Mechanochemical modification of kaolin surfaces for immobilization and delivery of pesticides in alginate-chitosan composite beads

The surface modification with poly(methyl hydrosiloxane) (PMHS) using a grinding method as a pesticide carrier had been successfully achieved. The characteristics of the modified kaolin were represented by Fourier transform infrared, X-Ray diffraction, BET specific surface area measurements, laser particle size analysis, transmission electron microscopy and contact angle measurement. Subsequently, immobilization of acetamiprid onto clay’s surface was carried out by means of freeze-drying technology. And the drug-loaded clays were encapsulated in alginate-chitosan composite beads by extrusion into calcium chloride solution. The composite beads showed regularly spherical shapes and uniform sizes with diameters of 1.44 ± 0.24–1.75 ± 0.19 mm. The immobilization and release of acetamiprid were carried out to examine the effect of the modified kaolin on the properties of the composite bead. The results showed that the intensive force of superfine pulverization during the grinding process was effective to increase the specific surface areas of the modified kaolin with particle size reduction. The modified kaolins as promising carrier materials had improved the drug loading rate and encapsulation efficiency from 4.15 and 42.01 % for alginate-chitosan composite beads to 6.02 and 82.95 %, which were higher than 4.33 and 54.29 % for SA-CS-kaolin composite beads, respectively. The controlled-release formulation containing the modified kaolin had shown slow and sustained release properties to promote the efficient use of organic pesticide to reduce pollution effect on the environment.

[1]  M. C. Hermosín,et al.  Adsorption of pesticides from water by functionalized organobentonites. , 2005, Journal of agricultural and food chemistry.

[2]  T. Aminabhavi,et al.  Preparation and characterization of interpenetrating network beads of poly(vinyl alcohol)‐grafted‐poly(acrylamide) with sodium alginate and their controlled release characteristics for cypermethrin pesticide , 2002 .

[3]  G. Lagaly.  Pesticide–clay interactions and formulations , 2001 .

[4]  B. Frisken,et al.  Revisiting the method of cumulants for the analysis of dynamic light-scattering data. , 2001, Applied optics.

[5]  T. K. Van,et al.  Preparation and evaluation of controlled-release formulations of 2,6-dichlorobenzonitrile , 1984 .

[6]  Nicholas A. Peppas,et al.  A simple equation for description of solute release I. Fickian and non-fickian release from non-swellable devices in the form of slabs, spheres, cylinders or discs , 1987 .

[7]  Lijie Dong,et al.  Novel‐modified kaolin for enhancing the mechanical and thermal properties of poly(vinyl chloride) , 2012 .

[8]  Lei Jiang,et al.  Magnetically Induced Reversible Transition between Cassie and Wenzel States of Superparamagnetic Microdroplets on Highly Hydrophobic Silicon Surface , 2012 .

[9]  Haydn H. Murray,et al.  Traditional and new applications for kaolin, smectite, and palygorskite: a general overview , 2000 .

[10]  Richard M. Johnson,et al.  Leaching of Alachlor from Alginate-Encapsulated Controlled-Release Formulations , 1996 .

[11]  S. Boyd,et al.  Polarity Effect on Dichlorobenzene Sorption by Hexadecyltrimethylammonium-Exchanged Clays , 2000 .

[12]  E. Morillo,et al.  Ethylcellulose formulations for controlled release of the herbicide alachlor in a sandy soil. , 2007, Journal of agricultural and food chemistry.

[13]  F. Flores-Céspedes,et al.  Use of bentonite and activated carbon in controlled release formulations of carbofuran. , 2005, Journal of agricultural and food chemistry.

[14]  K. Kuroda,et al.  One-step exfoliation of kaolinites and their transformation into nanoscrolls. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[15]  G. Ding,et al.  Wetting on nanoporous alumina surface: transition between Wenzel and Cassie states controlled by surface structure. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[16]  M. Rinaudo,et al.  Chitin and chitosan: Properties and applications , 2006 .

[17]  Roger St. C. Smart,et al.  Nanomorphology of Kaolinites: Comparative SEM and AFM Studies , 1998 .

