Article pubs.acs.org/IECR
Experimental Results and Theoretical Modeling of the Growth Kinetics of Polyamine-Derived Silica Particles Ahmad Seyfaee,† Frances Neville,*,‡ and Roberto Moreno-Atanasio† †
School of Engineering, The University of Newcastle, Callaghan, New South Wales 2308, Australia School of Environmental and Life Sciences, The University of Newcastle, Callaghan, New South Wales 2308, Australia
‡
S Supporting Information *
ABSTRACT: Polyamine-derived silica particles are proposed to grow due to primary particle (25 nm) are formed via aggregation of primary particles with a diameter of around 25 nm.38 To model the particle growth, a semiempirical mathematical model based on the DLS results has been proposed and developed. This model uses the final particle diameter as an input parameter. The comparison of the model results with DLS experimental data (Figures 5 and 6) showed the necessity of other particle population existence in order to predict the experimental data accurately. Depending on the TMOMS and PEI/PB concentrations, different numbers of primary particle populations were required to fit our model to the experimental data. The higher the TMOMS concentration, the more populations were needed. However, this process only took place if the concentration of TMOMS was high enough to produce particles with a diameter greater than 350 nm. The exponent n, for production of primary particles, was found to be even for the best fits. This value was 2 for all of the first and second populations of particles (k2α3) and was 1 for all of third populations (k2α). These exponents clearly indicate that the production rate of particles in the third population is slower than in the other cases. The modeling shows that aggregation rates of primary particles increased with TMOMS and PEI/PB concentration. However, the primary particle production rate coefficients increased with decreasing concentrations of TMOMS while maintaining the same PEI concentration. Nevertheless, the equilibrium diameter of the particle was mainly related to TMOMS concentration. In conclusion, our model has demonstrated the complexity of PEI−silica particle formation as the result of a sensitive balance between primary particle production and aggregation and it has aided us to achieve a better understanding of how to control the growth of TMOMS silica particles catalyzed by polyethylenimine.
CONCLUSIONS In this paper, we have confirmed that there is a minimum concentration of TMOMS that is required for particle formation to occur. In addition, we have determined that
The paper was written through contributions of all authors. All authors have given approval to the final version of the paper.
■
ASSOCIATED CONTENT
S Supporting Information *
Mathematical derivation of the theoretical model; (Table S1) parameter results of modeling for different particle synthesis ratios with the full detailed number results. This material is available free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*F. Neville. E-mail:
[email protected]; Frances.
[email protected]. Phone: +61 (0)249216458. Fax: +61 (0) 249216920.
■
Author Contributions
Notes
The authors declare no competing financial interest. 2473
DOI: 10.1021/acs.iecr.5b00093 Ind. Eng. Chem. Res. 2015, 54, 2466−2475
Article
Industrial & Engineering Chemistry Research
■
Rijeka, Croatia, 2011 (ISBN: 978-953-307-191-6. DOI: 10.5772/ 14905. (6) Patwardhan, S. V. Biomimetic and Bioinspired Silica: Recent Developments and Applications. Chem. Commun. 