Chemistry of cysteine assembly on Au(100): electrochemistry, <i>in situ</i> STM and molecular modeling

Engelbrekt, Christian; Nazmutdinov, Renat R.; Zinkicheva, Tamara T.; Glukhov, Dmitrii V.; Yan, Jiawei; Mao, Bing‐Wei; Ulstrup, Jens; Zhang, Jingdong

doi:10.1039/c9nr02477h

Cited by 11 publications

(7 citation statements)

References 79 publications

(126 reference statements)

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“…The release of molecular hydrogen has not been experimentally confirmed . Abraham et al assumed that the physisorption occurs at room temperature, while chemisorption is possible at high temperatures, which is also supported by theoretical evidence of Engelbrekt et al Some studies that explored cystine binding to metals claimed both CYS and cystine bind in the same way, as thiolates. , Watanabe et al observed by surface-enhanced Raman scattering (SERS) that adsorbed cystine exists in an equilibrium with cysteine-thiolate, i.e., the breaking of the disulfide bond may follow adsorption. Cystines can chemisorb after disulfide bond breaking or physisorb without breaking. , The creation and adsorption of thiolates is likelier for longer incubation times, suggesting breaking of the disulfide bond and the adsorption of thiolates is thermodynamically more favorable, but kinetically impaired .…”

Section: Resultsmentioning

confidence: 70%

Combined NMR and Computational Study of Cysteine Oxidation during Nucleation of Metallic Clusters in Biological Systems

et al. 2021

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The widespread biomedical applications of silver and gold nanoparticles (AgNPs and AuNPs, respectively) prompt the need for mechanistic evaluation of their interaction with biomolecules. In biological media, metallic NPs are known to transform by various pathways, especially in the presence of thiols. The interplay between metallic NPs and thiols may lead to unpredictable consequences for the health status of an organism. This study explored the potential events occurring during biotransformation, dissolution, and reformation of NPs in the thiol-rich biological media. The study employed a model system evaluating the interaction of cysteine with small-sized AgNPs and AuNPs. The interplay of cysteine on transformation and reformation pathways of these NPs was experimentally investigated by nuclear magnetic resonance (NMR) spectroscopy and supported by light scattering techniques and transmission electron microscopy (TEM). As the main outcome, Ag-or Au-catalyzed oxidation of cysteine to cystine was found to occur through generation of reactive oxygen species (ROS). Computational simulations confirmed this mechanism and the role of ROS in the oxidative dimerization of biothiol during NPs reformation. The obtained results represent valuable mechanistic data about the complex events during the transport of metallic NPs in thiol-rich biological systems that should be considered for the future biomedical applications of metal-based nanomaterials.

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Section: Resultsmentioning

confidence: 70%

Combined NMR and Computational Study of Cysteine Oxidation during Nucleation of Metallic Clusters in Biological Systems

et al. 2021

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“…A bias voltage is applied across the metal support and the extremely sharp STM probe, generating tunneling currents, which are transformed to high-resolution conductivity images when the STM tip is scanned across the SAM-modified metal support. Zhang and associates have reported extensive in situ STM investigations using a wide range of alkanethiols on single-crystal gold [6,[64][65][66]. In situ STM combined with electrochemical control can also directly map real-time SAM dynamics and structural features.…”

Section: Microscopymentioning

confidence: 99%

Direct Electrochemical Enzyme Electron Transfer on Electrodes Modified by Self-Assembled Molecular Monolayers

et al. 2020

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Self-assembled molecular monolayers (SAMs) have long been recognized as crucial “bridges” between redox enzymes and solid electrode surfaces, on which the enzymes undergo direct electron transfer (DET)—for example, in enzymatic biofuel cells (EBFCs) and biosensors. SAMs possess a wide range of terminal groups that enable productive enzyme adsorption and fine-tuning in favorable orientations on the electrode. The tunneling distance and SAM chain length, and the contacting terminal SAM groups, are the most significant controlling factors in DET-type bioelectrocatalysis. In particular, SAM-modified nanostructured electrode materials have recently been extensively explored to improve the catalytic activity and stability of redox proteins immobilized on electrochemical surfaces. In this report, we present an overview of recent investigations of electrochemical enzyme DET processes on SAMs with a focus on single-crystal and nanoporous gold electrodes. Specifically, we consider the preparation and characterization methods of SAMs, as well as SAM applications in promoting interfacial electrochemical electron transfer of redox proteins and enzymes. The strategic selection of SAMs to accord with the properties of the core redox protein/enzymes is also highlighted.

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“…Since their first description, 1 thiol self-assembled monolayers (SAM) on gold surfaces and nanoparticles have been widely used in a variety of technological applications, [2][3][4][5][6][7][8][9][10][11][12][13] and studied with a wealth of diffraction, [14][15][16][17][18] spectroscopic 8,[19][20][21][22][23] and other surface science techniques. 24 In addition, thiol SAMs have been modeled theoretically by several ab initio (mainly density functional theory, DFT) [25][26][27][28][29][30][31][32] and molecular mechanics 27,28,[33][34][35][36][37][38] studies.…”

Section: Introductionmentioning

confidence: 99%

Structure and stability of 7-mercapto-4-methylcoumarin self-assembled monolayers on gold: an experimental and computational analysis

Marchi

Cara

Lupi

et al. 2022

Phys. Chem. Chem. Phys.

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Chemistry of cysteine assembly on Au(100): electrochemistry, in situ STM and molecular modeling

Abstract: Unique two-dimensional super-structures form when cysteine self-assembles on single-crystal Au(100) due to inter-molecular forces and adsorption energetics, addressed through a comprehensive experimental and quantum computational approach.

Cited by 11 publications

References 79 publications

Combined NMR and Computational Study of Cysteine Oxidation during Nucleation of Metallic Clusters in Biological Systems

Combined NMR and Computational Study of Cysteine Oxidation during Nucleation of Metallic Clusters in Biological Systems

Direct Electrochemical Enzyme Electron Transfer on Electrodes Modified by Self-Assembled Molecular Monolayers

Structure and stability of 7-mercapto-4-methylcoumarin self-assembled monolayers on gold: an experimental and computational analysis

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