Organosoluble Au<sub>102</sub>(SPh)<sub>44</sub> Nanomolecules: Synthesis, Isolation, Compositional Assignment, Core Conversion, Optical Spectroscopy, Electrochemistry, and Theoretical Analysis

Rambukwella, Milan; Sementa, Luca; Barcaro, Giovanni; Fortunelli, Alessandro; Dass, Amala

doi:10.1021/acs.jpcc.5b07520

Cited by 23 publications

(25 citation statements)

References 49 publications

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“…[32][33][34] Among the variously proposed mechanisms of cytotoxicity,t he one involving in the release of silver ions from Ag NPsh as received mosta ttention; [35][36][37][38][39] however,i tr equires furtherv alidation, as evidenceo fr eleased silver ions is far from sufficient (especially for thiolated Ag NPs). [40][41][42] Based on our findings,w ed emonstrate that DPV can be used for the rapid and preliminary evaluation of the cytotoxicity of thiolated Ag NPs. [40][41][42] Based on our findings,w ed emonstrate that DPV can be used for the rapid and preliminary evaluation of the cytotoxicity of thiolated Ag NPs.…”

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confidence: 74%

“…[38,39] Herein, we provide such evidenceb yu sing differential pulse voltammetry (DPV), am ethodw hichh as been widely used in the metal nanoclusters field. [40][41][42] Based on our findings,w ed emonstrate that DPV can be used for the rapid and preliminary evaluation of the cytotoxicity of thiolated Ag NPs. Furthermore, we reveal that the cytotoxicity of thiolatedA gN Ps is size dependent in the investigated size range.Initially,t he Ag 14 SG 11 (where, SG = l-reduced glutathiolate) (Ag 14 for short) nanoclustersa nd approximately 8nmn anoparticles [43] were employed as the model nanoparticles for this study.C haracterization of silver ions released from Ag NPs by using mass spectrometry is challenging, owing to the interference of the fragmentation of silver nanoclusters or silver nanocrystals( see FigureS1).…”

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confidence: 74%

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Size‐Dependent Cytotoxicity of Thiolated Silver Nanoparticles Rapidly Probed by using Differential Pulse Voltammetry

et al. 2016

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Thiolateds ilver nanoparticles have recently received extensive interests in terms of their syntheses, properties, and applications;h owever,t heir cytotoxicity has not been paid great attention.S ome issues relatedt ot he cytotoxicity remained unresolved:W hat is the relationship betweens ize and cytotoxicity? How to rapidly probe their cytotoxicity?, ands of orth. In this work, differential pulse voltammetry (DPV) is, for the first time, introduced to rapidly and preliminarily evaluate the cytotoxicity of silver nanoparticles on the basis of the finding that the silver-ion signal intensity probedb yD PV is positively correlated to the cytotoxicity of silver nanoparticles. It is found that the cytotoxicity of silver nanoparticles is size dependent in the investigated size range, that is, with increasing size, the cytotoxicityi ncreases. Our work advances one step toward monitoring and understanding the cytotoxicity of thiolated silver nanoparticles.Silver nanoparticles (Ag NPs, including the ultrasmall nanoparticles, so-called nanoclusters, [1,2] and their larger counterparts, nanocrystals [3,4] )h ave been increasingly used for practical applicationsa nd research purposes, [5][6][7][8][9][10][11][12][13][14][15][16] owing to their relatively low cost (compared with Au, Pt, etc.) andi ntriguing physicochemicalp roperties (enhanced Ramans cattering, [17,18] bright fluorescence, [19,20] antimicrobial property, [21][22][23] etc.). However, the large-scale employment of Ag NPs may pose at hreat to human health and the environment. [24,25] Some previous studies indeed revealed the toxicityo fA gN Ps, [26][27][28][29][30][31] with af ew works present differing views on whether or not Ag NPs are cytotoxic. [32][33][34] Among the variously proposed mechanisms of cytotoxicity,t he one involving in the release of silver ions from Ag NPsh as received mosta ttention; [35][36][37][38][39] however,i tr equires furtherv alidation, as evidenceo fr eleased silver ions is far from sufficient (especially for thiolated Ag NPs). [38,39] Herein, we provide such evidenceb yu sing differential pulse voltammetry (DPV), am ethodw hichh as been widely used in the metal nanoclusters field. [40][41][42] Based on our findings,w ed emonstrate that DPV can be used for the rapid and preliminary evaluation of the cytotoxicity of thiolated Ag NPs. Furthermore, we reveal that the cytotoxicity of thiolatedA gN Ps is size dependent in the investigated size range.Initially,t he Ag 14 SG 11 (where, SG = l-reduced glutathiolate) (Ag 14 for short) nanoclustersa nd approximately 8nmn anoparticles [43] were employed as the model nanoparticles for this study.C haracterization of silver ions released from Ag NPs by using mass spectrometry is challenging, owing to the interference of the fragmentation of silver nanoclusters or silver nanocrystals( see FigureS1). Thei dentification of silver ions by using other well-recognized techniques such as HPLC, ICP-MS, and atomicf luorescence spectrometry is also difficult, owing to the influence of Ag NPs. DPV could o...

