P band intermediate state (PBIS) tailors photoluminescence emission at confined nanoscale interface

Yang, Taiqun; Shan, Bing-Qian; Huang, Fang; Yang, Songqiu; Peng, Bo; Yuan, En-Hui; Wu, Peng; Zhang, Kun

doi:10.1038/s42004-019-0233-1

Cited by 47 publications

(96 citation statements)

References 69 publications

(104 reference statements)

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“…Obviously, the change of optical properties is caused by the structural discrepancy of two intermediate states, suggesting the varied overlapping of the two p orbitals of O atoms from hydroxide groups and /or 4-NP (49). This finally determines the reaction kinetic of 4-NP reduction.…”

Section: Resultsmentioning

confidence: 99%

Surface Electronic State Mediates Proton Transfer at Metal Nanoscale Interface for Catalytic Hydride Reduction of −NO2 to −NH2

Shan¹,

Zhou²,

Ding³

et al. 2021

Preprint

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Concerted electron and proton transfer is a key step for the reversible conversion of molecular hydrogen in both heterogeneous nanocatalysis and metalloenzyme catalysis. (Gabor A. Somorjai, et al. PNAS, 2016, 113, 5159–5166) However, the activation mechanism involving electron and proton transfer dynamic remains elusive. (Starla D. Glover and Leif Hammarström et al., J. Am. Chem. Soc. 2021, 143, 560−576.) With the most widely used catalytic hydride reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) as a model reaction, we evaluate the catalytic activity of noble metal NPs trapped in porous silica in aqueous NaBH4 solution. By virtue of a novel combination of catalyst design, reaction kinetics, isotope labeling, and multiple spectroscopic techniques, we counter-intuitively demonstrates that, the hydrogen resource of the final product of 4-AP by hydride reduction is not originated from the NaBH4 reduced, and that metal NPs (Ag/Pt/Pd) is not a real catalytic active site for surface electron mediation. (Avelino Corma etal., Angew. Chem. Int. Ed. 2007, 46, 7266 –7269; ACS Catal. 2015, 5, 7114−7121.). A completely new ‘Surface Electronic State Mediated Proton Transfer’ mechanism was proposed to understand the catalytic hydride reduction of −NO2 to −NH2 at metal nanoscale interface. The similar concerted electron and proton transfer dynamic was only recently observed in the [FeFe]-hydrogenases for reversible proton reduction. (Gregory A. Voth et al., J. Phys. Chem. B 2013, 117, 4062−4071; J. Chem. Phys. 2014, 141, 22D527; Juan C. Fontecilla-Camps et al., Chem. Rev. 2007, 107, 4273-4303.) We believed that current research provide a completely new insights into the working mechanism of nanocatalysis and metalloenzyme catalysis involved by electron and proton transfer.

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Section: Resultsmentioning

confidence: 99%

Surface Electronic State Mediates Proton Transfer at Metal Nanoscale Interface for Catalytic Hydride Reduction of −NO2 to −NH2

Shan¹,

Zhou²,

Ding³

et al. 2021

Preprint

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“…This interpretation gives a completely new insight into the luminescent principle of MNCs, but we cannot completely preclude the role of the metal core for the PL emission. Very most recently, based on the complimentary characterizations of steady-state absorption, excitation, and time-resolved PL spectroscopy, we definitively identify that the induced p band intermediate state (PBIS) stems from the overlapping of p orbitals of the paired or more adjacent heteroatoms (O and S) from the surface-protected ligands on the metal NCs, which can be Very most recently, based on the complimentary characterizations of steady-state absorption, excitation, and time-resolved PL spectroscopy, we definitively identify that the induced p band intermediate state (PBIS) stems from the overlapping of p orbitals of the paired or more adjacent heteroatoms (O and S) from the surface-protected ligands on the metal NCs, which can be Very most recently, based on the complimentary characterizations of steady-state absorption, excitation, and time-resolved PL spectroscopy, we definitively identify that the induced p band intermediate state (PBIS) stems from the overlapping of p orbitals of the paired or more adjacent heteroatoms (O and S) from the surface-protected ligands on the metal NCs, which can be considered as a dark state at the metal-NCs interface to activate the triplet site of the surface chromophores by enhancing intersystem crossing [43]. Figure 15 showed that the water-soluble and oil-soluble MNCs with identical size synthesized by a ligand-exchange strategy (denoted as Au NCs@GSH and Au NCs@DT, respectively) exhibited the strong solvent-enhanced PL emission behavior, and that it is very interesting that the number and intensity of PL emission was strongly dependent on the type of used surface-protective ligands, even though the metal core remains intact.…”

Section: Our P Band Intermediate State (Pbis) Model Dominates the Phomentioning

confidence: 89%

“…We definitively confirmed that the pairing of surface ligands could serve as an exact chromophore for PL emission, which has nothing to do with the metal core. considered as a dark state at the metal-NCs interface to activate the triplet site of the surface chromophores by enhancing intersystem crossing [43]. Figure 15 showed that the water-soluble and oil-soluble MNCs with identical size synthesized by a ligand-exchange strategy (denoted as Au NCs@GSH and Au NCs@DT, respectively) exhibited the strong solvent-enhanced PL emission behavior, and that it is very interesting that the number and intensity of PL emission was strongly dependent on the type of used surface-protective ligands, even though the metal core remains intact.…”