2011, 47, 7567. (7) Global Information. http://www.giiresearch.com/press/ fd120989.shtml (accessed November 2014). (8) Liu, W.; Wu, W.; Selomulya, C.; Chen, X. D. A Single Step Assembly of Uniform Micro Particles for Controlled Release Applications. Soft Matter 2011, 7, 3323. (9) Gu, S.; Shi, Y.; Wang, L.; Liu, W.; Song, Z. Study on the Stability of Modified Colloidal Silica with Polymer in Aqueous Environment. Colloid Polym. Sci. 2014, 292, 267. (10) Patwardhan, S. V.; Emami, F. S.; Berry, R. J.; Jones, S. E.; Naik, R. R.; Deschaume, O.; Heinz, H.; Perry, C. C. Chemistry of Aqueous Silica Nanoparticle Surfaces and the Mechanism of Selective Peptide Adsorption. J. Am. Chem. Soc. 2012, 134, 6244. (11) Fickert, J.; Schaeffel, D.; Koynov, K.; Landfester, K.; Crespy, D. Silica Nano Capsules for Redox-Responsive Delivery. Colloid Polym. Sci. 2014, 292, 251. (12) Neville, F.; Broderick, M. J. F.; Gibson, T.; Millner, P. A. Fabrication and Activity of Silicate Nanoparticles and NanosilicateEntrapped Enzymes Using Polyethyleneimine as a Biomimetic Polymer. Langmuir 2011, 27, 279. (13) Neville, F.; Murphy, T.; Webber, G. B.; Wanless, E. J.; Jameson, G. J. Fabrication and Characterisation of Biomimetic Silicate Nanoparticles. In Proceedings of Chemeca: Engineering a Better World, Sydney, Australia, September 18−21, 2011, Paper No. 0125. (14) Neville, F.; Mohd Zin, A.; Jameson, G. J.; Wanless, E. J. Preparation and Characterization of Colloidal Silica Particles under Mild Conditions. J. Chem. Educ. 2012, 89, 940. (15) Neville, F.; Murphy, T.; Jameson, G. J.; Wanless, E. J. The Formation of Polyethyleneimine-Trimethoxymethylsilane OrganicInorganic Hybrid Particles. Colloids Surf., A 2013, 431, 42. (16) Roach, P.; Farrar, D.; Perry, C. C. Surface Tailoring for Controlled Protein Adsorption: Effect of Topography at the Nanometer Scale and Chemistry. J. Am. Chem. Soc. 2006, 128, 3939. (17) Neville, F.; Pchelintsev, N. A.; Broderick, M. J. F.; Gibson, T.; Millner, P. A. Novel One-pot Synthesis and Characterization of Bioactive Thiol-Silicate Nanoparticles for Biocatalytic and Biosensor Applications. Nanotechnology 2009, 20, 055612. (18) Iler, R. K. The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties and Biochemistry of Silica; Wiley: New York, 1979. (19) LaMer, V. K.; Dinegar, R. H. Theory, Production and Mechanism of Formation of Monodispersed Hydrosols. J. Am. Chem. Soc. 1950, 172, 4847. (20) Bogush, G. H.; Zukoski IV, C. F. Studies of the Kinetics of the Precipitation of Uniform Silica Particles through the Hydrolysis and Condensation of Silicon Alkoxides. J. Colloid Interface Sci. 1991, 142, 1. (21) Matsoukas, T.; Gulari, E. Dynamics of Growth of Silica Particles from Ammonia-Catalyzed Hydrolysis of Tetra-ethyl-orthosilicate. J. Colloid Interface Sci. 1988, 124, 252. (22) Flory, P. J. Molecular Size Distribution in Linear Condensation Polymers. J. Am. Chem. Soc. 1936, 58, 1877. (23) Stockmayer, W. H. Theory of Molecular Size Distribution and Gel Formation in Branched-Chain Polymers. J. Chem. Phys. 1943, 11, 45. (24) Bogush, G. H.; Zukoski IV, C. F. Uniform Silica Particle Precipitation: An Aggregative Growth Model. J. Colloid Interface Sci. 1991, 142, 19. (25) Bailey, J. K.; Mecartney, M. L. Formation of Colloidal Silica Particles from Alkoxides. Colloids Surf. 1992, 63, 151. (26) Masalov, V. M.; Sukhinina, N. S.; Kudrenko, E. A.; Emelchencko, G. A. Mechanism of Formation and Nanostructure of Stöber Silica Particles. Nanotechnology 2011, 22, 275718. (27) Van Blaaderen, A.; Van Geest, J.; Vrij, A. Monodisperse Colloidal Silica Spheres from Tetraalkoxysilanes: Particle Formation and Growth Mechanism. J. Colloid Interface Sci. 1992, 154, 481.
ACKNOWLEDGMENTS A.S. is the recipient of an international postgraduate research scholarship of the University of Newcastle.
■
ABBREVIATIONS DLS = dynamic light scattering PB = phosphate buffer PEI = polyethylenimine TEOS = tetraethoxysilane TMOMS = trimethoxymethylsilane TMOS = tetramethoxysilane
■
NOMENCLATURE
Letter Definition Unit
C(t) = concentration of primary particles at time t (mol·L−1) C∞ = final concentration of primary particles (mol·L−1) D = particle diameter (nm) D∞ = equilibrium diameter (nm) k1 = rate constant for aggregation of primary particles (s−1) k2 = rate constant for production of primary particles (s−1· (mol−1·L)m−1) kH = hydrolysis constant in the model of Bogush and Zukoski20 (s−1) m = exponent representing the production of primary particles (m = 2 or 4) Mw = molecular weight (g/mol) Ni = number of particles in each population, i Ni0 = number of particles in each population, i, at the start of growth-region (t = 0) n = exponent representing the production of primary particles (1 or 2) r = rate of reaction (mol·s−1) t = time (s) Vsolution = volume of liquid in control volume around particle (L) Vparticle = volume of the particle (nm3) X = cubed diameter difference (D3 − D3∞) (nm3) X0 = cubed diameter difference (D30 − D3∞) (nm3)
