Abstract
Spherical silica particles are traditionally made via Stöber and modified-Stöber processes, which commonly use environmental toxins as reagents. Here we report a process to synthesise spherical silica particles using environmentally friendly biomolecules (phosphatidylcholine and soy lecithin) and employing water and soybean oil as solvents, rather than potentially harmful organic solvents. This scalable method represents an important step towards sustainable industrial silica syntheses. Under mildly acidic conditions phosphatidylcholine and soy lecithin can control the condensation of sodium silicate to form discrete, spherical silica particles. Silica particles with diameters ranging between 329 and 2232 nm were readily produced using phosphatidylcholine as the templating agent and soybean oil as the solvent in the presence of sodium silicate. Narrower size distributions (262–1272 nm) were achieved using soy lecithin as the templating agent in an aqueous acetate buffer solution containing sodium silicate. Silica particles grown using low concentrations of phosphatidylcholine and soy lecithin as templating agents formed by a combination of coalescence and Ostwald ripening, whilst particles grown at high concentrations predominantly formed through Ostwald ripening behaviour. The possibility of sustainably producing spherical silica particles in a simple biomolecule-templated synthesis is shown.
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References
Alothman Z (2012) A review: fundamental aspects of silicate mesoporous materials. Materials (Basel) 5:2874–2902. https://doi.org/10.3390/ma5122874
Anderson MT, Martin JE, Odinek JG, Newcomer PP (1998) Effect of methanol concentration on CTAB micellization and on the formation of surfactant-templated silica (STS). Chem Mater 10:1490–1500. https://doi.org/10.1021/cm970240m
Banta RA, Collins TW, Curley RA et al (2018) Nanopatterned protein-polysaccharide thin films by humidity regulated phase separation. J Colloid Interface Sci. https://doi.org/10.1016/j.jcis.2018.07.109
Bebensee F, Voigts F, Maus-Friedrichs W (2008) The adsorption of oxygen and water on Ca and CaO films studied with MIES, UPS and XPS. Surf Sci 602:1622–1630. https://doi.org/10.1016/j.susc.2008.02.011
Cabezas DM, Diehl BWK, Tomás MC (2009) Sunflower lecithin: application of a fractionation process with absolute ethanol. JAOCS J Am Oil Chem Soc 86:189–196. https://doi.org/10.1007/s11746-008-1336-5
Cabezas DM, Diehl BWK, Tomás MC (2016) Emulsifying properties of hydrolysed and low HLB sunflower lecithin mixtures. Eur J Lipid Sci Technol 118:975–983. https://doi.org/10.1002/ejlt.201500182
Capello C, Fischer U, Hungerbühler K (2007) What is a green solvent? A comprehensive framework for the environmental assessment of solvents. Green Chem 9:927–934. https://doi.org/10.1039/b617536h
Chen Y, Feng Y, Deveaux JG et al (2019) Biomineralization forming process and bio-inspired nanomaterials for biomedical application: a review. Minerals 9:68. https://doi.org/10.3390/min9020068
Cho C-S (2012) Design and development of degradable polyethylenimines for delivery of DNA and small interfering RNA: an updated review. ISRN Mater Sci. https://doi.org/10.5402/2012/798247
Coradin T, Durupthy O, Livage J (2002) Interactions of amino-containing peptides with sodium silicate and colloidal silica: a biomimetic approach of silicification. Langmuir 18:2331–2336
Coradin T, Coupé A, Livage J (2003) Interactions of bovine serum albumin and lysozyme with sodium silicate solutions. Colloids Surfaces B Biointerfaces 29:189–196. https://doi.org/10.1016/S0927-7765(02)00208-4
Demadis KD, Pachis K, Ketsetzi A, Stathoulopoulou A (2009) Bioinspired control of colloidal silica in vitro by dual polymeric assemblies of zwitterionic phosphomethylated chitosan and polycations or polyanions. Adv Colloid Interface Sci 151:33–48. https://doi.org/10.1016/j.cis.2009.07.005
