Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes
Amphiphilic nonionic ligands, synthesized with a fixed hydrophobic moiety formed by a thiolated alkyl chain and an aromatic ring, and with a hydrophilic tail composed of a variable number of oxyethylene units, were used to functionalize spherical gold nanoparticles (AuNPs) in water. Steady-state and...
| Main Authors: | , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2018-03-01
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| Series: | Nanomaterials |
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| Online Access: | http://www.mdpi.com/2079-4991/8/3/168 |
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| author | Joao Paulo Coelho José Osío Barcina Elena Junquera Emilio Aicart Gloria Tardajos Sergio Gómez-Graña Pablo Cruz-Gil Cástor Salgado Pablo Díaz-Núñez Ovidio Peña-Rodríguez Andrés Guerrero-Martínez |
| author_facet | Joao Paulo Coelho José Osío Barcina Elena Junquera Emilio Aicart Gloria Tardajos Sergio Gómez-Graña Pablo Cruz-Gil Cástor Salgado Pablo Díaz-Núñez Ovidio Peña-Rodríguez Andrés Guerrero-Martínez |
| author_sort | Joao Paulo Coelho |
| collection | DOAJ |
| description | Amphiphilic nonionic ligands, synthesized with a fixed hydrophobic moiety formed by a thiolated alkyl chain and an aromatic ring, and with a hydrophilic tail composed of a variable number of oxyethylene units, were used to functionalize spherical gold nanoparticles (AuNPs) in water. Steady-state and time-resolved fluorescence measurements of the AuNPs in the presence of α-cyclodextrin (α-CD) revealed the formation of supramolecular complexes between the ligand and macrocycle at the surface of the nanocrystals. The addition of α-CD induced the formation of inclusion complexes with a high apparent binding constant that decreased with the increasing oxyethylene chain length. The formation of polyrotaxanes at the surface of AuNPs, in which many α-CDs are trapped as hosts on the long and linear ligands, was demonstrated by the formation of large and homogeneous arrays of self-assembled AuNPs with hexagonal close packing, where the interparticle distance increased with the length of the oxyethylene chain. The estimated number of α-CDs per polyrotaxane suggests a high rigidization of the ligand upon complexation, allowing for nearly perfect control of the interparticle distance in the arrays. This degree of supramolecular control was extended to arrays formed by AuNPs stabilized with polyethylene glycol and even to binary arrays. Electromagnetic simulations showed that the enhancement and distribution of the electric field can be finely controlled in these plasmonic arrays. |
| first_indexed | 2024-12-11T16:41:49Z |
| format | Article |
| id | doaj.art-e309f92e6cf04b068c82054ef9583921 |
| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-12-11T16:41:49Z |
| publishDate | 2018-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-e309f92e6cf04b068c82054ef95839212022-12-22T00:58:18ZengMDPI AGNanomaterials2079-49912018-03-018316810.3390/nano8030168nano8030168Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin PolyrotaxanesJoao Paulo Coelho0José Osío Barcina1Elena Junquera2Emilio Aicart3Gloria Tardajos4Sergio Gómez-Graña5Pablo Cruz-Gil6Cástor Salgado7Pablo Díaz-Núñez8Ovidio Peña-Rodríguez9Andrés Guerrero-Martínez10Departamento de Química Física, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040 Madrid, SpainDepartamento de Química Orgánica, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040 Madrid, SpainDepartamento de Química Física, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040 Madrid, SpainDepartamento de Química Física, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040 Madrid, SpainDepartamento de Química Física, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040 Madrid, SpainDepartamento de Química en Ciencias Farmacéuticas, Universidad Complutense de Madrid, Plaza Ramón y Cajal s/n, 28040 Madrid, SpainDepartamento de Química Orgánica, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040 Madrid, SpainDepartamento de Química Orgánica, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040 Madrid, SpainInstituto de Fusión Nuclear, Universidad Politécnica de Madrid, José Gutiérrez Abascal 2, 28006 Madrid, SpainInstituto de Fusión Nuclear, Universidad Politécnica de Madrid, José Gutiérrez Abascal 2, 28006 Madrid, SpainDepartamento de Química Física, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040 Madrid, SpainAmphiphilic nonionic ligands, synthesized with a fixed hydrophobic moiety formed by a thiolated alkyl chain and an aromatic ring, and with a hydrophilic tail composed of a variable number of oxyethylene units, were used to functionalize spherical gold nanoparticles (AuNPs) in water. Steady-state and time-resolved fluorescence measurements of the AuNPs in the presence of α-cyclodextrin (α-CD) revealed the formation of supramolecular complexes between the ligand and macrocycle at the surface of the nanocrystals. The addition of α-CD induced the formation of inclusion complexes with a high apparent binding constant that decreased with the increasing oxyethylene chain length. The formation of polyrotaxanes at the surface of AuNPs, in which many α-CDs are trapped as hosts on the long and linear ligands, was demonstrated by the formation of large and homogeneous arrays of self-assembled AuNPs with hexagonal close packing, where the interparticle distance increased with the length of the oxyethylene chain. The estimated number of α-CDs per polyrotaxane suggests a high rigidization of the ligand upon complexation, allowing for nearly perfect control of the interparticle distance in the arrays. This degree of supramolecular control was extended to arrays formed by AuNPs stabilized with polyethylene glycol and even to binary arrays. Electromagnetic simulations showed that the enhancement and distribution of the electric field can be finely controlled in these plasmonic arrays.http://www.mdpi.com/2079-4991/8/3/168supramolecular chemistryself-assemblygold nanoparticlecyclodextrinpolyrotaxanearrayhot spotsurface-enhanced spectroscopy |
| spellingShingle | Joao Paulo Coelho José Osío Barcina Elena Junquera Emilio Aicart Gloria Tardajos Sergio Gómez-Graña Pablo Cruz-Gil Cástor Salgado Pablo Díaz-Núñez Ovidio Peña-Rodríguez Andrés Guerrero-Martínez Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes Nanomaterials supramolecular chemistry self-assembly gold nanoparticle cyclodextrin polyrotaxane array hot spot surface-enhanced spectroscopy |
| title | Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes |
| title_full | Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes |
| title_fullStr | Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes |
| title_full_unstemmed | Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes |
| title_short | Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes |
| title_sort | supramolecular control over the interparticle distance in gold nanoparticle arrays by cyclodextrin polyrotaxanes |
| topic | supramolecular chemistry self-assembly gold nanoparticle cyclodextrin polyrotaxane array hot spot surface-enhanced spectroscopy |
| url | http://www.mdpi.com/2079-4991/8/3/168 |
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