Amphiphilic N-Heterocyclic Carbene-Stabilized Gold Nanoparticles and Their Self-Assembly in Polar SolventsClick to copy article linkArticle link copied!
Abstract
Soft matter-directed self-assembly of amphiphilic inorganic nanoparticles (NPs) has recently emerged as a promising approach to access NP ensembles with superior collective properties. While thiol-terminated molecules are primarily employed to tether the amphiphilic ligand to the metal, concerns remain regarding the stabilities of the resulting NPs and their corresponding aggregates. As an alternative, we report amphiphilic N-heterocyclic carbene (NHC)-functionalized gold nanoparticles (AuNPs). To accomplish this, an amphiphilic NHC-AuI complex based on an asymmetric triethylene glycol-/dodecyl-functionalized benzimidazole was first synthesized and used to prepare the corresponding stable amphiphilic NHC-decorated AuNPs. The resulting NPs were comprehensively characterized using both solution- and solid-state-based techniques such as proton nuclear magnetic resonance spectroscopy, dynamic light scattering, transmission electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. By optimizing the self-assembly behavior of these amphiphilic AuNPs in deionized water, ethanol, and their mixtures, we were able to fine-tune the plasmonic properties of the AuNPs in the wide range of 525–640 nm. Furthermore, when treated with thiols, the ensembles showed greater stability compared to their parent discrete AuNP counterparts at room temperature.
Cited By
This article is cited by 49 publications.
- Justin T. Lomax, Eden Goodwin, Mark D. Aloisio, Alex J. Veinot, Ishwar Singh, Wai-Tung Shiu, Maram Bakiro, Jordan Bentley, Joseph F. DeJesus, Peter G. Gordon, Lijia Liu, Seán T. Barry, Cathleen M. Crudden, Paul J. Ragogna. Deposition of N-Heterocyclic Carbenes on Reactive Metal Substrates─Applications in Area-Selective Atomic Layer Deposition. Chemistry of Materials 2024, 36
(11)
, 5500-5507. https://doi.org/10.1021/acs.chemmater.4c00412
- Moushakhi Ghosh, Paramita Saha, Sumit Roy, Sudip Barman, Pramod Pillai, Abhishek Dey, Shabana Khan. Cyclic(alkyl)(amino)carbene-Stabilized Gold Nanoparticles for Selective CO2 Reduction. ACS Catalysis 2024, 14
(9)
, 7011-7019. https://doi.org/10.1021/acscatal.3c05727
- Alexandre Porcheron, Omar Sadek, Salem Ba Sowid, Nathalie Bridonneau, Laura Hippolyte, Dimitri Mercier, Philippe Marcus, Lukmonjon Mutalliev, Clément Chauvier, Corinne Chanéac, Louis Fensterbank, François Ribot. Direct Synthesis of Mesoionic Carbene (MIC)-Stabilized Gold Nanoparticles from 1,2,3-Triazolium Salts. Chemistry of Materials 2023, 35
(17)
, 6865-6876. https://doi.org/10.1021/acs.chemmater.3c01162
- Paul A. Lummis, Kimberly M. Osten, Tetyana I. Levchenko, Maryam Sabooni Asre Hazer, Sami Malola, Bryan Owens-Baird, Alex J. Veinot, Emily L. Albright, Gabriele Schatte, Shinjiro Takano, Kirill Kovnir, Kevin G. Stamplecoskie, Tatsuya Tsukuda, Hannu Häkkinen, Masakazu Nambo, Cathleen M. Crudden. NHC-Stabilized Au10 Nanoclusters and Their Conversion to Au25 Nanoclusters. JACS Au 2022, 2
(4)
, 875-885. https://doi.org/10.1021/jacsau.2c00004
- Diep. T. H. Nguyen, Marilyne Bélanger-Bouliga, Lorianne R. Shultz, Arunava Maity, Titel Jurca, Ali Nazemi. Robust Water-Soluble Gold Nanoparticles via Polymerized Mesoionic N-Heterocyclic Carbene–Gold(I) Complexes. Chemistry of Materials 2021, 33
(24)
, 9588-9600. https://doi.org/10.1021/acs.chemmater.1c02899
