyl-β-cyclodextrin/pluronic-based polyrotaxanes via heterogeneous reaction as potential niemann-pick type C therapeutics. Biomacromolecules 14:4189–4197CrossRefGoogle Scholar
- Nakanishi K (1962) Infrared adsorption spectroscopy—practical. Holden-Day, Inc., Tokyo; Nankodo Company Ltd. San FranciscoGoogle Scholar
- Patel P, Deshpande A (2014) Patent review on cyclodextrin based nanosponges prepared by different methods: physicochemical characterization, factors influencing formation and applications. World J Pharm Sci 2:380–385Google Scholar
- Roik NV, Belyakova LA (2011) Interaction of supramolecular centers of silica surface with aromatic amino acids. J. Colloid Interface Sci 362: 172–179Google Scholar
- Salis A, Casula MR, Bhattacharyya MS, Pinna M, Solinas V, Monduzzi M (2010) Physical and chemical lipase adsorption on SBA-15: effect of different interactions on enzyme loading and catalytic performance. Chem Cat Chem 2:322–329Google Scholar
- Unger KK (1979) Porous silica—its properties and use as support in column liquid chromatography. Elsevier, AmsterdamGoogle Scholar