[18]  Cornejo,et al.  Organosmectites as sorbent and carrier of the herbicide bentazone , 2000, The Science of the total environment.

[19]  Susmita Gupta,et al.  Adsorption of a few heavy metals on natural and modified kaolinite and montmorillonite: a review. , 2008, Advances in colloid and interface science.

[20]  M. Carretero,et al.  Clay minerals and their beneficial effects upon human health. A review , 2002 .

[21]  I. Onyido,et al.  Environmentally Friendly Formulations of Trifluralin Based on Alginate Modified Starch , 2012 .

[22]  W. Weber,et al.  Evaluation of shale and organoclays as sorbent additives for low-permeability soil containment barriers. , 2001, Environmental science & technology.

[23]  E. González-Pradas,et al.  Controlled release of carbofuran from an alginate-bentonite formulation: water release kinetics and soil mobility. , 2000, Journal of Agricultural and Food Chemistry.

[24]  C. Yeom,et al.  Characterization of sodium alginate and poly(vinyl alcohol) blend membranes in pervaporation separation , 1998 .

[25]  J. W. Kuan,et al.  Slow release formulations of metribuzin based on alginate-kaolin-linseed oil☆ , 1993 .

[26]  U. Mingelgrin,et al.  Sorption of organic compounds of varying hydrophobicities from water and industrial wastewater by long- and short-chain organoclays , 2004 .

[27]  C. Muzny,et al.  Surfactant Adsorption on a Clay Mineral: Application of Radiation Scattering , 1997 .

[28]  Puxin Zhu,et al.  A starch/milled-montmorillonite nanocomposite for warp sizing , 2012 .

[29]  Dennis E. Koppel,et al.  Analysis of Macromolecular Polydispersity in Intensity Correlation Spectroscopy: The Method of Cumulants , 1972 .

[30]  S. Provencher.  A constrained regularization method for inverting data represented by linear algebraic or integral equations , 1982 .

[31]  I. Lindup,et al.  Controlled Release of Imidacloprid from a Lignin Matrix: Water Release Kinetics and Soil Mobility Study , 1998 .

[32]  A. L. Demirel,et al.  Tuning the surface hydrophobicity of polymer/nanoparticle composite films in the Wenzel regime by composition. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[33]  R. Frost,et al.  Modification of Kaolinite Surfaces by Mechanochemical Treatment , 2001 .

[34]  O. D. Dailey.  Volatilization of alachlor from polymeric formulations. , 2004, Journal of agricultural and food chemistry.

[35]  W. Doane,et al.  Encapsulation of atrazine within a starch matrix by extrusion processing , 1991 .

[36]  S. Nekkaa,et al.  Effects of Kaolin Surface Treatments on the Thermomechanical Properties and on the Degradation of Polypropylene , 2012 .

[37]  A. Pourjavadi,et al.  New polysaccharide‐g‐polyacrylonitrile copolymers: synthesis and thermal characterization , 2003 .

[38]  Q. Lin,et al.  Clean and rapid synthesis of double metal cyanide complexes using mechanochemistry , 2011 .

[39]  Bo Zheng,et al.  A dual-responsive supramolecular polymer gel formed by crown ether based molecular recognition. , 2011, Angewandte Chemie.

[40]  B. Yue,et al.  Highly stable phospholipid unilamellar vesicles from spontaneous vesiculation: A DLS and SANS study. , 2005, The journal of physical chemistry. B.

[41]  V. Hasırcı,et al.  Pesticide and model drug release from carboxymethylceullose microspheres. , 1996, Journal of microencapsulation.

[42]  L. Pérez-Maqueda,et al.  Effects of Dry Grinding on the Structural Changes of Kaolinite Powders , 2004 .

[43]  M. Sánchez-Martín,et al.  Organo-clays as adsorbents for azinphosmethyl and dichlorvos in aqueous medium , 1994 .

[44]  E. González-Pradas,et al.  Use of activated bentonites in controlled-release formulations of atrazine. , 2004, Journal of Agricultural and Food Chemistry.

[45]  Atul Gupta,et al.  Controlled release of the fungicide thiram from starch–alginate–clay based formulation , 2009 .