High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control Mechanisms

Mesoporous silica nanostructures (MSNs) attract high interest due to their unique and tunable physical chemical features, including high specific surface area and large pore volume, that hold a great potential in a variety of fields, i.e., adsorption, catalysis, and biomedicine. An essential feature...

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Main Authors: Federica Rizzi, Rachele Castaldo, Tiziana Latronico, Pierluigi Lasala, Gennaro Gentile, Marino Lavorgna, Marinella Striccoli, Angela Agostiano, Roberto Comparelli, Nicoletta Depalo, Maria Lucia Curri, Elisabetta Fanizza
Format: Article
Language:English
Published: MDPI AG 2021-07-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/26/14/4247
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author Federica Rizzi
Rachele Castaldo
Tiziana Latronico
Pierluigi Lasala
Gennaro Gentile
Marino Lavorgna
Marinella Striccoli
Angela Agostiano
Roberto Comparelli
Nicoletta Depalo
Maria Lucia Curri
Elisabetta Fanizza
author_facet Federica Rizzi
Rachele Castaldo
Tiziana Latronico
Pierluigi Lasala
Gennaro Gentile
Marino Lavorgna
Marinella Striccoli
Angela Agostiano
Roberto Comparelli
Nicoletta Depalo
Maria Lucia Curri
Elisabetta Fanizza
author_sort Federica Rizzi
collection DOAJ
description Mesoporous silica nanostructures (MSNs) attract high interest due to their unique and tunable physical chemical features, including high specific surface area and large pore volume, that hold a great potential in a variety of fields, i.e., adsorption, catalysis, and biomedicine. An essential feature for biomedical application of MSNs is limiting MSN size in the sub-micrometer regime to control uptake and cell viability. However, careful size tuning in such a regime remains still challenging. We aim to tackling this issue by developing two synthetic procedures for MSN size modulation, performed in homogenous aqueous/ethanol solution or two-phase aqueous/ethyl acetate system. Both approaches make use of tetraethyl orthosilicate as precursor, in the presence of cetyltrimethylammonium bromide, as structure-directing agent, and NaOH, as base-catalyst. NaOH catalyzed syntheses usually require high temperature (>80 °C) and large reaction medium volume to trigger MSN formation and limit aggregation. Here, a successful modulation of MSNs size from 40 up to 150 nm is demonstrated to be achieved by purposely balancing synthesis conditions, being able, in addition, to keep reaction temperature not higher than 50 °C (30 °C and 50 °C, respectively) and reaction mixture volume low. Through a comprehensive and in-depth systematic morphological and structural investigation, the mechanism and kinetics that sustain the control of MSNs size in such low dimensional regime are defined, highlighting that modulation of size and pores of the structures are mainly mediated by base concentration, reaction time and temperature and ageing, for the homogenous phase approach, and by temperature for the two-phase synthesis. Finally, an in vitro study is performed on bEnd.3 cells to investigate on the cytotoxicity of the MNSs.
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spelling doaj.art-350f708eb8ca494d865335868828dc912023-11-22T04:30:49ZengMDPI AGMolecules1420-30492021-07-012614424710.3390/molecules26144247High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control MechanismsFederica Rizzi0Rachele Castaldo1Tiziana Latronico2Pierluigi Lasala3Gennaro Gentile4Marino Lavorgna5Marinella Striccoli6Angela Agostiano7Roberto Comparelli8Nicoletta Depalo9Maria Lucia Curri10Elisabetta Fanizza11Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari, ItalyInstitute for Polymers, Composites and Biomaterials, Italian National Research Council, via Campi Flegrei 34, Pozzuoli, 80078 Naples, ItalyDepartment of Bioscience, Biotechnology and Biopharmaceutics, University of Bari, via Orabona 4, 70126 Bari, ItalyDepartment of Chemistry, University of Bari, via Orabona 4, 70126 Bari, ItalyInstitute for Polymers, Composites and Biomaterials, Italian National Research Council, via Campi Flegrei 34, Pozzuoli, 80078 Naples, ItalyInstitute for Polymers, Composites and Biomaterials, Italian National Research Council, Piazzale E. Fermi 1, Portici, 80055 Naples, ItalyInstitute for Physical Processes, Italian National Research Council, c/o Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari, ItalyDepartment of Chemistry, University of Bari, via Orabona 4, 70126 Bari, ItalyInstitute for Physical Processes, Italian National Research Council, c/o Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari, ItalyInstitute for Physical Processes, Italian National Research Council, c/o Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari, ItalyDepartment of Chemistry, University of Bari, via Orabona 4, 70126 Bari, ItalyDepartment of Chemistry, University of Bari, via Orabona 4, 70126 Bari, ItalyMesoporous silica nanostructures (MSNs) attract high interest due to their unique and tunable physical chemical features, including high specific surface area and large pore volume, that hold a great potential in a variety of fields, i.e., adsorption, catalysis, and biomedicine. An essential feature for biomedical application of MSNs is limiting MSN size in the sub-micrometer regime to control uptake and cell viability. However, careful size tuning in such a regime remains still challenging. We aim to tackling this issue by developing two synthetic procedures for MSN size modulation, performed in homogenous aqueous/ethanol solution or two-phase aqueous/ethyl acetate system. Both approaches make use of tetraethyl orthosilicate as precursor, in the presence of cetyltrimethylammonium bromide, as structure-directing agent, and NaOH, as base-catalyst. NaOH catalyzed syntheses usually require high temperature (>80 °C) and large reaction medium volume to trigger MSN formation and limit aggregation. Here, a successful modulation of MSNs size from 40 up to 150 nm is demonstrated to be achieved by purposely balancing synthesis conditions, being able, in addition, to keep reaction temperature not higher than 50 °C (30 °C and 50 °C, respectively) and reaction mixture volume low. Through a comprehensive and in-depth systematic morphological and structural investigation, the mechanism and kinetics that sustain the control of MSNs size in such low dimensional regime are defined, highlighting that modulation of size and pores of the structures are mainly mediated by base concentration, reaction time and temperature and ageing, for the homogenous phase approach, and by temperature for the two-phase synthesis. Finally, an in vitro study is performed on bEnd.3 cells to investigate on the cytotoxicity of the MNSs.https://www.mdpi.com/1420-3049/26/14/4247mesoporous silica nanoparticleshigh specific surface areacolloidal synthesis
spellingShingle Federica Rizzi
Rachele Castaldo
Tiziana Latronico
Pierluigi Lasala
Gennaro Gentile
Marino Lavorgna
Marinella Striccoli
Angela Agostiano
Roberto Comparelli
Nicoletta Depalo
Maria Lucia Curri
Elisabetta Fanizza
High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control Mechanisms
Molecules
mesoporous silica nanoparticles
high specific surface area
colloidal synthesis
title High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control Mechanisms
title_full High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control Mechanisms
title_fullStr High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control Mechanisms
title_full_unstemmed High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control Mechanisms
title_short High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control Mechanisms
title_sort high surface area mesoporous silica nanoparticles with tunable size in the sub micrometer regime insights on the size and porosity control mechanisms
topic mesoporous silica nanoparticles
high specific surface area
colloidal synthesis
url https://www.mdpi.com/1420-3049/26/14/4247
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