Gold Nanoparticles Modification with Liquid Crystalline Polybenzylic Dendrons via 1,3-Dipolar Cycloaddition
A series of six polybenzylic dendrons with an alkynyl focal point were synthesized for their incorporation to gold nanoparticles. Five of these compounds showed columnar mesomorphism in a wide range of temperatures. These dendrons were reacted with gold nanoparticles stabilized with a combination of...
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| Format: | Article |
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MDPI AG
2022-11-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/12/22/4026 |
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| author | José Antonio Ulloa Joaquín Barberá José Luis Serrano |
| author_facet | José Antonio Ulloa Joaquín Barberá José Luis Serrano |
| author_sort | José Antonio Ulloa |
| collection | DOAJ |
| description | A series of six polybenzylic dendrons with an alkynyl focal point were synthesized for their incorporation to gold nanoparticles. Five of these compounds showed columnar mesomorphism in a wide range of temperatures. These dendrons were reacted with gold nanoparticles stabilized with a combination of a dodecanethiol and 11-azidoundecane-1-thiol. The azido group of the last compound allowed the functionalization of the nanoparticles with the six polybenzylic dendrons by 1,3-dipolar cycloaddition between their alkynyl groups and the terminal azido groups of the thiols. A high efficiency of the cycloaddition process (47–69%) was confirmed by several experimental techniques and no decomposition or aggregation phenomena were detected in the dendron-coated nanoparticles. The involved mechanism and the resulting percentage composition of the final materials are discussed. The results of the ulterior growth of the nanoparticles by thermal treatment are influenced by the size and the shape of the dendron and the temperature of the process. The structures of the final nanoparticles were investigated by TEM, DSC, TGA, NMR and UV-Vis spectroscopy. These nanoparticles do not show liquid crystal properties. However, a melting process between a crystalline and a fluid phase is observed. In the solid phase, the nanomaterials prepared show a short-range interaction between nanoparticles with a 2D local hexagonal order. A near-field effect was observed in the UV-vis spectra by coupling of different surface plasmon resonance bands (SPR) probably due to the short-range interactions. The main novelty of this work lies in the scarcity of previous studies of gold nanoparticles coated with dendrons forming themselves columnar mesophases. Most of the studies reported in the literature deal with gold nanoparticles coated with calamitic mesogens. Additionally, the effect of the thermal treatment, which in a previous paper was shown to increase the mean size of the nanoparticles without increasing their size polydispersity, has been studied in these materials. |
| first_indexed | 2024-03-09T18:06:30Z |
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| id | doaj.art-ea5c45adfa5d4340a073668e7ea61f5b |
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| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-09T18:06:30Z |
| publishDate | 2022-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-ea5c45adfa5d4340a073668e7ea61f5b2023-11-24T09:28:28ZengMDPI AGNanomaterials2079-49912022-11-011222402610.3390/nano12224026Gold Nanoparticles Modification with Liquid Crystalline Polybenzylic Dendrons via 1,3-Dipolar CycloadditionJosé Antonio Ulloa0Joaquín Barberá1José Luis Serrano2Departamento de Polímeros, Facultad de Ciencias Químicas, Universidad de Concepción, Casilla 160-C, Calle Edmundo Larenas 129, Concepción 4070371, ChileDepartamento de Química Orgánica, Facultad de Ciencias, Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-Universidad de Zaragoza, 50009 Zaragoza, SpainDepartamento de Química Orgánica, Facultad de Ciencias, Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-Universidad de Zaragoza, 50009 Zaragoza, SpainA series of six polybenzylic dendrons with an alkynyl focal point were synthesized for their incorporation to gold nanoparticles. Five of these compounds showed columnar mesomorphism in a wide range of temperatures. These dendrons were reacted with gold nanoparticles stabilized with a combination of a dodecanethiol and 11-azidoundecane-1-thiol. The azido group of the last compound allowed the functionalization of the nanoparticles with the six polybenzylic dendrons by 1,3-dipolar cycloaddition between their alkynyl groups and the terminal azido groups of the thiols. A high efficiency of the cycloaddition process (47–69%) was confirmed by several experimental techniques and no decomposition or aggregation phenomena were detected in the dendron-coated nanoparticles. The involved mechanism and the resulting percentage composition of the final materials are discussed. The results of the ulterior growth of the nanoparticles by thermal treatment are influenced by the size and the shape of the dendron and the temperature of the process. The structures of the final nanoparticles were investigated by TEM, DSC, TGA, NMR and UV-Vis spectroscopy. These nanoparticles do not show liquid crystal properties. However, a melting process between a crystalline and a fluid phase is observed. In the solid phase, the nanomaterials prepared show a short-range interaction between nanoparticles with a 2D local hexagonal order. A near-field effect was observed in the UV-vis spectra by coupling of different surface plasmon resonance bands (SPR) probably due to the short-range interactions. The main novelty of this work lies in the scarcity of previous studies of gold nanoparticles coated with dendrons forming themselves columnar mesophases. Most of the studies reported in the literature deal with gold nanoparticles coated with calamitic mesogens. Additionally, the effect of the thermal treatment, which in a previous paper was shown to increase the mean size of the nanoparticles without increasing their size polydispersity, has been studied in these materials.https://www.mdpi.com/2079-4991/12/22/4026gold nanoparticles modificationliquid crystalline dendronsclick-chemistrynanoparticles functionalization |
| spellingShingle | José Antonio Ulloa Joaquín Barberá José Luis Serrano Gold Nanoparticles Modification with Liquid Crystalline Polybenzylic Dendrons via 1,3-Dipolar Cycloaddition Nanomaterials gold nanoparticles modification liquid crystalline dendrons click-chemistry nanoparticles functionalization |
| title | Gold Nanoparticles Modification with Liquid Crystalline Polybenzylic Dendrons via 1,3-Dipolar Cycloaddition |
| title_full | Gold Nanoparticles Modification with Liquid Crystalline Polybenzylic Dendrons via 1,3-Dipolar Cycloaddition |
| title_fullStr | Gold Nanoparticles Modification with Liquid Crystalline Polybenzylic Dendrons via 1,3-Dipolar Cycloaddition |
| title_full_unstemmed | Gold Nanoparticles Modification with Liquid Crystalline Polybenzylic Dendrons via 1,3-Dipolar Cycloaddition |
| title_short | Gold Nanoparticles Modification with Liquid Crystalline Polybenzylic Dendrons via 1,3-Dipolar Cycloaddition |
| title_sort | gold nanoparticles modification with liquid crystalline polybenzylic dendrons via 1 3 dipolar cycloaddition |
| topic | gold nanoparticles modification liquid crystalline dendrons click-chemistry nanoparticles functionalization |
| url | https://www.mdpi.com/2079-4991/12/22/4026 |
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