- Jindong Ren, Matthias Freitag, Christian Schwermann, Anne Bakker, Saeed Amirjalayer, Andreas Rühling, Hong-Ying Gao, Nikos L. Doltsinis, Frank Glorius, Harald Fuchs. A Unidirectional Surface-Anchored N-Heterocyclic Carbene Rotor. Nano Letters 2020, 20
(8)
, 5922-5928. https://doi.org/10.1021/acs.nanolett.0c01884
- Shahar Dery, Iris Berg, Suhong Kim, Albano Cossaro, Alberto Verdini, Luca Floreano, F. Dean Toste, Elad Gross. Strong Metal–Adsorbate Interactions Increase the Reactivity and Decrease the Orientational Order of OH-Functionalized N-Heterocyclic Carbene Monolayers. Langmuir 2020, 36
(3)
, 697-703. https://doi.org/10.1021/acs.langmuir.9b02401
- Siming Yu, Rong Wen, Haiyang Wang, Yongchao Zha, Lin Qiu, Bo Li, Wei Xue, Dong Ma. Chitosan-graft-Poly(l-lysine) Dendron-Assisted Facile Self-Assembly of Au Nanoclusters for Enhanced X-ray Computer Tomography Imaging and Precise MMP-9 Plasmid shRNA Delivery. Chemistry of Materials 2019, 31
(11)
, 3992-4007. https://doi.org/10.1021/acs.chemmater.9b00507
- Christene
A. Smith, Mina R. Narouz, Paul A. Lummis, Ishwar Singh, Ali Nazemi, Chien-Hung Li, Cathleen M. Crudden. N-Heterocyclic Carbenes in Materials Chemistry. Chemical Reviews 2019, 119
(8)
, 4986-5056. https://doi.org/10.1021/acs.chemrev.8b00514
- Michael
J. Trujillo, Shelby L. Strausser, Jeffrey C. Becca, Joseph F. DeJesus, Lasse Jensen, David M. Jenkins, Jon P. Camden. Using SERS To Understand the Binding of N-Heterocyclic Carbenes to Gold Surfaces. The Journal of Physical Chemistry Letters 2018, 9
(23)
, 6779-6785. https://doi.org/10.1021/acs.jpclett.8b02764
- Anne Bakker, Alexander Timmer, Elena Kolodzeiski, Matthias Freitag, Hong Ying Gao, Harry Mönig, Saeed Amirjalayer, Frank Glorius, Harald Fuchs. Elucidating the Binding Modes of N-Heterocyclic Carbenes on a Gold Surface. Journal of the American Chemical Society 2018, 140
(38)
, 11889-11892. https://doi.org/10.1021/jacs.8b06180
- Omar Sadek, Jad Rabah, Salem Ba Sowid, Dimitri Mercier, Philippe Marcus, Clément Chauvier, François Ribot, Louis Fensterbank, Emmanuel Maisonhaute. Tailored functional monolayers made from mesoionic carbenes. Electrochimica Acta 2024, 507 , 145189. https://doi.org/10.1016/j.electacta.2024.145189
- Constantin Eisen, Bernhard K. Keppler, Jia Min Chin, Xiaodi Su, Michael R. Reithofer. Fabrication of azido-PEG-NHC stabilized gold nanoparticles as a functionalizable platform. Chemical Science 2024, 15
(44)
, 18524-18533. https://doi.org/10.1039/D4SC04112G
- Nathaniel Ukah, Hermann A. Wegner. On-surface synthesis – Ullmann coupling reactions on N-heterocyclic carbene functionalized gold nanoparticles. Nanoscale 2024, 16
(39)
, 18524-18533. https://doi.org/10.1039/D4NR03065F
- Polina M. Ivantcova, Eugene L. Kolychev, Artem A. Sizikov, Elizaveta N. Mochalova, Vladimir R. Cherkasov, Maxim P. Nikitin. Carbene-coated metal nanoparticles for in vivo applications. Colloids and Surfaces B: Biointerfaces 2024, 242 , 114097. https://doi.org/10.1016/j.colsurfb.2024.114097
- Lucille Kuster, Marilyne Bélanger-Bouliga, Thomas E. Shaw, Titel Jurca, Ali Nazemi, Mathieu Frenette. Insight into the nature of carbon–metal bonding for
N
-heterocyclic carbenes in gold/silver complexes and nanoparticles using DFT-correlated Raman spectroscopy: strong evidence for π-backbonding. Nanoscale 2024, 16
(23)
, 11052-11068. https://doi.org/10.1039/D4NR00143E