Fragou F, Moularas C, Adamska K et al (2020) Mn(II)-based catalysts supported on nanocarbon-coated silica nanoparticles for alkene epoxidation. ACS Appl Nano Mater 3:5583–5592. https://doi.org/10.1021/acsanm.0c00849
Galarneau A, Renard G, Mureseanu M et al (2007) Synthesis of sponge mesoporous silicas from lecithin/dodecylamine mixed-micelles in ethanol/water media: a route towards efficient biocatalysts. Microporous Mesoporous Mater 104:103–114. https://doi.org/10.1016/j.micromeso.2007.01.017
Gautier C, Abdoul-Aribi N, Roux C et al (2008) Biomimetic dual templating of silica by polysaccharide/protein assemblies. Colloids Surfaces B Biointerfaces 65:140–145. https://doi.org/10.1016/j.colsurfb.2008.03.005
Gong C, Sun S, Zhang Y et al (2019) Hierarchical nanomaterials via biomolecular self-assembly and bioinspiration for energy and environmental applications. Nanoscale 11:4147–4182. https://doi.org/10.1039/C9NR00218A
Gustus R, Gruber W, Wegewitz L et al (2014) Decomposition of amorphous Si2C by thermal annealing. Thin Solid Films 552:232–240. https://doi.org/10.1016/j.tsf.2013.12.033
Han Y, Lu Z, Teng Z et al (2017) Unraveling the growth mechanism of silica particles in the stöber method: in situ seeded growth model. Langmuir 33:5879–5890. https://doi.org/10.1021/acs.langmuir.7b01140
Heintze C, Formanek P, Pohl D et al (2020) An intimate view into the silica deposition vesicles of diatoms. BMC Mater 2:11. https://doi.org/10.1186/s42833-020-00017-8
Himpsel FJ, McFeely FR, Taleb-Ibrahimi A et al (1988) Microscopic structure of the SiO2/Si interface. Phys Rev B 38:6084–6096. https://doi.org/10.1103/PhysRevB.38.6084
Hollinger G, Himpsel FJ (1984) Probing the transition layer at the SiO 2 -Si interface using core level photoemission. Appl Phys Lett 44:93–95. https://doi.org/10.1063/1.94565
Huang Y, Pemberton JE (2010) Synthesis of uniform, spherical sub-100nm silica particles using a conceptual modification of the classic LaMer model. Colloids Surfaces A Physicochem Eng Asp 360:175–183. https://doi.org/10.1016/j.colsurfa.2010.02.031
Hyde EDER, Seyfaee A, Neville F, Moreno-Atanasio R (2016) Colloidal silica particle synthesis and future industrial manufacturing pathways: a review. Ind Eng Chem Res 55:8891–8913. https://doi.org/10.1021/acs.iecr.6b01839
Jackson E, Ferrari M, Cuestas-Ayllon C et al (2015) Protein-templated biomimetic silica nanoparticles. Langmuir 31:3687–3695. https://doi.org/10.1021/la504978r
Jia J, Zhou X, Caruso RA, Antonietti M (2004) Synthesis of microporous silica templated by gelatin. Chem Lett 33:202–203. https://doi.org/10.1246/cl.2004.202
Keane DA, Hanrahan JP, Copley MP et al (2010) A modified Stöber process for the production of mesoporous Sub 2 micron silica microspheres; applications in HPLC. J Porous Mater 17:145–152. https://doi.org/10.1007/s10934-009-9274-7
Kolbe F, Daus F, Geyer A, Brunner E (2020) Phosphate-silica interactions in diatom biosilica and synthetic composites studied by rotational echo double resonance (REDOR) NMR spectroscopy. Langmuir 36:4332–4338. https://doi.org/10.1021/acs.langmuir.0c00336
Kotzsch A, Gröger P, Pawolski D et al (2017) Silicanin-1 is a conserved diatom membrane protein involved in silica biomineralization. BMC Biol 15:9–11. https://doi.org/10.1186/s12915-017-0400-8
Kröger N, Lorenz S, Brunner E, Sumper M (2014) Self-assembly of highly phosphorylated silaffins and their function in biosilica morphogenesis. Science (80-) 298:584–586. https://doi.org/10.1126/science.1076221
Kuno T, Nonoyama T, Hirao K, Kato K (2011) Influence of the charge relay effect on the silanol condensation reaction as a model for silica biomineralization. Langmuir 27:13154–13158. https://doi.org/10.1021/la202576v
