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Nonsurfactant Supramolecular Synthesis of Ordered Mesoporous Silica
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. (Nanotechnology and Functional Materials)
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. (Nanotechnology and Functional Materials)
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
2009 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 131, no 9, 3189-3191 p.Article in journal (Refereed) Published
Abstract [en]

Hoogsteen-bonded tetrads and pentamers are formed by a large variety of organic molecules through H-donor and acceptor groups capable of inducing self-organization to form columnar and hexagonal mesophases. The biological importance of such macromolecular structures is exemplified by the assembly of guanosine-rich groups of telomere units and their implication in chromosomal replication. Folic acid is composed of a pterin group, chemically and structurally similar to guanine, conjugated to an l-glutamate moiety via a p-amino benzoic acid. Our aim has been to develop a delivery vehicle for folic acid and at the same time provide a novel synthetic route for ordered mesoporous materials without the use of amphiphilic surfactants. We present a new nonsurfactant route for the synthesis of highly ordered mesoporous materials, based on the supramolecular templating of stacked arrays of the tetramer-forming pterin groups of folic acid under a variety of synthetic conditions. This method leads to hexagonally ordered mesoporous structures with gyroid, spherical, and chiral morphologies with pores on the order of 25−30 Å in diameter and surface areas above 1000 m2/g. More importantly circular dichroism studies reveal that the folate template possesses a chiral signature within the pores in the as-synthesized solid and that chirality is transferred from the folate template to the pore surface via the aminopropyl triethoxysilane costructure directing agent used in the supramolecular assembly. This novel templating approach for ordered mesoporous materials breaks the hegemony of surfactant micellar systems for the preparation of these exciting high surface area solids and opens new opportunities for structural control, design of pore geometry, and novel applications.

Place, publisher, year, edition, pages
2009. Vol. 131, no 9, 3189-3191 p.
National Category
Engineering and Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-99093DOI: 10.1021/ja8096477ISI: 000264792400033PubMedID: 19220057OAI: oai:DiVA.org:uu-99093DiVA: diva2:202102
Available from: 2009-03-06 Created: 2009-03-06 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Novel Syntheses, Structures and Functions of Mesoporous Silica Materials
Open this publication in new window or tab >>Novel Syntheses, Structures and Functions of Mesoporous Silica Materials
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The field of mesoporous silica has been studied for about 20 years but it is still an area attracting a lot of attention. The use of novel templating molecules and several issues related to the synthesis and fine structural details are still poorly understood. These aspects are of special relevance to the theme of this thesis, which includes novel work on three fronts; the synthesis, characterization and applications of mesoporous materials.

The work described in this thesis aims to contribute to the mesoporous field by developing novel methods of mesoporous silica synthesis without relying on surfactant micelles as the templating agent but focusing instead on the stacking arrangement of aromatic molecules such as folic acid. The novel route presented here leads to 2D hexagonal structures with p6mm symmetry possessing high mesoporosity and large surface areas. The versatility of this route at various synthesis temperatures and using hydrothermal treatments has also been investigated.

A novel strategy is also proposed for the synthesis of mesocaged materials with Pm3n symmetry structures. The mechanism relies on the penetration of the neutral propylamino moiety of a co-structure directing agent into the hydrophobic core of the surfactant micelles. Beside these novel pathways, the effect of hydrothermal treatment (HT) at 100 oC on the 3D cubic Ia3d structure (AMS-6) over a long period of time was also examined, and the results show a phase transformation from a 3D cubic Ia3d to a 2D hexagonal p6mm structure and a return to the 3D cubic Ia3d structure at a later stage in the synthesis. This unexpected result is discussed.

In this work, the detailed structural characterization of mesoporous materials using electron microscopy techniques is an important task. In particular, to extend previous knowledge, the fine structural details of mesocaged materials possessing Pm3n symmetry prepared with various amphiphilic surfactants under acidic and alkaline conditions has been investigated using electron crystallography and sorption studies. The results show subtle fine structural differences with materials prepared under alkaline conditions exhibiting the largest mesocage sizes. The cage and window sizes are primarily determined by the charge density of the surfactant and the thickness of the hydration layer surrounding the surfactant micelles.

The relationship between the mesoporous structure and its function has been investigated by evaluating the rate of release of amphiphilic molecules, used as model molecules, from the internal pore structures of mesoporous materials with different pore geometries. In a similar study, the rate of proton diffusion from a liquid surrounding the mesoporous nanoparticles into the pore system of AMS-n was also assessed. The results show that the diffusion coefficients for the proton absorption process are higher than those for the release of the surfactant template molecules, with more complex 3D mesocaged particles showing the highest diffusion coefficients in both cases.

Finally, the quantity of CO2 adsorption was measured by modifying the internal surfaces of mesocaged material with n-propylamino groups. Results show that the cage-connecting window sizes limit the surface coverage of n-propylamino groups by pore blocking and affect the volume of CO2 adsorption. In addition, at the molecular level, CO2 adsorption shows physisorption or chemisorption depending on the localized distribution of n-propylamino groups, as studied by in-situ infrared spectroscopy.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2010. 82 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 733
National Category
Materials Engineering
Research subject
Materials Science
Identifiers
urn:nbn:se:uu:diva-122289 (URN)978-91-554-7786-8 (ISBN)
Public defence
2010-05-21, Siegbahnsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:00 (English)
Opponent
Supervisors
Available from: 2010-04-28 Created: 2010-04-07 Last updated: 2010-05-18

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Atluri, RambabuGarcia-Bennett, Alfonso

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