Abstract
Monodispersed spherical silica nanoparticles with a cubic mesostructure were synthesized in a fast and innovative way using triethanolamine (TEA) and the triblock copolymer Pluronic® F127 as particle growth inhibitors to control the particle size in a range from 420 to 62 nm. In this study, we described a synthesis of mesoporous silica nanoparticles (MSNs) with MCM-48 structure at room temperature with adequate control of particle monodispersity, shape, and size using TEA. Based on particle characterization, TEA can efficiently act as catalyst and at the same time as particle growth controlling additive. A mixture of TEA and Pluronic® F127 additives was used to obtain very small MSNs (62 nm), whereby the quality of MCM-48 silica is associated with the composition of the additives used and thus also with the final particle size. A finely dispersed and high-quality MCM-48 material with ~ 100% yield, excellent textural properties, and a particle size of 295 nm was synthesized within only 35 min using excess TEA as particle size controlling and dispersion agent together with ammonia as additional catalyst. Solvent extraction combined with ion exchange removed the surfactant efficiently. All prepared MSNs showed good textural properties, tunable particle sizes with narrow size distributions, and good dispersity in water, which make them highly promising as carriers for biomolecules in biomedical applications.
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References
Andersson J, Areva S, Spliethoff B, Lindén M (2005) Sol-gel synthesis of a multifunctional, hierarchically porous silica/apatite composite. Biomaterials 26:6827–6835. https://doi.org/10.1016/j.biomaterials.2005.05.002
Angelos S, Liong M, Choi E, Zink JI (2008) Mesoporous silicate materials as substrates for molecular machines and drug delivery. Chem Eng J 137:4–13. https://doi.org/10.1016/j.cej.2007.07.074
Bandyopadhyay M, Birkner A, van den Berg MWE, Klementiev KV, Schmidt W, Grünert W, Gies H (2005) Synthesis and characterization of mesoporous MCM-48 containing TiO2 nanoparticles. Chem Mater 17:3820–3829. https://doi.org/10.1021/cm0484854
Bharti C, Nagaich U, Pal AK, Gulati N (2015) Mesoporous silica nanoparticles in target drug delivery system: a review. Int J Pharm Investig 5:124–133. https://doi.org/10.4103/2230-973X.160844
Boote B, Subramanian H, Koodali RT (2007) Rapid and facile synthesis of siliceous MCM-48 mesoporous materials. Chem Commun:4543–4545. https://doi.org/10.1039/B706633C
Borodina E, Karpov SI, Selemenev VF, Schwieger W, Maracke S, Fröba M, Rößner F (2015) Surface and texture properties of mesoporous silica materials modified by silicon-organic compounds containing Quarternary amino groups for their application in base-catalyzed reactions. Microporous Mesoporous Mater 203:224–231. https://doi.org/10.1016/j.micromeso.2014.10.009
Brunauer S, Deming LS, Deming WE, Teller E (1940) On a theory of the van der Waals adsorption of gases. J Am Chem Soc 62:1723–1732. https://doi.org/10.1021/ja01864a025
Cho E-B, Volkov DO, Sokolov I (2011) Ultrabright fluorescent silica mesoporous silica nanoparticles: control of particle size and dye loading. Adv Funct Mater 21:3129–3135. https://doi.org/10.1002/adfm.201100311
Das D, Yang Y, O’Brien JS, Breznan D, Nimesh S, Bernatchez S, Hill M, Sayari A, Vincent R, Kumarathasan P (2014) Synthesis and physicochemical characterization of mesoporous SiO2 nanoparticles. J Nanomater 2014:1–12. https://doi.org/10.1155/2014/176015