Le CTM, Houri A, Balage N et al (2019) Interaction of small ionic species with phospholipid membranes: the role of metal coordination. Front Mater. https://doi.org/10.3389/fmats.2018.00080
Lechner CC, Becker CFW (2015) Silaffins in silica biomineralization and biomimetic silica precipitation. Mar Drugs 13:5297–5333. https://doi.org/10.3390/md13085297
Lifshitz IM, Slyozov VV (1961) The kinetics of precipitation from supersaturated solid solutions. J Phys Chem Solids 19:35–50. https://doi.org/10.1016/0022-3697(61)90054-3
Lopez P, Gautier C, Livage J, Coradin T (2006) Mimicking biogenic silica nanostructures formation. Curr Nanosci 1:73–83. https://doi.org/10.2174/1573413052953156
Lorber B, Fischer F, Bailly M et al (2012) Protein analysis by dynamic light scattering: methods and techniques for students. Biochem Mol Biol Educ 40:372–382. https://doi.org/10.1002/bmb.20644
Lotty O, Hobbs R, O’Regan C et al (2013) Self-seeded growth of germanium nanowires: coalescence and ostwald ripening. Chem Mater 25:215–222. https://doi.org/10.1021/cm3032863
Luo L, Liang Y, Erichsen ES, Anwander R (2017) Monodisperse mesoporous silica nanoparticles of distinct topology. J Colloid Interface Sci 495:84–93. https://doi.org/10.1016/j.jcis.2017.01.107
Lv X, Zhang L, Xing F, Lin H (2016) Controlled synthesis of monodispersed mesoporous silica nanoparticles: Particle size tuning and formation mechanism investigation. Microporous Mesoporous Mater 225:238–244. https://doi.org/10.1016/j.micromeso.2015.12.024
Ma Y, Ardell AJ (2007) Coarsening of γ (Ni–Al solid solution) precipitates in a γ′ (Ni3Al) matrix. Acta Mater 55:4419–4427. https://doi.org/10.1016/j.actamat.2007.04.008
Mann S (2001) Biomineralization: principles and concepts in bioinorganic materials chemistry. Oxford University Press
Manzano M, Vallet-Regí M (2020) Mesoporous silica nanoparticles for drug delivery. Adv Funct Mater 30:1902634. https://doi.org/10.1002/adfm.201902634
Masse S, Laurent G, Chuburu F et al (2008) Modification of the stöber process by a polyazamacrocycle leading to unusual core-shell silica nanoparticles. Langmuir 24:4026–4031. https://doi.org/10.1021/la703828v
Meier M, Ungerer J, Klinge M, Nirschl H (2018) Synthesis of nanometric silica particles via a modified Stöber synthesis route. Colloids Surfaces A Physicochem Eng Asp 538:559–564. https://doi.org/10.1016/j.colsurfa.2017.11.047
Möller K, Bein T (2016) Talented mesoporous silica nanoparticles. Chem Mater 15:14. https://doi.org/10.1021/acs.chemmater.6b03629
Murai K, Higuchi M, Kuno T, Kato K (2014) Silica mineralization by a peptide template having a high charge relay effect. ChemPlusChem 79:531–535. https://doi.org/10.1002/cplu.201300321
Murdan S (2005) A review of pluronic lecithin organogel as a topical and transdermal drug delivery system. Hosp Pharm 12:267–270
Naderizadeh S, Athanassiou A, Bayer IS (2018) Interfacing superhydrophobic silica nanoparticle films with graphene and thermoplastic polyurethane for wear/abrasion resistance. J Colloid Interface Sci 519:285–295. https://doi.org/10.1016/j.jcis.2018.02.065
Nałȩcz-Jawecki G, Grabińska-Sota E, Narkiewicz P (2003) The toxicity of cationic surfactants in four bioassays. Ecotoxicol Environ Saf 54:87–91. https://doi.org/10.1016/S0147-6513(02)00025-8
Nandy S, Kundu D, Naskar MK (2014) Synthesis of mesoporous Stöber silica nanoparticles: the effect of secondary and tertiary alkanolamines. J Sol-Gel Sci Technol 72:49–55. https://doi.org/10.1007/s10971-014-3420-7
Nozawa K, Gailhanou H, Raison L et al (2005) Smart control of monodisperse stöber silica particles: effect of reactant addition rate on growth process. Langmuir 21:1516–1523. https://doi.org/10.1021/la048569r
Pamirsky IE, Golokhvast KS (2013) Silaffins of diatoms: From applied biotechnology to biomedicine. Mar Drugs 11:3155–3167. https://doi.org/10.3390/md11093155
