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Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

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Front. Mater. Sci.    2017, Vol. 11 Issue (4) : 395-409    https://doi.org/10.1007/s11706-017-0400-1
RESEARCH ARTICLE
Layered double hydroxide using hydrothermal treatment: morphology evolution, intercalation and release kinetics of diclofenac sodium
Mathew JOY1,2(), Srividhya J. IYENGAR1,2, Jui CHAKRABORTY2, Swapankumar GHOSH1()
1. Project Management Division, CSIR-Central Glass & Ceramic Research Institute, Kolkata-700032, India
2. Bioceramics & Coating Division, CSIR-Central Glass & Ceramic Research Institute, Kolkata-700032, India
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Abstract

The present work demonstrates the possibilities of hydrothermal transformation of Zn–Al layered double hydroxide (LDH) nanostructure by varying the synthetic conditions. The manipulation in washing step before hydrothermal treatment allows control over crystal morphologies, size and stability of their aqueous solutions. We examined the crystal growth process in the presence and the absence of extra ions during hydrothermal treatment and its dependence on the drug (diclofenac sodium (Dic-Na)) loading and release processes. Hexagonal plate-like crystals show sustained release with ~90% of the drug from the matrix in a week, suggesting the applicability of LDH nanohybrids in sustained drug delivery systems. The fits to the release kinetics data indicated the drug release as a diffusion-controlled release process. LDH with rod-like morphology shows excellent colloidal stability in aqueous suspension, as studied by photon correlation spectroscopy.
Keywords layered double hydroxide      crystal morphology      hydrothermal treatment      drug loading     
Corresponding Author(s): Mathew JOY,Swapankumar GHOSH   
Online First Date: 07 November 2017    Issue Date: 29 November 2017
 Cite this article:   
Mathew JOY,Srividhya J. IYENGAR,Jui CHAKRABORTY, et al. Layered double hydroxide using hydrothermal treatment: morphology evolution, intercalation and release kinetics of diclofenac sodium[J]. Front. Mater. Sci., 2017, 11(4): 395-409.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-017-0400-1
https://academic.hep.com.cn/foms/EN/Y2017/V11/I4/395
Fig.1  XRD patterns of LCp, LHb and their drug-loaded counterparts, LCpDic and LHbDic, showing high intense basal reflections.
Sample Cell parameters d(003)/Å d(006)/Å l/Å
a/Å c/Å
LCp 3.07 22.8 7.60 3.8 7.59
LCpDic 3.07 65.88 21.9 11.22 22.2
LHa 3.06 22.59 7.53 3.75 7.5
LHaDic 3.06 23.04 7.68 3.82 7.6
LHb 3.07 26.8 8.93 4.42 8.8
LHbDic 3.07 67.05 22.35 11.38 22.5
Tab.1  Calculated lattice parameters and interlayer spacing of various LDH samples
Fig.2  Scheme 1 ?(a) The sketch showing probable orientation of Dic-Na drug in the interlayer gallery of LHbDic. (b) The chemical structure of Dic-Na.
Fig.3  FTIR spectra of pristine and diclofenac-loaded LDHs.
Fig.4  (a) FESEM image of LCp. (b)(c) Bright-field TEM images of hydrothermally prepared LHa and LHb respectively when viewed in the [001] zone axis. Insets of (b) and (c) show the SAED patterns.
Fig.5  Scheme 2 Schematic representation of the formation of LHb crystals and the loading of drug into the sample.
Fig.6  (a) TG and (b) DTA plots of LHb (i), LHbDic (ii) and pure Dic-Na (iii). The derivative of TG data of LHbDic is shown as dotted line.
Sample Weight remaining/% Adsorbed moisture/% Weight content of structural ions/% Drug loading/% Chloride loading/(meq·g −1)
LHb 74.0 2.0 24.0 0.59
LHbDic 51.0 2.4 16.5 30.1
LCp 71.0 1.0 28.0 0.56
LCpDic 54.2 4.8 21.4 19.6
LHa 83.2 1.9 14.9 0.073
LHaDic 76.6 2.0 13.7 7.7
Tab.2  Analyses of thermogravimetry data and chloride ion saturation into the LDH structure
Fig.7  Zeta potentials of various LDH and drug-loaded samples with different pH values varying from neutral to alkaline.
Fig.8  (a) The decay of auto correlation function with time obtained from DLS for LHa (i) and LHb (ii). The inset shows the hydrodynamic size of LHa (dotted line) and LHb.(b)Zav size and PDI as a function of temperature for LHa.
Fig.9  (a) Release profiles of diclofenac drug from LHaDic (i), LCpDic (ii) and LHbDic (iii). Contact angle microscopic images of water droplets in(b) LHb and (c) LHbDic surface.
Kinetic model Mathematical form Parameter, R2
LHbDic LCpDic
First-order model ln( Ct/C0) = −kdt 0.872 0.823
Parabolic diffusion model (1− Ct/C0)/t = kdt−0.5 + a 0.973 0.800
Elovich model 1− Ct/C0 = alnt + b 0.985 0.979
Ritger–Peppas equation Ct/C0 = kd(t−a)n 0.991 0.986
Tab.3  Linear correlation coefficient (R2) values of different kinetic models for LHbDic and LCpDic
Fig.10  Fits to drug release data of LHbDic for different kinetic models: (a) first-order model; (b) parabolic diffusion model; (c)Elovich model; (d) R-P equation.
Fig.11  Fits to drug release data of LCpDic for different kinetic models: (a) first-order model; (b) parabolic diffusion model; (c) Elovich model; (d) R-P equation.
  Fig. S1 The XRD pattern of LHa. The vertical drop-lines correspond to JCPDS No. 38-0486 shown for comparison of reflection positions and intensity.
  Fig. S2 TG curves: (a) LHa (i), LHaDic (ii); (b) LCp (iii), LCpDic (iv). The derivatives of TG data of LHaDic and LCpDic are shown as dotted lines.
Sample Composition by weight /%
Zn Al Nitrate Carbonate
LCp 43.63 8.62 18.6 0.56
LHa 43.53 5.95 13.34 0.26
LHb 43.45 8.34 17.89 0.64
  Table S1 Summary of chemical analysis data of pristine LDH
Sample Drug content /%
LHaDic 5.7
LHbDic 32.45
LCpDic 22.5
  Table S2 Drug content value calculated from HPLC data
  Fig. S3 The conductivity changes of LHb suspension while varying the pH of surrounding medium from 6 to 13.
  Fig. S4 The high-quality phase data associated with LHb samples from positive to negative with zeta potential while varying the pH value of surrounding medium from 6 to13.
  Fig. S5Zav and mean count rate of LDH dispersion plotted as function of time for (a) LHa and (b) LHaDic.
  Fig. S6 Hydrodynamic size of LHbDic (in dotted line) and LCpDic.
  Fig. S7 Nitrogen isotherms and their pore size distribution profiles for drug-loaded LDH particles.
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