Doadrio JC, Sousa EMB, Izquierdo-Barba I, Doadrio AL, Perez-Pariente J, Vallet-Regí M (2006) Functionalization of mesoporous materials with long alkyl chains as a strategy for controlling drug delivery pattern. J Mater Chem 16:462–466. https://doi.org/10.1039/B510101H
Du X, He J (2011) Spherical silica micro/nanomaterials with hierarchical structures: synthesis and applications. Nanoscale 3:3984–4002. https://doi.org/10.1039/C1NR10660K
Effati E, Pourabbas B (2012) One-pot synthesis of sub-50 nm vinyl- and acrylate-modified silica nanoparticles. Powder Technol 219:276–283. https://doi.org/10.1016/j.powtec.2011.12.062
Grün M, Lauer I, Unger KK (1997) The synthesis of micrometer- and submicrometer-size spheres of ordered mesoporous oxide MCM-41. Adv Mater 9:254–257. https://doi.org/10.1002/adma.19970090317
Guan B, Cui Y, Ren Z, Qiao Z, Wang L, Liu Y, Huo Q (2012) Highly ordered periodic mesoporous organosilica nanoparticles with controllable pore structures. Nanoscale 4:6588–6596. https://doi.org/10.1039/C2NR31662E
Guan B, Yu L, Lou XWD (2016) Formation of asymmetric bowl-like mesoporous particles via emulsion-induced Interface anisotropic assembly. J Am Chem Soc 138:11306–11311. https://doi.org/10.1021/jacs.6b06558
Guan B, Zhang SL, Lou XWD (2018) Realization of walnut-shaped particles with macro−/mesoporous open channels through pore architecture manipulation and their use in electrocatalytic oxygen reduction. Angew Chem Int Ed 57:6176–6180. https://doi.org/10.1002/anie.201801876
He Q, Shi J (2011) Mesoporous silica nanoparticle based nano drug delivery systems: synthesis, controlled drug release and delivery, pharmacokinetics and biocompatibility. J Mater Chem 21:5845–5855. https://doi.org/10.1039/C0JM03851B
Hoffmann F, Cornelius M, Morell J, Fröba M (2006) Silica-based mesoporous organic-inorganic hybrid materials. Angew Chem Int Ed 45:3216–3251. https://doi.org/10.1002/anie.200503075
Jin X, Wang Q, Sun J, Panezai H, Bai S, Wu X (2017) Dual (pH- and temperature-) stimuli responsive nanocarrier with bimodal mesoporous silica nanoparticles core and copolymer shell for controlled ibuprofen-releasing: fractal feature and diffusion mechanism. Microporous Mesoporous Mater 254:77–85. https://doi.org/10.1016/j.micromeso.2017.05.003
Kickelbick G (2007) Hybrid materials: synthesis, characterization and applications. Wiley-VCH, Weinheim
Kim T-W, Kleitz F, Paul B, Ryoo R (2005) MCM-48-like large mesoporous silicas with tailored pore structure: facile synthesis domain in a ternary triblock copolymer-butanol-water system. J Am Chem Soc 127:7601–7610. https://doi.org/10.1021/ja042601m
Kim T-W, Chung P-W, Lin VS-Y (2010) Facile synthesis of monodisperse spherical MCM-48 mesoporous silica nanoparticles with controlled particle size. Chem Mater 22:5093–5104. https://doi.org/10.1021/cm1017344
Kleitz F, Choi SH, Ryoo R (2003) Cubic Ia3d large mesoporous silica: synthesis and replication to platinum nanowires, carbon nanorods and carbon nanotubes. Chem Commun:2136–2137. https://doi.org/10.1039/b306504a
Kobler J, Möller K, Bein T (2008) Colloidal suspensions of functionalized mesoporous silica nanoparticles. ACS Nano 2:791–799. https://doi.org/10.1021/nn700008s
Kuśtrowski P, Chmielarz L, Dziembaj R, Cool P, Vansant EF (2005) Modification of MCM-48-, SBA-15-, MCF-, and MSU-type mesoporous silicas with transition metal oxides using the molecular designed dispersion method. J Phys Chem B 109:11552–11558. https://doi.org/10.1021/jp050696o