Park SK, Do KK, Kim HT (2002) Preparation of silica nanoparticles: determination of the optimal synthesis conditions for small and uniform particles. Colloids Surfaces A Physicochem Eng Asp 197:7–17. https://doi.org/10.1016/S0927-7757(01)00683-5
Patwardhan SV, Staniland SS (2019) Biomineralisation: how Nature makes nanomaterials. In: Green NanomaterialsFrom bioinspired synthesis to sustainable manufacturing of inorganic nanomaterials, 1st edn. IOP Publishing, Bristol, UK, pp 1–21
Perrett S, Buell AK, Knowles TPJ (eds) (2019) Biological and bio-inspired nanomaterials. Springer Singapore, Singapore
Plumeré N, Ruff A, Speiser B et al (2012) Stöber silica particles as basis for redox modifications: Particle shape, size, polydispersity, and porosity. J Colloid Interface Sci 368:208–219. https://doi.org/10.1016/j.jcis.2011.10.070
Post P, Wurlitzer L, Maus-Friedrichs W, Weber A (2018) Characterization and applications of nanoparticles modified in-flight with silica or silica-organic coatings. Nanomaterials 8:530. https://doi.org/10.3390/nano8070530
Prasomsri T, Jiao W, Weng SZ, Garcia Martinez J (2015) Mesostructured zeolites: bridging the gap between zeolites and MCM-41. Chem Commun 51:8900–8911. https://doi.org/10.1039/C4CC10391B
Rahman IA, Padavettan V (2012) Synthesis of Silica nanoparticles by Sol-Gel: Size-dependent properties, surface modification, and applications in silica-polymer nanocompositesa review. J Nanomater. https://doi.org/10.1155/2012/132424
Ramanathan R, Campbell JL, Soni SK et al (2011) Cationic amino acids specific biomimetic silicification in ionic liquid: a quest to understand the formation of 3-D structures in diatoms. PLoS ONE 6:e17707. https://doi.org/10.1371/journal.pone.0017707
Sadri R, Hosseini M, Kazi SN et al (2017) A bio-based, facile approach for the preparation of covalently functionalized carbon nanotubes aqueous suspensions and their potential as heat transfer fluids. J Colloid Interface Sci 504:115–123. https://doi.org/10.1016/j.jcis.2017.03.051
Santos J, Calero N, Trujillo-Cayado LA et al (2017) Assessing differences between Ostwald ripening and coalescence by rheology, laser diffraction and multiple light scattering. Colloids Surfaces B Biointerfaces 159:405–411. https://doi.org/10.1016/j.colsurfb.2017.08.015
Shaikh I, Jadhav K, Gide P et al (2006) Topical delivery of aceclofenac from lecithin organogels: preformulation study. Curr Drug Deliv 3:417–427. https://doi.org/10.2174/156720106778559010
Slowing II, Vivero-Escoto JL, Trewyn BG, Lin VS-Y (2010) Mesoporous silica nanoparticles: structural design and applications. J Mater Chem 20:7924. https://doi.org/10.1039/c0jm00554a
Sobańska AW (2020) Emerging or underestimated silica-based stationary phases in liquid chromatography. Crit Rev Anal Chem. https://doi.org/10.1080/10408347.2020.1760782
Soleimani M, Rutten L, Maddala SP et al (2020) Modifying the thickness, pore size, and composition of diatom frustule in Pinnularia sp. with Al3+ ions. Sci Rep 10:19498. https://doi.org/10.1038/s41598-020-76318-5
Sprenger KG, Prakash A, Drobny G, Pfaendtner J (2018) Investigating the role of phosphorylation in the binding of silaffin peptide R5 to silica with molecular dynamics simulations. Langmuir 34:1199–1207. https://doi.org/10.1021/acs.langmuir.7b02868
Stovpiaga EY, Kurdyukov DA, Kukushkina YA et al (2015) Monodisperse spherical silica particles with controlled-varied diameter of micro- and mesopores. Glas Phys Chem 41:316–323. https://doi.org/10.1134/S1087659615030153
Sumper M, Kröger N (2004) Silica formation in diatoms: The function of long-chain polyamines and silaffins. J Mater Chem 14:2059–2065. https://doi.org/10.1039/b401028k
Sumper M, Lorenz S, Brunner E (2003) Biomimetic control of size in the polyamine-directed formation of silica nanospheres. Angew Chemie Int Ed 42:5192–5195. https://doi.org/10.1002/anie.200352212