Section: Our P Band Intermediate State (Pbis) Model Dominates the Phomentioning

confidence: 99%

“…So far, two main approaches-the bottom-up and top-down strategies-have been developed for the synthesis of emission wavelength adjustable luminescent MNCs with high quantum yield (QY) in large quantities, as illustrated in Figure 1 [8][9][10]14,15,34]. The size effect (including metal corearchitecture) [35][36][37][38][39][40], ligand effect (charge-donating capability [33], chirality [41,42], hydrophily [43]), valance state of surface metals [33,44], and superlattice structures of assembly of metal clusters [45,46] have been intensively studied. It is important to note that especially for the bottom-up synthetic strategy, a common feature of luminescence metal NCs is that the templates used for the synthesis as protective ligands, such as nonconjugated polymers, proteins, amino acid molecules, and even small chemical molecules, always contain electron-rich heteroatoms, including oxygen (O), nitrogen (N), sulfur (S), phosphorus (P), and others, emphasizing the dominant role of the surface ligand to tune the PL properties.…”

Section: Introductionmentioning

confidence: 99%

“…(d) Time-resolved luminescence decay profiles of solvent-induced luminescent Au NCs@GSH and Au NCs@DT. Reprinted with permission from Ref [43]…”

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confidence: 99%

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Origin of the Photoluminescence of Metal Nanoclusters: From Metal-Centered Emission to Ligand-Centered Emission

et al. 2020

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Recently, metal nanoclusters (MNCs) emerged as a new class of luminescent materials and have attracted tremendous interest in the area of luminescence-related applications due to their excellent luminous properties (good photostability, large Stokes shift) and inherent good biocompatibility. However, the origin of photoluminescence (PL) of MNCs is still not fully understood, which has limited their practical application. In this mini-review, focusing on the origin of the photoemission emission of MNCs, we simply review the evolution of luminescent mechanism models of MNCs, from the pure metal-centered quantum confinement mechanics to ligand-centered p band intermediate state (PBIS) model via a transitional ligand-to-metal charge transfer (LMCT or LMMCT) mechanism as a compromise model.

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Tuning the Optical Properties of Au Nanoclusters by Designed Proteins

López‐Martínez

Gianolio

Garcia‐Orrit

et al. 2021

Advanced Optical Materials

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but also by the ligands coordinated to them, as reported in recent studies. [2] In this sense, the coordination of metal-NCs with biomolecules is an emerging area of research since this biomolecular capping can endow multiple capabilities to the NCs, including biocompatibility, stability in biological media, and biological functionality (e.g., binding and inhibitory functions) resulting in hybrid bionanomaterials with a plethora of potential applications. [3] In this context, it has been shown that the capping and stabilization of metal NCs with peptides and proteins affect the optical properties of the NCs and the interaction with living matter by means of specific biological interplay. [4] Taking into account the role of the stabilizing agents on the NCs properties, an extra level of tailoring can be achieved by exploiting protein engineering. Metal coordinating engineered proteins are strongly inspired by natural metalloproteins, whose metalbinding capabilities allow to perform multiple functions, such as storage and transport, [5,6] sensing, [7,8] or catalysis. [9,10] In this framework, designed repeat proteins emerged as an interesting option to display custom metal coordination sites. Repeat proteins can be used as building blocks due to their modularity, regular geometry, and small size; allowing the design of both simple, but also more complex supramolecular assemblies and multifunctional systems. [11][12][13][14] The possibility of adding tailored chemical Gold nanoclusters (AuNCs) are nanomaterials with interesting photoluminescent properties that can be endowed with biomolecular recognition and biocompatibility when stabilized with proteins. The interplay between the optical features of AuNCs and the function added by the protein makes them perfect candidates for generating hybrid protein-inorganic nanomaterials. Focusing on protein stabilized-AuNCs, hitherto most of the work has covered the use of natural proteins for in situ growth of AuNCs. However, the exploitation of design proteins for such endeavors enables fine-tuning of the photoluminescent assets of AuNCs. In this work, rational protein engineering of modular protein scaffolds is applied for capping of non-emissive, non-passivated naked AuNCs, resulting in a fast and easy method for the synthesis of customizable and emissive protein-AuNC nanomaterials. Tuning of the photoluminescent properties of the final hybrid module is obtained by appropriate choice of the coordination residues grafted on the same protein scaffold. The effects of ligands and coordination bonds are studied using time-resolved photo luminescence and X-ray absorbance spectroscopies, shedding light on the mechanisms behind the emerging properties of these hybrid materials. Moreover, the described versatile strategy opens new avenues for the synthesis of on-demand photoluminescent hybrids for a wide spectrum of optical applications.

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P band intermediate state (PBIS) tailors photoluminescence emission at confined nanoscale interface

Cited by 47 publications

References 69 publications

Surface Electronic State Mediates Proton Transfer at Metal Nanoscale Interface for Catalytic Hydride Reduction of −NO2 to −NH2

Surface Electronic State Mediates Proton Transfer at Metal Nanoscale Interface for Catalytic Hydride Reduction of −NO2 to −NH2

Origin of the Photoluminescence of Metal Nanoclusters: From Metal-Centered Emission to Ligand-Centered Emission

Tuning the Optical Properties of Au Nanoclusters by Designed Proteins

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