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Size‐Dependent Cytotoxicity of Thiolated Silver Nanoparticles Rapidly Probed by using Differential Pulse Voltammetry

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“…This is expected as the surface availability of the nanomolecule decreases as the size increases steric effect by para -tert-butyl groups becomes significant compared to smaller core-size Au 36 (SR) 24 . Similarly, it was found that physicochemical differences between thiophenol, 4-methoxybenzene thiol, 4-methylbenzene thiol, and 4-bromobenzene thiol are subtle and results in same composition of AuNMs (Nimmala and Dass, 2014 ; Chen et al, 2015a ; Rambukwella et al, 2015 ; Rambukwella and Dass, 2017 ). Although, Au 36 (SR) 24 NMs system was reported (Das et al, 2014 ) with bulky cyclopentane thiol, exclusive formation of Au 36 (SR) 24 is dominated by electronic effect by aromatic nature of the ligand rather than steric effect.…”

Section: Ligand Effect Demonstrated By Direct Synthesismentioning

confidence: 93%

Ligand Structure Determines Nanoparticles' Atomic Structure, Metal-Ligand Interface and Properties

et al. 2018

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The nature of the ligands dictates the composition, molecular formulae, atomic structure and the physical properties of thiolate protected gold nanomolecules, Aun(SR)m. In this review, we describe the ligand effect for three classes of thiols namely, aliphatic, AL or aliphatic-like, aromatic, AR, or bulky, BU thiol ligands. The ligand effect is demonstrated using three experimental setups namely: (1) The nanomolecule series obtained by direct synthesis using AL, AR, and BU ligands; (2) Molecular conversion and interconversion between Au38(S-AL)24, Au36(S-AR)24, and Au30(S-BU)18 nanomolecules; and (3) Synthesis of Au38, Au36, and Au30 nanomolecules from one precursor Aun(S-glutathione)m upon reacting with AL, AR, and BU ligands. These nanomolecules possess unique geometric core structure, metal-ligand staple interface, optical and electrochemical properties. The results unequivocally demonstrate that the ligand structure determines the nanomolecules' atomic structure, metal-ligand interface and properties. The direct synthesis approach reveals that AL, AR, and BU ligands form nanomolecules with unique atomic structure and composition. Similarly, the nature of the ligand plays a pivotal role and has a significant impact on the passivated systems such as metal nanoparticles, quantum dots, magnetic nanoparticles and self-assembled monolayers (SAMs). Computational analysis demonstrates and predicts the thermodynamic stability of gold nanomolecules and the importance of ligand-ligand interactions that clearly stands out as a determining factor, especially for species with AL ligands such as Au38(S-AL)24.

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“…8,9,17 A set of eleven ligands, included in experimental or theoretical reports devoted to the study of thiolated gold clusters, is considered along this study. The first set of eight achiral ligands includes para-mercaptobenzoic acid (p-MBA), 18 SPh, 19,20 SPhNO 2 , 21 cyclohexanethiol (S-c-C 6 H 11 ), 1,22,23 2-phenylethylthiolate (2-PET), 24 mercaptopropionic acid (MPA that has been considered in gold nanoparticles), 25 besides the amply used SCH 3 ligand during calculations. Starting from the experimental Au 18 cluster protected by 14 S-c-C 6 H 11 ligands, a set of initial structures was built; some of them are depicted in Fig.…”

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Ligand effects on the optical and chiroptical properties of the thiolated Au₁₈ cluster

Tlahuice‐Flores

2016

Phys. Chem. Chem. Phys.