Greek Letters
α = conversion coefficient (mol·L−1·nm−3) ρparticle = particle density (g·nm−3)
Subscript and Superscript
0 = start of reaction ∞ = end of reaction i = ith type representation
■
REFERENCES
(1) Stö ber, W.; Fink, A.; Bohn, E. Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range. J. Colloid Interface Sci. 1968, 26, 62. (2) Topuz, B.; Ciftcioglu, M. Permeation of Pure Gases through Silica Membranes with Controlled Pore Structures. Desalination 2006, 200, 80. (3) Luckarift, H. R.; Spain, J. C.; Naik, R. R.; Stone, M. O. Enzyme Immobilization in a Biomimetic Silica Support. Nat. Biotechnol. 2004, 22, 211. (4) Bell, N. C.; Minelli, C.; Tompkins, J.; Stevens, M. M.; Shard, A. G. Emerging Techniques for Sub Micrometer Particle Sizing Applied to Stöber Silica. Langmuir 2012, 29, 10860. (5) Jin, R. H.; Yuan, J. J. Learning from Biosilica: Nanostructured Silicas and Their Coatings on Substrates by Programmable Approaches. In Advances in Biomimetics; George, A.; Ed.; InTech: 2474
DOI: 10.1021/acs.iecr.5b00093 Ind. Eng. Chem. Res. 2015, 54, 2466−2475
Article
Industrial & Engineering Chemistry Research (28) Neville, F.; Seyfaee, A. Real-Time Monitoring of in Situ Polyethyleneimine-Silica Particle Formation. Langmuir 2013, 29, 14681. (29) Goeppert, A.; Czaun, M.; May, R. B.; Suraya Prakesh, G. K.; Olah, G. A.; Narayanan, S. R. Carbon Dioxide Capture from the Air Using a Polyamine based Regenerable Solid Adsorbent. J. Am. Chem. Soc. 2011, 133, 20164. (30) Tang, F.; Li, L.; Chen, D. Mesoporous Silica Nanoparticles: Synthesis, Biocompatibility and Drug Delivery. Adv. Mater. 2012, 24, 1504. (31) Xia, T.; Kovochich, M.; Liong, M.; Meng, H.; Kabehie, S.; George, S.; Zink, J. I.; Nel, A. I. Polyethyleneimine Coating Enhances the Cellular Uptake of Mesoporous Silica Nanoparticles and Allows Safe Delivery of siRNA and DNA Constructs. ACS Nano 2009, 3, 3273. (32) Emami, F. S.; Puddu, V.; Berry, R. J.; Varshney, V.; Patwardhan, S. V.; Perry, C. C.; Heinz, H. Prediction of Specific Biomolecule Adsorption on Silica Surfaces as a Function of pH and Particle Size. Chem. Matter 2014, 26, 5275. (33) Hyde, D. E.; Moreno-Atanasio, R.; Millner, P. A.; Neville, F. Surface Charge Control through the Reversible Adsorption of a Biomimetic Polymer on Silica Particles. J. Phys. Chem. B 2014, 119, 1726. (34) Malay, O.; Yilgor, I.; Menceloglu, Y. Z. Effects of Solvent on TEOS Hydrolysis Kinetics and Silica Particle Size under Basic Conditions. J. Sol-Gel Sci. Technol. 2013, 67, 351. (35) Chen, S. L.; Dong, P.; Yang, G. H.; Yang, J. J. Kinetics of Formation of Monodisperse Colloidal Silica Particles through the Hydrolysis and Condensation of Tetraethylorthosilicate. Ind. Eng. Chem. Res. 1996, 35, 4487. (36) Elfimova, E.; Ivanov, A. O.; Yu. Zubarev, A. Evolution of the Fractal-like Aggregate System in Colloids. Phys. Rev. E 2006, 74, 021408. (37) Chen, S. L.; Dong, P.; Yang, G. H.; Yang, J. J. Characteristic Aspects of Formation of New Particles During the Growth of Monosized Silica Seeds. J. Colloid Interface Sci. 1996, 180, 237. (38) Seyfaee, A.; Moreno-Atanasio, R.; Neville, F. High Resolution Analysis of the Influence of Reactant Concentration on Nucleation Time and Growth of Polyethyleneimine-Trimethoxymethylsilane Particles. Colloid Polym. Sci. 2014, 292, 2673. (39) Sada, E.; Kumazawa, H.; Koresawa, E. Reaction Kinetics and Size Control in the Formation of Monosized Silica Spheres by Controlled Hydrolysis of Tetraethyl Orthosilicate in Ethanol. Chem. Eng. J. 1990, 44, 133. (40) Pearson, K. Notes on Regression and Inheritance in the Case of Two Parents. Proc. R. Soc. London 1895, 58, 240. (41) Zhao, S.; Xu, D.; Ma, H.; Sun, Z.; Guan, J. Controllable Preparation and Formation Mechanism of Monodispersed Silica Particles with Binary Sizes. J. Colloid Interface Sci. 2012, 388, 40.
2475
DOI: 10.1021/acs.iecr.5b00093 Ind. Eng. Chem. Res. 2015, 54, 2466−2475
