Sensitive Detection of Polycyclic Aromatic Molecules: Surface Enhanced Raman Scattering via π–π Stacking

Yua, Yuan; Yu, Xiaohua; Zhang, Qiang; Chang, Mengfang; Li, Lei; Yang, Taiqun; Chen, Yuting; Pan, Haifeng; Zhang, Sanjun; Li, Li; Xu, Jianhua

doi:10.1021/acs.analchem.5b04487

Cited by 22 publications

(16 citation statements)

References 41 publications

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“…Moreover, distance‐dependent SERS using spacers or self‐assembled monolayers is limited by defect‐induced signals, poor reproducibility, and chemical interference . Although the chemical enhancement pathway assumes lesser significance at higher concentration of analyte due to nonspecific multilayer analyte adsorptions, it often leads to strong intermolecular interactions (Columbic, π–π, charge transfer) resulting in spectral shift and associated irregularities . Importantly, the state of charge on the molecule is a strongly dependent on the pH of the medium and therefore demands the stability of the SERS substrate over a wide pH range.…”

Section: Introductionmentioning

confidence: 99%

Surface‐enhanced Raman scattering platform operating over wide pH range with minimal chemical enhancement effects: Test case of tyrosine

Moronshing

Bhaskar

Mondal

et al. 2019

J Raman Spectroscopy

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Decoupling the contributions of electromagnetic and chemical enhancements in surface-enhanced Raman scattering (SERS) would lead to greater reliability and applicability in biological systems that involve large, localized pH gradients. However, suppressing short-range, chemical enhancement effects in SERS has proved challenging due to unavoidable charge-transfer interactions between analyte and the SERS platforms. This extends to both lithographically fabricated top-down and self-assembled bottom-up SERS platforms. Here, we employ a Soret effect-driven monodisperse nanoparticle assembly (Soret colloids [SCs]) with negligible surface charge (ξ < 16 mV) that provides exceptional SERS enhancement (analytical enhancement factor~10 6 ) contributed predominantly by excitation of localized surface plasmon resonance (electromagnetic enhancement) with minimal electrostatic or charge-transfer-based short-range interactions. Significantly, the low ξ of SCs is invariant over a wide pH range (pH 4-7) indicating minimal electrostatic surface charge. The interaction of such SCs with ionic analytes such as tyrosine leads to uniform SERS dictated by electromagnetic enhancement mechanism. The absence of contribution from chemical enhancement is clearly established by the vibrational fingerprints of tyrosine that are devoid of any spectral shifts originating from charge transfer between tyrosine and SCs. Accordingly, all features of the tyrosine that are independent of pH such as C-H stretch (2,700-3,000 cm −1 ) and C-C stretch (1,440 cm −1 ) and C-C-C bending (1,010 cm −1 ) are completely preserved without any spectral shifts. Simultaneously, pH-dependent vibrational features of tyrosine such as N-H stretch (1,545 cm −1 ), C¼O stretch (1,700 cm −1 ), COO − stretch (1,640 cm −1 ), C-O stretch (1,240 cm −1 ), and amide III bands (1,246 and 1,260 cm −1 ) are clearly observed. The intensities of such bands correspond exactly to the ionic state of tyrosine as dictated by the pH of the medium. This is reinforced by the crossover in the intensity of the pH-dependent vibrational modes (C-O vs. COOstretch, COO − vs. NH 3 + stretch) that coincides with the isoelectric pH of tyrosine. Finally, reliable quantification of the charge and concentration of tyrosine using SCs

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Section: Introductionmentioning

confidence: 99%

Surface‐enhanced Raman scattering platform operating over wide pH range with minimal chemical enhancement effects: Test case of tyrosine

Moronshing

Bhaskar

Mondal

et al. 2019

J Raman Spectroscopy

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“…For the detection of aromatic organics, π-π stacking could also be used, where the modifying molecules could be aromatic molecules and also special materials like graphene or carbon nitride with absorption ability [21,22]. The capture strategies by making use of electrostatic or hydrophobic interaction could effectively enhance the detection activity to targets, but the selectivity is still weak due to the low selectivity of these interactions.…”

Section: Electrostatic or Hydrophobic Interactionmentioning

confidence: 99%

Precision Target Guide Strategy for Applying SERS into Environmental Monitoring

Ouyang¹,

Li²,

Zhu³

et al. 2017

Raman Spectroscopy and Applications

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Surface enhanced Raman spectroscopy (SERS) is a promising analytical technique that exhibits various applications in trace detection and identification. When it is applied into environmental monitoring, we should concern several key points to improve detection sensitivity and selectivity for the detection in complex matrix. In this tutorial review, we mainly focus on the strategies for improving the use of SERS into environmental application. The strategies are summarized for enhancing the ability of the substrate to selectively capture specific targets, and for achieving separation and concentration of the analytes from the matrix and the assembly structures for multiple phase detection. We have also introduced several newly developed detection systems using portable instruments and miniaturized devices that are more suitable for infield applications. In addition, we discuss the present challenges that hide it from wide real application and give the outlook for the future development in applying SERS in environmental monitoring.

