Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018 ph-responsive and Magnetic Fe 3 O 4 @Silica@MIL-100(Fe)/β-CD Nanocomposite as Drug Nanocarrier: Loading and Release Study of Cephalexin Aseman Lajevardi 1, Moayad Hossaini Sadr* 2, Mohammad Tavakkoli Yaraki 3, 4, Alireaza Badiei 5, Mahsa Armaghan 1 1 Department of Chemistry, Islamic Azad University science and research Branch, Tehran, Iran. 2 Department of Chemistry, Faculty of Science, Azarbaijan Shahid Madani University, Tabriz,Iran. 3 Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive, Singapore 117585, Singapore 4 Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, 138634, Singapore 5 School of Chemistry, College of Science, University of Tehran, Tehran, Iran. *Corresponding Author: M. Hossaini Sadr, E-mail: sadr@azaruniv.edu, hosainis@yahoo.com 1
Table of Content Page Calibration Curve of Cephalexin (Fig. S1)... 3 Freundlich and Temkin isotherm model... 4 (Fig.S2) and (Fig.S3).... 5 Dubinin Radushkevich isotherm model (Fig.S4)... 6 7 (Fig.S5)... 7 (Fig.S6).. 8 Parameter isotherm model (Table.S1)..... 9 Reference....... 10 2
Fig. S1. Calibration curve of Cephalexin 3
Freundlich isotherm model Freundlich model is an empirical isotherm equation used for heterogeneous surface and multilayer adsorption. This model does not predict the maximum adsorption capacity and is expressed as follows 1 : q e = K F (C e ) 1/n Eq. (1) Where K F is Freundlich isotherm constant and shows the adhesion ability of the adsorbate on the sorbent. 1/n is calculated from the slope of the linearized plots of logq e versus logc e. (Fig.S2) Values of (1/n < 1) indicate a favorable adsorption process.as 1/n gets closer to 0, the adsorbent surface becomes more heterogeneous. If this value is above 1, the adsorption is unfavorable 2. Temkin isotherm model Temkin isotherm describes the interaction between the adsorbent and adsorbate This isotherm is defined as follows 3 : q e = Bln(K T ) + Bln(C e ) Eq. (2) B is a constant related to the heat of adsorption (J/mol). This equation has been expressed based on chemical adsorption. The B and K T values are obtained from q e versus lnc e plot fthe or the adsorbent (FigS3). 4
Fig. S2. Freundlich isotherm model Fig. S3. Temkin isotherm model 5
Dubinin Radushkevich isotherm model Radushkevich and Dubinin have expressed that the adsorption process is related to the porous structure of the adsorbent. This isotherm can be express as follows: ln (q e ) = ln (X m ) βε 2 Eq. (3) Where β and X m (maximum drug adsorption capacity) are obtained from the plot of ln (q e ) vs. ɛ 2 (Fig.S4).ɛ is calculated from the following equation: ε = RTln(1 + 1 C e ) Eq. (4) Where R is the gas constant, T is the absolute temperature (K) of adsorption process equilibrium. Also, the β constant is related to the adsorption free energy (E) for one mole of the drug. Adsorption energy is calculated by the following equation: E = 1 2β Eq. (5) If the value of E is below 8 kj/mol, the drug adsorption process is physical nature 4. Parameters and regression coefficients of isotherms models on the adsorbent in Table S1. 6
Fig. S4. D-R isotherm model Fig. S5. Drug sorption capacity of (a): Fe 3 O 4 @Silica@MIL-100 (Fe)/β-CD and (b): Fe 3 O 4 @Silica/β-CD(system without MOF) 7
Fig. S6. The drug release of (a): Fe 3 O 4 @Silica@MIL-100 (Fe)/β-CD and (b): Fe 3 O 4 @Silica/β-CD(system without MOF) 8
TableS1.Parameters and regression coefficients for Freundlich,Temkin, and D-R models Isotherm model Parameters Regression coefficient Freundlich n q e = K F (C e ) 1/n K F R 2 T=25 o C 2.007 0.63 0.83 T=30 o C 1.81 0.39 0.87 T=35 o C 1.8 0.29 0.9 T=40 o C Temkin B 1.63 K T 0.19 R 2 0.94 q e = Bln(K T ) + Bln(C e ) T=25 o C 0.58 4.1 0.92 T=30 o C 0.53 2.009 0.95 T=35 o C 0.45 1.63 0.96 T=40 o C D-R n 4 1.04 E(kJ.mol 1 ) R 2 0.96 ln (q e ) = ln (X m ) βε 2 T=25 o C 1.75 1.58 0.87 T=30 o C 1.41 1.12 0.83 T=35 o C 1.21 1 0.81 T=40 o C 0.98 0.9 0.73 9
References: 1 H. M. F. Freundlich, J. Phys. Chem, 1906, 57, 1100 1107. 2 H. Freundlich, Zeitschrift für Phys. Chemie, 1907, 57, 385 470. 3 M. I. Temkin and V. Pyzhev, Acta physiochim. URSS, 1940, 12, 217 222. 4 M. M. Dubinin, in Dokl. Akad. Nauk. SSSR., 1947, vol. 55, pp. 327 329. 10