Tengjisi HY, Yang G et al (2021) Biomimetic core–shell silica nanoparticles using a dual-functional peptide. J Colloid Interface Sci 581:185–194. https://doi.org/10.1016/j.jcis.2020.07.107
Thommes M (2010) Physical adsorption characterization of nanoporous materials. Chemie Ing Tech 82:1059–1073. https://doi.org/10.1002/cite.201000064
Tilburey GE, Blundell TJ, Argent SP, Perry CC (2019) Azamacrocycles and tertiary amines can be used to form size tuneable hollow structures or monodisperse oxide nanoparticles depending on the “M” source. Dalt Trans 48:15470–15479. https://doi.org/10.1039/c9dt02080b
Trinh TT, Jansen APJ, Van Santen RA (2006) Mechanism of oligomerization reactions of silica. J Phys Chem B 110:23099–23106. https://doi.org/10.1021/jp063670l
Trofimova EY, Kurdyukov DA, Yakovlev SA et al (2013) Monodisperse spherical mesoporous silica particles: Fast synthesis procedure and fabrication of photonic-crystal films. Nanotechnology. https://doi.org/10.1088/0957-4484/24/15/155601
Wagner C (1961) Theorie der Alterung von Niederschlägen durch Umlösen (Ostwald-Reifung). Berichte der Bunsengesellschaft für Phys Chemie 65:581–591. https://doi.org/10.1002/BBPC.19610650704
Wallace AF, DeYoreo JJ, Dove PM (2009) Kinetics of silica nucleation on carboxyl- and amine-terminated surfaces: Insights for biomineralization. J Am Chem Soc 131:5244–5250. https://doi.org/10.1021/ja809486b
Wang J, Sugawara-Narutaki A, Fukao M et al (2011) Two-phase synthesis of monodisperse silica nanospheres with amines or ammonia catalyst and their controlled self-assembly. ACS Appl Mater Interfaces 3:1538–1544. https://doi.org/10.1021/am200104m
Wang Q, Zhang C, Shen G et al (2014) Fluorescent carbon dots as an efficient siRNA nanocarrier for its interference therapy in gastric cancer cells. J Nanobiotechnol 12:58. https://doi.org/10.1186/s12951-014-0058-0
Wenzl S, Hett R, Richthammer P, Sumper M (2008) Silacidins: Highly acidic phosphopeptides from diatom shells assist in silica precipitation in vitro. Angew Chemie Int Ed 47:1729–1732. https://doi.org/10.1002/anie.200704994
Wysokowski M, Jesionowski T, Ehrlich H (2018) Biosilica as a source for inspiration in biological materials science. Am Mineral 103:665–691. https://doi.org/10.2138/am-2018-6429
Xia L (2014) The structure evolution of biomimetic silica directed by poly(L-lysine). Adv Mater Res 926–930:292–295. https://doi.org/10.4028/www.scientific.net/AMR.926-930.292
Yang H-W, Kang N, Myung S-T et al (2018) Exceptional effect of benzene in uniform carbon coating of SiOx nanocomposite for high-performance Li-ion batteries. J Electrochem Soc 165:A1247–A1253. https://doi.org/10.1149/2.0291807jes
Yi Z, Dumée LF, Garvey CJ et al (2015) A new insight into growth mechanism and kinetics of mesoporous silica nanoparticles by in situ small angle X-ray scattering. Langmuir 31:8478–8487. https://doi.org/10.1021/acs.langmuir.5b01637
Zhao Z, Wang X, Jiao Y et al (2016) Facile, low-cost, and scalable fabrication of particle size and pore structure tuneable monodisperse mesoporous silica nanospheres as supports for advanced solid acid catalysts. RSC Adv 6:9072–9081. https://doi.org/10.1039/c5ra26432d
Acknowledgements
We wish to thank Dr John Hanrahan for useful discussions and Dr. Joe McGrath for running the BET analysis.
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This research was funded by AMBER through Science Foundation Ireland (Grant No.: 12/RC/2278) and Glantreo Ltd.
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Curley, R., Banta, R.A., Garvey, S. et al. Biomimetic spherical silica production using phosphatidylcholine and soy lecithin. Appl Nanosci 11, 1721–1735 (2021). https://doi.org/10.1007/s13204-021-01839-y
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DOI: https://doi.org/10.1007/s13204-021-01839-y