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“…It has been generally accepted that SERS enhancement may come from both physical enhancement (electric field) and chemical enhancement. 17 Physical enhancement is mainly achieved through fabricating typical nanostructures, in order to obtain higher local electric field enhancements. Chemical enhancement is achieved through the interactions between adsorbed molecules and the metal surface.…”

Section: Introductionmentioning

confidence: 99%

“…18 By introducing abundant nanogaps, nanobridges, sharp protrusions, or crevices into the nanostructures, SERS signals with high EFs of 10 7 -10 14 , as well as improved uniformity and reproducibility, have been obtained. 17,19 In recent years, various nanostructures have been used for SERS detection in DA molecules. 20 An LOD of 1.05 pM DA level has been obtained by using an Ag/MIL-101 nanostructure, 11 an LOD of 0.1 mM by using flower-like gold nanostructures electrodeposited on indium tin oxide glass, 13,20 an LOD of 1 nM with graphene-Au nanopyramid heterostructure, 13 and an LOD of 0.006 pM has been achieved with Au@Ag nanorod dimers.…”

Section: Introductionmentioning

confidence: 99%

“…The characteristic Raman peaks of the benzene ring between 1,300 and 1,700 cm −1 disappear because the π-π stacking in the DA powder attenuates the vibration of the benzene group. 17 DFT simulations indicate that a Raman peak at ~1,490 cm −1 appears after the formation of the amide bond (curve c), and its vibration is enhanced when the amide bond is located in the vicinity of Ag (curve d). The peak at ~1,490 cm −1 is conspicuous on the experimental SERS spectrum of DA (curve e), showing that the DA molecules are adsorbed on the Ag NPs through the chemical bonding between amino and carboxyl groups.…”

mentioning

confidence: 99%

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Sensitive determination of dopamine levels via surface-enhanced Raman scattering of Ag nanoparticle dimers

Yu¹,

He²,

Yang³

et al. 2018

IJN

Self Cite

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BackgroundDopamine (DA) is an important neurotransmitter in the hypothalamus and pituitary gland, which can produce a direct influence on mammals’ emotions in midbrain. Additionally, the level of DA is highly related with some important neurologic diseases such as schizophrenia, Parkinson, and Huntington’s diseases, etc. In light of the important roles that DA plays in the disease modulation, it is of considerable significance to develop a sensitive and reproducible approach for monitoring DA.PurposeThe objective of this study was to develop an efficient approach to quantitatively monitor the level of DA using Ag nanoparticle (NP) dimers and enhanced Raman spectroscopy.MethodsAg NP dimers were synthesized for the sensitive detection of DA via surface-enhanced Raman scattering (SERS). Citrate was used as both the capping agent of NPs and sensing agent to DA, which is self-assembled on the surface of Ag NP dimers by reacting with the surface carboxyl group to form a stable amide bond. To improve accuracy and precision, the multiplicative effects model for surface-enhanced Raman spectroscopy was utilized to analyze the SERS assays.ResultsA low limits of detection (LOD) of 20 pM and a wide linear response range from 30 pM to 300 nM were obtained for DA quantitative detection. The SERS enhancement factor was theoretically valued at approximately 107 by discrete dipole approximation. DA was self-assembled on the citrate capped surface of Ag NPs dimers through the amide bond. The adsorption energy was estimated to be 256 KJ/mol using the Langmuir isotherm model. The density functional theory was used to simulate the spectral characteristics of SERS during the adsorption of DA on the surface of the Ag dimers. Furthermore, to improve the accuracy and precision of quantitative analysis of SERS assays with a multiplicative effects model for surface-enhanced Raman spectroscopy.ConclusionA LOD of 20 pM DA-level was obtained, and the linear response ranged from 30 pM to 300 nM for quantitative DA detection. The absolute relative percentage error was 4.22% between the real and predicted DA concentrations. This detection scheme is expected to have good applications in the prevention and diagnosis of certain diseases caused by disorders in the DA level.

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Sensitive Detection of Polycyclic Aromatic Molecules: Surface Enhanced Raman Scattering via π–π Stacking

Cited by 22 publications

References 41 publications

Surface‐enhanced Raman scattering platform operating over wide pH range with minimal chemical enhancement effects: Test case of tyrosine

Surface‐enhanced Raman scattering platform operating over wide pH range with minimal chemical enhancement effects: Test case of tyrosine

Precision Target Guide Strategy for Applying SERS into Environmental Monitoring

Sensitive determination of dopamine levels via surface-enhanced Raman scattering of Ag nanoparticle dimers

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