Lang N, Tuel A (2004) A fast and efficient ion-exchange procedure to remove surfactant molecules from MCM-41 materials. Chem Mater 16:1961–1966. https://doi.org/10.1021/cm030633n
Lelong G, Bhattacharyya S, Kline S, Cacciaguerra T, Gonzalez MA, Saboungi M-L (2008) Effect of surfactant concentration on the morphology and texture of MCM-41 materials. J Phys Chem C 112:10674–10680. https://doi.org/10.1021/jp800898n
Lind A, du Fresne von Hohenesche C, Smått J-H, Lindén M, Unger KK (2003) Spherical silica agglomerates possessing hierarchical porosity prepared by spray drying of MCM-41 and MCM-48 nanospheres. Microporous Mesoporous Mater 66:219–227. https://doi.org/10.1016/j.mi8cromeso.2003.09.011
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
Möller K, Kobler J, Bein T (2007) Colloidal suspensions of nanometer-sized mesoporous silica. Ad. Funct Mater 17:605–612. https://doi.org/10.1002/adfm.200600578
Nandy S, Kundu D, Naskar MK (2014) Synthesis of mesoporous Stöber silica nanoparticles: the effect of secondary and tertiary alkanolamines. J Sol-Gel Sci Techn 72:49–55. https://doi.org/10.1007/s10971-014-3420-7
Nooney RI, Thirunavukkarasu D, Chen Y, Josephs R, Ostafin AE (2002) Synthesis of nanoscale mesoporous silica spheres with controlled particle size. Chem Mater 14:4721–4728. https://doi.org/10.1021/cm0204371
Pajchel L, Kolodziejski W (2018) Synthesis and characterization of MCM-48/hydroxyapatite composites for drug delivery: ibuprofen incorporation, location and release studies. Mat Sci Eng C-Mater 91:734–742. https://doi.org/10.1016/j.msec.2018.06.028
Pardo-Tarifa F, Montes V, Claure M, Cabrera S, Kusar H, Marinas A, Boutonnet M (2017) Silica with 3D mesocellular pore structure used as support for cobalt Fischer-Tropsch catalyst. Synth Catal 2:1–11. https://doi.org/10.4172/2574-0431.100017
Peng R, Zhao D, Dimitrijevic NM, Rajh T, Koodali RT (2012) Room temperature synthesis of Ti-MCM-48 and Ti-MCM-41 mesoporous materials and their performance on photocatalytic splitting of water. J Phys Chem C 116:1605–1613. https://doi.org/10.1021/jp210448v
Polshettiwar V, Cha D, Zhang X, Basset JM (2010) High-surface-area silica nanospheres (KCC-1) with a fibrous morphology. Angew Chem Int Ed 49:9652–9656. https://doi.org/10.1002/anie.201003451
Qiao Z-A, Zhang L, Guo M, Liu Y, Huo Q (2009) Synthesis of mesoporous silica nanoparticles via controlled hydrolysis and condensation of silicon alkoxide. Chem Mater 21:3823–3829. https://doi.org/10.1021/cm901335k
Schiller R, Weiss CK, Geserick J, Hüsing N, Landfester K (2009) Synthesis of mesoporous silica particles and capsules by miniemulsion technique. Chem Mater 21:5088–5098. https://doi.org/10.1021/cm901858v
Schubert U (2015) Chemistry and fundamentals of the sol–gel process. Wiley-VCH, Weinheim
Shahbazi MA, Herranz B, Santos HA (2012) Nanostructured porous Si-based nanoparticles for targeted drug delivery. Biomatter 2:296–312. https://doi.org/10.4161/biom.22347
Solovyov LA, Belousov OV, Dinnebier RE, Shmakov AN, Kirik SD (2005) X-ray diffraction structure analysis of MCM-48 mesoporous silica. J Phys Chem B 109:3233–3237. https://doi.org/10.1021/jp0482868
Stöber W, Fink A, Bohn E (1968) Controlled growth of monodispersed silica spheres in the micron size range. J Colloid Interface Sci 26:62–69. https://doi.org/10.1016/0021-9797(68)90272-5
