The structure and binding mode of citrate in the stabilization of gold nanoparticles

Hind Abdullah Moteg Aljohni; Edy Abou-Hamad; Abdesslem Jedidi; Cory M. Widdifield; Jasmine Viger-Gravel; Shiv Sangaru; David Gajan; Dalaver H. Anjum; Samy Ould-Chikh; Mohamed N. Hedhili; Andrei Gurinov; Michael J. Kelly; Mohamad El Eter; Luigi Cavallo; Jean-Marie Basset; Jean-Marie Basset

doi:10.1038/nchem.2752

The structure and binding mode of citrate in the stabilization of gold nanoparticles

Hind Abdullah Moteg Aljohni, Edy Abou-Hamad, Abdesslem Jedidi, Cory M. Widdifield, Jasmine Viger-Gravel, Shiv Sangaru, David Gajan, Dalaver H. Anjum, Samy Ould-Chikh, Mohamed N. Hedhili, Andrei Gurinov, Michael J. Kelly, Mohamad El Eter, Luigi Cavallo, Jean-Marie Basset, Jean-Marie Basset

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223 Scopus citations

Abstract

Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by 13C and 23Na solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1κO1) mode is favoured at high citrate:gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Auδ+ are observed. 23Na NMR experiments show that Na+ ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e− L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.

Original language	English (US)
Pages (from-to)	890-895
Number of pages	6
Journal	Nature Chemistry
Volume	9
Issue number	9
DOIs	https://doi.org/10.1038/nchem.2752
State	Published - Mar 27 2017

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work received support from the King Abdullah University of Science and Technology (KAUST) and ERC Advanced Grant No. 320860. For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia.

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10.1038/nchem.2752

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Aljohni, H. A. M., Abou-Hamad, E., Jedidi, A., Widdifield, C. M., Viger-Gravel, J., Sangaru, S., Gajan, D., Anjum, D. H., Ould-Chikh, S., Hedhili, M. N., Gurinov, A., Kelly, M. J., El Eter, M., Cavallo, L., Basset, J.-M., & Basset, J.-M. (2017). The structure and binding mode of citrate in the stabilization of gold nanoparticles. Nature Chemistry, 9(9), 890-895. https://doi.org/10.1038/nchem.2752

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title = "The structure and binding mode of citrate in the stabilization of gold nanoparticles",

abstract = "Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by 13C and 23Na solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1κO1) mode is favoured at high citrate:gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Auδ+ are observed. 23Na NMR experiments show that Na+ ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e− L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.",

author = "Aljohni, {Hind Abdullah Moteg} and Edy Abou-Hamad and Abdesslem Jedidi and Widdifield, {Cory M.} and Jasmine Viger-Gravel and Shiv Sangaru and David Gajan and Anjum, {Dalaver H.} and Samy Ould-Chikh and Hedhili, {Mohamed N.} and Andrei Gurinov and Kelly, {Michael J.} and {El Eter}, Mohamad and Luigi Cavallo and Jean-Marie Basset and Jean-Marie Basset",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: This work received support from the King Abdullah University of Science and Technology (KAUST) and ERC Advanced Grant No. 320860. For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia.",

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Aljohni, HAM, Abou-Hamad, E, Jedidi, A, Widdifield, CM, Viger-Gravel, J, Sangaru, S, Gajan, D, Anjum, DH, Ould-Chikh, S, Hedhili, MN, Gurinov, A, Kelly, MJ, El Eter, M, Cavallo, L, Basset, J-M & Basset, J-M 2017, 'The structure and binding mode of citrate in the stabilization of gold nanoparticles', Nature Chemistry, vol. 9, no. 9, pp. 890-895. https://doi.org/10.1038/nchem.2752

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AU - Aljohni, Hind Abdullah Moteg

AU - Abou-Hamad, Edy

AU - Jedidi, Abdesslem

AU - Widdifield, Cory M.

AU - Viger-Gravel, Jasmine

AU - Sangaru, Shiv

AU - Gajan, David

AU - Anjum, Dalaver H.

AU - Ould-Chikh, Samy

AU - Hedhili, Mohamed N.

AU - Gurinov, Andrei

AU - Kelly, Michael J.

AU - El Eter, Mohamad

AU - Cavallo, Luigi

AU - Basset, Jean-Marie

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: This work received support from the King Abdullah University of Science and Technology (KAUST) and ERC Advanced Grant No. 320860. For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia.

PY - 2017/3/27

Y1 - 2017/3/27

N2 - Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by 13C and 23Na solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1κO1) mode is favoured at high citrate:gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Auδ+ are observed. 23Na NMR experiments show that Na+ ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e− L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.

AB - Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by 13C and 23Na solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1κO1) mode is favoured at high citrate:gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Auδ+ are observed. 23Na NMR experiments show that Na+ ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e− L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.

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SP - 890

EP - 895

JO - Nature Chemistry

JF - Nature Chemistry

IS - 9

ER -

The structure and binding mode of citrate in the stabilization of gold nanoparticles

Abstract

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CCDC 1472104: Experimental Crystal Structure Determination : tri-sodium citrate hydrate

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The structure and binding mode of citrate in the stabilization of gold nanoparticles

Abstract

Bibliographical note

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CCDC 1472104: Experimental Crystal Structure Determination : tri-sodium citrate hydrate

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