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The effect of chiral and achiral ligands protecting the inner Au 9 core of the Au 18 (SR) 14 cluster is studied based on density functional theory (DFT) and its corrected long-range interaction (DFT-D) approach. It was found that the electronic properties (energy levels) depend on the specific ligands, which induce distinct distortions on the Au-S framework. However, the substitution of S-c-C 6 H 11 as SCH 3 ligands may be considered to be correct given the obtained resemblance to the displayed bonding, optical and chiroptical properties. A further comparison of the CD and UV spectra displayed by the In 2015, the structure of thiolated Au 18 cluster protected by S-c-C 6 H 11 ligands was solved by means of X-Ray diffractions studies but its CD spectrum was missed. 1In contrast, previous theoretical models 2 and experimental reports had established the Au 18 cluster to be chiral whereby its CD spectra were known. 3 In the experimental report of the Au 18 (SR) 14 cluster the lack of a CD signal was attributed to the presence of a symmetry plane. However, in a recent computational study, the C 1 symmetry was preferred over the C s symmetry by circa 3.0 eV. 4 This result supports the hypotheses that the Au 9 inner core is intrinsically chiral while the cyclohexyl (S-c-C 6 H 11 ) ligand is achiral. In this communication a systematic study of the influence of chiral and achiral ligands on the structural, optical and chiroptical properties of the thiolated Au 18 cluster has been conducted. The importance of this study lies in the photochemical properties of the Au 18 cluster and in its potential applications. 5Two sets of ligands were selected: one set comprised eight achiral ligands and a second set, three chiral ligands. All calculations are based on density functional theory (DFT) 6 and/or its corrected long-range interaction (DFT-D) 7 approach.It is important to mention that the consideration of long-range forces (van der Waals interactions) is important when the organic part of the ligand is constituted by chemical groups that are expected to interact among themselves (interligand interaction) and with the environment. The ligand effects on the structure of thiolated Au 15 cluster was reported in 2013, and the consideration of the N-acetyl-L-cysteine (NAC) as a ligand resulted in a lower energy isomer. 8 Moreover, the effect of ligands on the optical properties of various protected gold clusters has been found or computationally predicted, for example, into the thiolated Au 25 cluster the ligands effect was revealed as a distortion into the Au-S framework, 9 and on the structure of the Au 24 cluster where thiolate or selenolate ligands organized forming various kind of motifs. 10

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Organosoluble Au₁₀₂(SPh)₄₄ Nanomolecules: Synthesis, Isolation, Compositional Assignment, Core Conversion, Optical Spectroscopy, Electrochemistry, and Theoretical Analysis

Cited by 23 publications

References 49 publications

Size‐Dependent Cytotoxicity of Thiolated Silver Nanoparticles Rapidly Probed by using Differential Pulse Voltammetry

Size‐Dependent Cytotoxicity of Thiolated Silver Nanoparticles Rapidly Probed by using Differential Pulse Voltammetry

Ligand Structure Determines Nanoparticles' Atomic Structure, Metal-Ligand Interface and Properties

Ligand effects on the optical and chiroptical properties of the thiolated Au₁₈ cluster

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Organosoluble Au102(SPh)44 Nanomolecules: Synthesis, Isolation, Compositional Assignment, Core Conversion, Optical Spectroscopy, Electrochemistry, and Theoretical Analysis

Cited by 23 publications

References 49 publications

Size‐Dependent Cytotoxicity of Thiolated Silver Nanoparticles Rapidly Probed by using Differential Pulse Voltammetry

Size‐Dependent Cytotoxicity of Thiolated Silver Nanoparticles Rapidly Probed by using Differential Pulse Voltammetry

Ligand Structure Determines Nanoparticles' Atomic Structure, Metal-Ligand Interface and Properties

Ligand effects on the optical and chiroptical properties of the thiolated Au18 cluster

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Organosoluble Au₁₀₂(SPh)₄₄ Nanomolecules: Synthesis, Isolation, Compositional Assignment, Core Conversion, Optical Spectroscopy, Electrochemistry, and Theoretical Analysis

Ligand effects on the optical and chiroptical properties of the thiolated Au₁₈ cluster