- Iris Berg, Luca Schio, Justus Reitz, Elena Molteni, Linoy Lahav, Carolina Gutiérrez Bolaños, Andrea Goldoni, Cesare Grazioli, Guido Fratesi, Max M. Hansmann, Luca Floreano, Elad Gross. Self‐Assembled Monolayers of N‐Heterocyclic Olefins on Au(111). Angewandte Chemie International Edition 2023, 62
(46)
https://doi.org/10.1002/anie.202311832
- Iris Berg, Luca Schio, Justus Reitz, Elena Molteni, Linoy Lahav, Carolina Gutiérrez Bolaños, Andrea Goldoni, Cesare Grazioli, Guido Fratesi, Max M. Hansmann, Luca Floreano, Elad Gross. Self‐Assembled Monolayers of N‐Heterocyclic Olefins on Au(111). Angewandte Chemie 2023, 135
(46)
https://doi.org/10.1002/ange.202311832
- Robert Richstein, Constantin Eisen, Lingcong Ge, Monnaya Chalermnon, Florian Mayer, Bernhard K. Keppler, Jia Min Chin, Michael R. Reithofer. NHC stabilized copper nanoparticles
via
reduction of a copper NHC complex. Chemical Communications 2023, 59
(64)
, 9738-9741. https://doi.org/10.1039/D3CC02745G
- Marilyne Bélanger-Bouliga, Nadjib Kihal, Hanae Mahious, Phuong Trang Nguyen, Steve Bourgault, Ali Nazemi. Synthesis and characterization of tetraphenylethylene-functionalized
N
-heterocyclic carbene-stabilized gold nanoparticles with aggregation-induced emission. Canadian Journal of Chemistry 2023, 101
(7)
, 477-486. https://doi.org/10.1139/cjc-2022-0260
- Constantin Eisen, Lingcong Ge, Elena Santini, Jia Min Chin, Robert T. Woodward, Michael R. Reithofer. Hyper crosslinked polymer supported NHC stabilized gold nanoparticles with excellent catalytic performance in flow processes. Nanoscale Advances 2023, 5
(4)
, 1095-1101. https://doi.org/10.1039/D2NA00799A
- Gurkiran Kaur, Rebekah L. Thimes, Jon P. Camden, David M. Jenkins. Fundamentals and applications of N-heterocyclic carbene functionalized gold surfaces and nanoparticles. Chemical Communications 2022, 58
(95)
, 13188-13197. https://doi.org/10.1039/D2CC05183D
- Bei He, Jingbo Ai, Junli Ren, Lihong Zhao, He Zhao, Chuanfu Liu, Huiming Fan. Alkyl ketene dimer grafted cationic cellulose stabilizing nano magnesium oxide for efficient protection of acidic paper. Cellulose 2022, 29
(16)
, 8863-8877. https://doi.org/10.1007/s10570-022-04812-2
- Sophie R. Thomas, Wenjie Yang, David J. Morgan, Thomas E. Davies, Jiao Jiao Li, Roland A. Fischer, Jun Huang, Nikolaos Dimitratos, Angela Casini. Bottom‐up Synthesis of Water‐Soluble Gold Nanoparticles Stabilized by N‐Heterocyclic Carbenes: From Structural Characterization to Applications. Chemistry – A European Journal 2022, 28
(56)
https://doi.org/10.1002/chem.202201575
- Hui Shen, Guolong Tian, Zhen Xu, Lingzheng Wang, Qingyuan Wu, Yuhao Zhang, Boon K. Teo, Nanfeng Zheng. N-heterocyclic carbene coordinated metal nanoparticles and nanoclusters. Coordination Chemistry Reviews 2022, 458 , 214425. https://doi.org/10.1016/j.ccr.2022.214425
- Juan C. Flores, Gustavo F. Silbestri, Ernesto de Jesús. Water-soluble transition-metal complexes with hydrophilic N-heterocyclic carbene ligands for aqueous-phase applications. 2022, 169-242. https://doi.org/10.1016/bs.adomc.2022.02.002
- Constantin Eisen, Jia Min Chin, Michael R. Reithofer. Catalytically Active Gold Nanomaterials Stabilized by
N
‐heterocyclic Carbenes. Chemistry – An Asian Journal 2021, 16
(20)
, 3026-3037. https://doi.org/10.1002/asia.202100731
- Maximilian Koy, Peter Bellotti, Mowpriya Das, Frank Glorius. N-Heterocyclic carbenes as tunable ligands for catalytic metal surfaces. Nature Catalysis 2021, 4