Uhlig H, Gimpel M-L, Inayat A, Gläser R, Schwieger W, Einicke W-D, Enke D (2013) Transformation of porous glasses into MCM-41 containing geometric bodies. Microporous Mesoporous Mater 182:136–146. https://doi.org/10.1016/j.micromeso.2013.08.035
Uhlig H, Muenster T, Kloess G, Ebbinghaus SG, Einicke W-D, Gläser R, Enke D (2018) Synthesis of MCM-48 granules with bimodal pore systems via pseudomorphic transformation of porous glass. Microporous Mesoporous Mater 257:185–192. https://doi.org/10.1016/j.micromeso.2017.08.033
Urata C, Aoyama Y, Tonegawa A, Yamauchi Y, Kuroda K (2009) Dialysis process for the removal of surfactants to form colloidal mesoporous silica nanoparticles. Chem Commun:5094–5096. https://doi.org/10.1039/B908625K
Ver Meer MA, Narasimhan B, Shanks BH, Mallapragada SK (2010) Effect of mesoporosity on thermal and mechanical properties of polystyrene/silica composites. ACS Appl Mater Interfaces 2:41–47. https://doi.org/10.1021/am900540x
Verho O, Gao F, Johnston EV, Wan W, Nagendiran A, Zheng H, Bäckvall J-E, Zou X (2014) Mesoporous silica nanoparticles applied as a support for Pd and Au nanocatalysts in cycloisomerization reactions. APL Mater 2:113316. https://doi.org/10.1063/1.4901293
Vinu A, Gokulakrishnan N, Balasubramanian VV, Alam S, Kapoor MP, Ariga K, Mori T (2008) Three-dimensional ultralarge-pore IA3d mesoporous silica with various pore diameters and their application in biomolecule immobilization. Chem Eur J 141:1529–11538. https://doi.org/10.1002/chem.200801304
Wang Y, Sun L, Jiang T, Zhang J, Zhang C, Sun C, Deng Y, Sun J, Wang S (2014) The investigation of MCM-48-type and MCM-41-type mesoporous silica as oral solid dispersion carriers for water insoluble cilostazol. Drug Dev Ind Pharm 40:819–828. https://doi.org/10.3109/03639045.2013.788013
Xu B, Ju Y, Song G, Cui Y (2013) tLyP-1-Conjugated mesoporous silica nanoparticles for tumor targeting and penetrating hydrophobic drug delivery. J Nanopart Res 15:2105–2112. https://doi.org/10.1007/s11051-013-2105-4
Yanes RE, Tamanoi F (2012) Development of mesoporous silica nanomaterials as a vehicle for anticancer drug delivery. Ther Deliv 3:389–404. https://doi.org/10.4155/tde.12.9
Zhang K, Zhang Y, Hou Q-W, Yuan E-H, Jiang JG, Albela B, He M-Y, Bonneviot L (2011) Novel synthesis and molecularly scaled surface hydrophobicity control of colloidal mesoporous silica. Microporous Mesoporous Mater 143:401–405. https://doi.org/10.1016/j.micromeso.2011.03.026
Zhang L, Zhang G, Wang S, Peng J, Cui W (2017) Sulfoethyl functionalized silica nanoparticle as an adsorbent to selectively adsorb silver ions from aqueous solutions. J Taiwan Inst Chem E 71:330–337. https://doi.org/10.1016/j.jtice.2017.01.001
Acknowledgements
The authors would like to thank Christian Splith from the University of Leipzig for the contribution in taking SEM images of the nanoparticles.
Funding
The authors received financial support from the Institute of Chemical Technology, Faculty of Chemistry and Mineralogy, University of Leipzig, and the German Academic Exchange Service (DAAD) for this research work.
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Yismaw, S., Kohns, R., Schneider, D. et al. Particle size control of monodispersed spherical nanoparticles with MCM-48-type mesostructure via novel rapid synthesis procedure. J Nanopart Res 21, 258 (2019). https://doi.org/10.1007/s11051-019-4699-7
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DOI: https://doi.org/10.1007/s11051-019-4699-7