Plasmon-Enhanced Autocatalytic N-Demethylation

Tesema, Tefera E.; Annesley, Christopher J.; Habteyes, Terefe G.

doi:10.1021/acs.jpcc.8b07078

Cited by 28 publications

(65 citation statements)

References 76 publications

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“…Different photochemical N -dealkylation methods using various photocatalysts have been developed for the synthesis of various N -dealkylated chemicals [ 155 , 156 , 157 , 158 , 159 , 160 , 161 , 162 , 163 ]. An early report by Pandey et al [ 160 ] showed that the photolysis of a tertiary N -methyl amine using dicyanonaphtalene 128a as electron acceptor in the presence of sodium hydroxide in methanol led to high yields of N -demethylated products ( 51c , 94c , 129c , and 130c ) ( Figure 18 ).…”

Section: Photochemical N -Dealkylationmentioning

confidence: 99%

N-Dealkylation of Amines

2022

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N-dealkylation, the removal of an N-alkyl group from an amine, is an important chemical transformation which provides routes for the synthesis of a wide range of pharmaceuticals, agrochemicals, bulk and fine chemicals. N-dealkylation of amines is also an important in vivo metabolic pathway in the metabolism of xenobiotics. Identification and synthesis of drug metabolites such as N-dealkylated metabolites are necessary throughout all phases of drug development studies. In this review, different approaches for the N-dealkylation of amines including chemical, catalytic, electrochemical, photochemical and enzymatic methods will be discussed.

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Section: Photochemical N -Dealkylationmentioning

confidence: 99%

N-Dealkylation of Amines

2022

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“…Recently, the plasmon-driven polymerization of thiols was visualized through TERS . Other interesting demonstrations include tracking tautomerization of porphycene at plasmonic hotspots, plasmon-enhanced N-demethylation of methylene blue, photoinduced and plasmon-driven cis–trans isomerization, , and photocatalytic reduction of CO 2 following visible light irradiation . The oxidative and reductive dimerization of p -nitrothiophenol (NTP) and p -aminothiophenol (ATP) to dimercaptoazobenzene (DMAB) on plasmonic substrates is of particular relevance to this work and has been extensively scrutinized by several groups. − Although controversial in its early days, − subsequent analyses of these dimerization processes convincingly established plasmon-enhanced DMAB formation.…”

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confidence: 99%

Nanoscale Chemical Reaction Imaging at the Solid–Liquid Interface via TERS

Bhattarai

El‐Khoury

2019

J. Phys. Chem. Lett.

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Plasmon-enhanced chemical transformations at the solid-liquid interface can be imaged with high sensitivity, chemical selectivity, and nanoscale precision through tip-enhanced Raman scattering (TERS). We demonstrate the latter for the first time through measurements aimed at (i) locating plasmonic hotspots at the solid-liquid interface at which chemical transformations take place, (ii) monitoring the evolution from reactants to products through their distinct Raman spectra, and (iii) 2D correlation analysis of Raman time trajectories to unambiguously extract the spectral components that mark chemical transformation and to understand the correlations between the product and parent signatures. For our proof-of-principle study, we select a model plasmonenhanced chemical process, namely, the dimerization of p-nitrothiophenol to dimercaptoazobenzene, but now, at the solid-liquid interface. Our plasmonic construct otherwise consists of chemically functionalized gold microplates in aqueous solution, which we image using a gold-coated TERS probe irradiated at 633-nm. Overall, we demonstrate chemical reaction imaging in aqueous solution via TERS for the first time, herein, at a pixel-limited lateral spatial resolution of 10 nm.

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“…The larger wavelength shift and broadening for thionine than for MB can be attributed to the replacement of the relatively bulky methyl groups at the N-terminus with hydrogen atoms that favors stronger thionine–surface interaction through the amine functional groups because there is less steric hindrance as the adsorption geometry reported by Guo et al suggests . The stronger surface–molecule interaction for thionine than for MB can be the thermodynamic driving force for the plasmon-driven N-demethylation of MB. ,, …”

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confidence: 93%

“…34 The stronger surface−molecule interaction for thionine than for MB can be the thermodynamic driving force for the plasmon-driven N-demethylation of MB. 32,36,48 The absorbance changes observed as a function of adsorption time are analyzed on the basis of adsorption isotherms obtained using the integral area under the curves in panels b and d of Figure 3. To facilitate the analysis, we define an adsorption parameter as η = I t /I m , where I t and I m are the integral areas at any time (t) and infinite time when a monolayer (m) surface coverage is assumed, respectively.…”

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confidence: 99%

Extracting Electronic Transition Bands of Adsorbates from Molecule–Plasmon Excitation Coupling

Tesema

Kookhaee

Habteyes

2020

J. Phys. Chem. Lett.

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The coupling between molecular electronic and particle plasmon excitations can result in various intriguing outcomes depending on how strongly or weakly the excitations couple to compete with their respective decay rates. In this work, using methylene blue and thionine dyes as model systems, we show that the electronic absorption band of resonant adsorbates can be determined with submonolayer sensitivity from the weak molecule−plasmon excitation coupling that results in the attenuation on the plasmonic absorption band. The extracted spectra are strongly similar to the absorption spectra of the corresponding molecules in solution, apart from the expected spectral red-shift and broadening. Interestingly, the adsorption isotherms determined on the basis of the magnitude of the attenuation correlate linearly with that determined from the adsorbate-induced plasmon resonance red-shift. The results demonstrate that in the weak coupling regimes the plasmon modes can be considered as an environment that supplies energy to and takes energy from the adsorbates.

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Plasmon-Enhanced Autocatalytic N-Demethylation

Cited by 28 publications

References 76 publications

N-Dealkylation of Amines

N-Dealkylation of Amines

Nanoscale Chemical Reaction Imaging at the Solid–Liquid Interface via TERS

Extracting Electronic Transition Bands of Adsorbates from Molecule–Plasmon Excitation Coupling

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