(5)
, 352-363. https://doi.org/10.1038/s41929-021-00607-z
- Marilyne Bélanger-Bouliga, Raja Mahious, Poulomsongo Iman Pitroipa, Ali Nazemi. Perylene diimide-tagged
N
-heterocyclic carbene-stabilized gold nanoparticles: How much ligand desorbs from surface in presence of thiols?. Dalton Transactions 2021, 50
(16)
, 5598-5606. https://doi.org/10.1039/D1DT00064K
- Sophie R. Thomas, Angela Casini. N-Heterocyclic carbenes as “smart” gold nanoparticle stabilizers: State-of-the art and perspectives for biomedical applications. Journal of Organometallic Chemistry 2021, 938 , 121743. https://doi.org/10.1016/j.jorganchem.2021.121743
- Moulali Vaddamanu, Arruri Sathyanarayana, Yamane Masaya, Shohei Sugiyama, Ozaki Kazuhisa, Kavitha Velappan, Muneshwar Nandeshwar, Kyohei Hisano, Osamu Tsutsumi, Ganesan Prabusankar. Acridine
N
‐Heterocyclic Carbene Gold(I) Compounds: Tuning from Yellow to Blue Luminescence. Chemistry – An Asian Journal 2021, 16
(5)
, 521-529. https://doi.org/10.1002/asia.202001380
- David Ventura-Espinosa, Santiago Martín, Hermenegildo García, Jose A. Mata. Ligand effects in the stabilization of gold nanoparticles anchored on the surface of graphene: Implications in catalysis. Journal of Catalysis 2021, 394 , 113-120. https://doi.org/10.1016/j.jcat.2020.12.027
- Xing‐Xing Gou, Tong Liu, Yao‐Yu Wang, Ying‐Feng Han. Ultrastable and Highly Catalytically Active N‐Heterocyclic‐Carbene‐Stabilized Gold Nanoparticles in Confined Spaces. Angewandte Chemie 2020, 132
(38)
, 16826-16832. https://doi.org/10.1002/ange.202006569
- Xing‐Xing Gou, Tong Liu, Yao‐Yu Wang, Ying‐Feng Han. Ultrastable and Highly Catalytically Active N‐Heterocyclic‐Carbene‐Stabilized Gold Nanoparticles in Confined Spaces. Angewandte Chemie International Edition 2020, 59
(38)
, 16683-16689. https://doi.org/10.1002/anie.202006569
- Anne Bakker, Matthias Freitag, Elena Kolodzeiski, Peter Bellotti, Alexander Timmer, Jindong Ren, Bertram Schulze Lammers, Daniel Moock, Herbert W. Roesky, Harry Mönig, Saeed Amirjalayer, Harald Fuchs, Frank Glorius. Ein elektronenreiches cyclisches (Alkyl)(amino)carben auf Au(111)‐, Ag(111)‐ und Cu(111)‐Oberflächen. Angewandte Chemie 2020, 132
(32)
, 13745-13749. https://doi.org/10.1002/ange.201915618
- Anne Bakker, Matthias Freitag, Elena Kolodzeiski, Peter Bellotti, Alexander Timmer, Jindong Ren, Bertram Schulze Lammers, Daniel Moock, Herbert W. Roesky, Harry Mönig, Saeed Amirjalayer, Harald Fuchs, Frank Glorius. An Electron‐Rich Cyclic (Alkyl)(Amino)Carbene on Au(111), Ag(111), and Cu(111) Surfaces. Angewandte Chemie International Edition 2020, 59
(32)
, 13643-13646. https://doi.org/10.1002/anie.201915618
- Liudmila Trotsiuk, Artsiom Antanovich, Anna Lizunova, Olga Kulakovich. Direct synthesis of amphiphilic polyvinylpyrrolidone-capped gold nanoparticles in chloroform. Colloid and Interface Science Communications 2020, 37 , 100289. https://doi.org/10.1016/j.colcom.2020.100289
- Joseph F. DeJesus, Lindy M. Sherman, Darius J. Yohannan, Jeffrey C. Becca, Shelby L. Strausser, Leonhard F. P. Karger, Lasse Jensen, David M. Jenkins, Jon P. Camden. A Benchtop Method for Appending Protic Functional Groups to N‐Heterocyclic Carbene Protected Gold Nanoparticles. Angewandte Chemie 2020, 132
(19)
, 7655-7660. https://doi.org/10.1002/ange.202001440
