Adsorption and photon-driven charge transfer of pyridine on a cobalt electrode analyzed by surface enhanced Raman spectroscopy and relevant theories

Xie, Yong; Wu, De‐Yin; Liu, G.K.; Huang, Zhi‐Zhong; Ren, Bin; Yan, Jiawei; Yang, Zhilin; Zhang, Tian

doi:10.1016/s0022-0728(03)00318-8

Cited by 30 publications

(8 citation statements)

References 58 publications

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“…This enhancement is comparable with the CT enhancement, which is often considered as the major contribution of the CE enhancement. In contrast to the CT enhancements of Py adsorbed on coinage metals 66,67,76,77 and cobalt, , we conclude that the binding interaction can be a very important factor in analyzing the SERS enhancement for Py binding to platinum.…”

Section: Resultscontrasting

confidence: 57%

Chemical Enhancement Effects in SERS Spectra: A Quantum Chemical Study of Pyridine Interacting with Copper, Silver, Gold and Platinum Metals

et al. 2008

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Using density functional theory, we have studied the interactions between pyridine (Py) and coinage metals (silver, copper, and gold) as well as the transition metal platinum. We present here a detailed analysis of the influence of chemical enhancement effects on the SERS signals. We analyze the differential Raman scattering cross sections of the a1 vibrational modes related to Py. The results show that the relative Raman intensities of SERS spectra depend strongly on the binding interaction between Py and the SERS active centers, the electronic property of metal materials, and the incident wavelengths. When the bonding between Py and a SERS site is very weak, analogous to physical adsorption, the Raman spectra of the adsorbed Py are similar to that of free Py. For Py interacting strongly with copper, gold, and platinum clusters, we find that the Raman intensities of the v 1, v 6a, v 9a, and v 8a modes of Py are enhanced, whereas the intensity of the v 12 mode decreases. To check the enhancement effect of the charge-transfer mechanism, we calculate the preresonance Raman spectra. For Py interacting with silver, copper, and gold clusters, the low-lying charge transfer states are formed from the valence shell s orbital of metal to the unoccupied π*-type orbitals (b1 and a2) of the Py ring; whereas for Py adsorbed on platinum clusters, the low-lying charge transfer states are formed due to the transitions from some d orbitals of the metal clusters to the two unoccupied π*-type orbitals of Py. The results show that the Raman spectral property depends strongly on the property of these excited states and the electronic structures of the metal materials.

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Section: Resultscontrasting

confidence: 57%

Chemical Enhancement Effects in SERS Spectra: A Quantum Chemical Study of Pyridine Interacting with Copper, Silver, Gold and Platinum Metals

et al. 2008

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“…The assembly of metal nanoparticles to build plasmonic substrates typically gives rise to plasmon coupling/hybridization effects, which are responsible for the greatest SERS enhancement factors. 88 , 89 Extremely high electric fields are confined within tiny interparticle distances in such structures; even if such hotspots represent a small fraction of the irradiated surface, they contribute most significantly to the recorded SERS signal. 90 − 93 Methods as simple as drop casting or precipitation of colloidal dispersions enable the production of plasmonic substrates with hotspots that can efficiently amplify the Raman signals from analyte molecules.…”

Section: Substrate Fabrication and Sers Enhancement Optimizationmentioning

confidence: 99%

“…In addition to their lower production cost, these substrates can be readily manufactured for worldwide commercialization. The assembly of metal nanoparticles to build plasmonic substrates typically gives rise to plasmon coupling/hybridization effects, which are responsible for the greatest SERS enhancement factors. , Extremely high electric fields are confined within tiny interparticle distances in such structures; even if such hotspots represent a small fraction of the irradiated surface, they contribute most significantly to the recorded SERS signal. − Methods as simple as drop casting or precipitation of colloidal dispersions enable the production of plasmonic substrates with hotspots that can efficiently amplify the Raman signals from analyte molecules. , However, the nature and efficiency of hotspots are strongly dependent on the specific arrangement of the individual NPs, interparticle spacing and orientation. In turn, small changes or perturbations in near-field enhancement ( E / E 0 ) would drastically alter SERS intensity, which scales as its fourth power ( E 4 / E 0 4 ). − Unfortunately, the source of SERS sensitivity may also be the predominant cause of poor reproducibility.…”