- Joseph F. DeJesus, Lindy M. Sherman, Darius J. Yohannan, Jeffrey C. Becca, Shelby L. Strausser, Leonhard F. P. Karger, Lasse Jensen, David M. Jenkins, Jon P. Camden. A Benchtop Method for Appending Protic Functional Groups to N‐Heterocyclic Carbene Protected Gold Nanoparticles. Angewandte Chemie International Edition 2020, 59
(19)
, 7585-7590. https://doi.org/10.1002/anie.202001440
- Guillem Fernández, Laura Bernardo, Ana Villanueva, Roser Pleixats. Gold nanoparticles stabilized by PEG-tagged imidazolium salts as recyclable catalysts for the synthesis of propargylamines and the cycloisomerization of γ-alkynoic acids. New Journal of Chemistry 2020, 44
(16)
, 6130-6141. https://doi.org/10.1039/D0NJ00284D
- Tongfan Hao, Haina Tan, Shanlong Li, Yuling Wang, Zhiping Zhou, Chunyang Yu, Yongfeng Zhou, Deyue Yan. Multilayer onion‐like vesicles self‐assembled from amphiphilic hyperbranched multiarm copolymers via simulation. Journal of Polymer Science 2020, 58
(5)
, 704-715. https://doi.org/10.1002/pol.20190163
- Adam J. Young, Constantin Eisen, Guilherme M.D.M. Rubio, Jia Min Chin, Michael R. Reithofer. pH responsive histidin-2-ylidene stabilized gold nanoparticles. Journal of Inorganic Biochemistry 2019, 199 , 110707. https://doi.org/10.1016/j.jinorgbio.2019.110707
- David Ventura-Espinosa, Santiago Martín, Jose A. Mata. The non-innocent role of graphene in the formation/immobilization of ultra-small gold nanoparticles functionalized with N-heterocyclic carbene ligands. Journal of Catalysis 2019, 375 , 419-426. https://doi.org/10.1016/j.jcat.2019.06.009
- Adam J. Young, Markus Sauer, Guilherme M. D. M. Rubio, Akiko Sato, Annette Foelske, Christopher J. Serpell, Jia Min Chin, Michael R. Reithofer. One-step synthesis and XPS investigations of chiral NHC–Au(0)/Au(
i
) nanoparticles. Nanoscale 2019, 11
(17)
, 8327-8333. https://doi.org/10.1039/C9NR00905A
- Yuan‐Yuan An, Jian‐Gang Yu, Ying‐Feng Han. Recent Advances in the Chemistry of
N
‐Heterocyclic‐Carbene‐Functionalized Metal‐Nanoparticles and Their Applications. Chinese Journal of Chemistry 2019, 37
(1)
, 76-87. https://doi.org/10.1002/cjoc.201800450
- Patricia Tegeder, Matthias Freitag, Kathryn M. Chepiga, Satoshi Muratsugu, Nadja Möller, Sebastian Lamping, Mizuki Tada, Frank Glorius, Bart Jan Ravoo. N‐Heterocyclic Carbene‐Modified Au–Pd Alloy Nanoparticles and Their Application as Biomimetic and Heterogeneous Catalysts. Chemistry – A European Journal 2018, 24
(70)
, 18682-18688. https://doi.org/10.1002/chem.201803274
- Lena Rakers, Luis M. Martínez-Prieto, Angela M. López-Vinasco, Karine Philippot, Piet W. N. M. van Leeuwen, Bruno Chaudret, Frank Glorius. Ruthenium nanoparticles ligated by cholesterol-derived NHCs and their application in the hydrogenation of arenes. Chemical Communications 2018, 54
(51)
, 7070-7073. https://doi.org/10.1039/C8CC02833H
- N. Bridonneau, L. Hippolyte, D. Mercier, D. Portehault, M. Desage-El Murr, P. Marcus, L. Fensterbank, C. Chanéac, F. Ribot. N-Heterocyclic carbene-stabilized gold nanoparticles with tunable sizes. Dalton Transactions 2018, 47
(19)
, 6850-6859. https://doi.org/10.1039/C8DT00416A
- Lisa Stephens, J. Daniel Padmos, Mina R. Narouz, Abrar Al-Rashed, Chien-Hung Li, Nicholas Payne, Matthew Zamora, Cathleen M. Crudden, Janine Mauzeroll, J. Hugh Horton. The Structural and Electrochemical Effects of N-Heterocyclic Carbene Monolayers on Magnesium. Journal of The Electrochemical Society 2018, 165
(13)
, G139-G145. https://doi.org/10.1149/2.0501811jes
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.