Section: Substrate Fabrication and Sers Enhancement Optimizationmentioning

confidence: 99%

Prospects of Surface-Enhanced Raman Spectroscopy for Biomarker Monitoring toward Precision Medicine

et al. 2022

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Future precision medicine will be undoubtedly sustained by the detection of validated biomarkers that enable a precise classification of patients based on their predicted disease risk, prognosis, and response to a specific treatment. Up to now, genomics, transcriptomics, and immunohistochemistry have been the main clinically amenable tools at hand for identifying key diagnostic, prognostic, and predictive biomarkers. However, other molecular strategies, including metabolomics, are still in their infancy and require the development of new biomarker detection technologies, toward routine implementation into clinical diagnosis. In this context, surface-enhanced Raman scattering (SERS) spectroscopy has been recognized as a promising technology for clinical monitoring thanks to its high sensitivity and label-free operation, which should help accelerate the discovery of biomarkers and their corresponding screening in a simpler, faster, and less-expensive manner. Many studies have demonstrated the excellent performance of SERS in biomedical applications. However, such studies have also revealed several variables that should be considered for accurate SERS monitoring, in particular, when the signal is collected from biological sources (tissues, cells or biofluids). This Perspective is aimed at piecing together the puzzle of SERS in biomarker monitoring, with a view on future challenges and implications. We address the most relevant requirements of plasmonic substrates for biomedical applications, as well as the implementation of tools from artificial intelligence or biotechnology to guide the development of highly versatile sensors.

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“…The most important factor for the substrates produced by this strategy is a lower production cost, and the substrates can be easily scaled up. Moreover, it is noticed that the SERS substrates formed by the assembly or fusion of MNPs with abundant hot spots give rise to plasmon coupling/hybridization effects, leading to very high SERS enhancement factors. , Therefore, plasmonic substrates with branched structures are the most popular in various SERS applications.…”

Section: Introductionmentioning

confidence: 99%

Bimetallic Ag–Cu Alloy SERS Substrates as Label-Free Biomedical Sensors: Femtomolar Detection of Anticancer Drug Mitoxantrone with Multiplexing

et al. 2023

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Surface-enhanced Raman spectroscopy (SERS) has been recognized as a promising label-free technology for clinical monitoring due to its high sensitivity and multiplexing ability, which should accelerate the screening of important drugs in the blood and plasma of cancer patients in a simpler, faster, and less-expensive manner. In this work, bimetallic Ag–Au and Ag–Cu alloy microflowers (MFs) with tunable surface compositions were fabricated on a glass cover slip by simple thermolysis of a metal alkyl ammonium halide precursor and used as SERS substrates for the sensitive detection of anticancer drug mitoxantrone (MTO). Two different laser excitation sources, 532 and 632.8 nm, were used to explore the possibility of surface-enhanced resonance Raman scattering. The Ag–Cu substrate showed superior detection capability over Ag–Au, whereby the sensor recorded a noteworthy “limit of detection” value of 1 fM for MTO. Theoretical electromagnetic field maps were simulated on appropriately chosen plasmonic systems to compare the electromagnetic field enhancements with the experimental SERS efficiencies of the substrates. Further, using a 10% Ag–Cu substrate, efficient multiplexing detection of MTO was demonstrated with another anticancer drug doxorubicin (DOX) in water and mouse blood plasma.

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Adsorption and photon-driven charge transfer of pyridine on a cobalt electrode analyzed by surface enhanced Raman spectroscopy and relevant theories

Cited by 30 publications

References 58 publications

Chemical Enhancement Effects in SERS Spectra: A Quantum Chemical Study of Pyridine Interacting with Copper, Silver, Gold and Platinum Metals

Chemical Enhancement Effects in SERS Spectra: A Quantum Chemical Study of Pyridine Interacting with Copper, Silver, Gold and Platinum Metals

Prospects of Surface-Enhanced Raman Spectroscopy for Biomarker Monitoring toward Precision Medicine

Bimetallic Ag–Cu Alloy SERS Substrates as Label-Free Biomedical Sensors: Femtomolar Detection of Anticancer Drug Mitoxantrone with Multiplexing

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