Cocaine Hydrochloride Structure in Solution Revealed by Three Chiroptical Methods

Fagan, Patrik; Kocourková, Lucie; Tatarkovič, Michal; Králík, František; Kuchař, Martin; Setnička, Vladimı́r; Bouř, Petr

doi:10.1002/cphc.201700452

Cited by 17 publications

(8 citation statements)

References 45 publications

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“…The chiroptical methods, specifically vibrational circular dichroism (VCD), electronic circular dichroism (ECD) and Raman optical activity (ROA), in combination with theoretical quantum chemical predictions can provide further 3D structural information on NPS in solution, which is crucial, e.g. for the understanding of their biological activity and toxicity [17][18][19]. The comparative analysis of experimental chiroptical properties and DFT calculations also allow the determination of the absolute configuration of individual separated enantiomers [20,21].…”

Section: Introductionmentioning

confidence: 99%

Methylone and pentylone: structural analysis of new psychoactive substances

et al. 2019

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Purpose The growing availability of new psychoactive substances with unknown toxicity is alarming all over the world. The simplicity of acquiring these drugs of abuse from internet markets has caused an increase in the total number of seizures. We present the first systematic spectroscopic study of methylone and pentylone, which are in the class of synthetic cathinones. Methods High performance liquid chromatography (HPLC) was used for the enantioseparation of methylone and pentylone. The substances were further analysed by the conventional methods of ultraviolet (UV) and infrared (IR) absorption and chiroptical methods, specifically electronic circular dichroism (ECD) and vibrational circular dichroism (VCD). The obtained data were supported with the density functional theory (DFT) calculations using the B3LYP or B3PW91 functional and 6-311++G(d,p) basis sets, including the solvent effects. Results The 3D structure of methylone and pentylone in solution was revealed. Moreover, the chiral separation of both studied substances was achieved and the absolute configuration of the respective enantiomers was determined. Conclusion Vibrational circular dichroism spectroscopy seems to be the best of the methods employed to distinguish structurally similar chiral substances, especially in combination with quantum chemical calculations. According to the structural analysis, 5 and 9 stable conformers of methylone and pentylone, respectively, were revealed in an aqueous solution. Finally, very good agreement between the experimental and simulated spectra was achieved.

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Section: Introductionmentioning

confidence: 99%

Methylone and pentylone: structural analysis of new psychoactive substances

et al. 2019

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“…Like its natural analogue, butylone exhibits psychostimulant effects (eg, hyperlocomotion) and causes the increase of extracellular dopamine concentration. [15][16][17][18][19][20][21][22][23][24] The ab initio calculations allow a detailed interpretation of the experimental spectra of chiral molecules in solution. 9 Most studies 11-13 published thus far have been focused on racemic cathinones, and stereo-specific drug interactions have been demonstrated for amphetamines.…”

Section: Introductionmentioning

confidence: 99%

“…Chiroptical spectroscopy, specifically Raman optical activity, electronic circular dichroism (ECD), and vibrational circular dichroism (VCD), combined with quantum-chemical calculations are an efficient tool for the determination of the absolute configuration of separated enantiomers and their molecular stereochemistry. [15][16][17][18][19][20][21][22][23][24] The ab initio calculations allow a detailed interpretation of the experimental spectra of chiral molecules in solution. It has been demonstrated that the application of several independent chiroptical methods for the determination of the 3D structure of a chiral substance significantly increases the reliability of the obtained results.…”

Section: Introductionmentioning

confidence: 99%

Structure determination of butylone as a new psychoactive substance using chiroptical and vibrational spectroscopies

et al. 2018

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Recently, there has been a worldwide substantial increase in the consumption of new psychoactive substances (NPS), compounds that mimic the structure of illicit drugs, such as amphetamines or ecstasy. The producers try to avoid the law by a slight modification of illicit structures, thereby developing dozens of temporarily legal NPS every year. The current trends in the detection and monitoring of such substances demand a fast and reliable analysis. Molecular spectroscopy represents a highly effective tool for the identification of NPS and chiroptical methods can provide further information on their 3D structure, which is the key for the determination of their biological activity. We present the first systematic study of NPS, specifically butylone, combining chiroptical and vibrational spectroscopies with ab initio calculations. According to density functional theory calculations, 6 stable lowest energy conformers of butylone were found and their molecular structure was described. For each conformer, the relative abundance based on the Boltzmann distribution was estimated, their population weighted spectra predicted and compared to the experimental results. Very good agreement between the experimental and the simulated spectra was achieved, which allowed not only the assignment of the absolute configuration, but also a precise description of the molecular structure.

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“…There has been much effort put into the development of reliable and fast analytical methods for the identification and quantification of PDE-5 inhibitors in different types of real samples. [21][22][23][24][25][26][27][28] Optical rotatory dispersion, vibrational circular dichroism (VCD), and electronic circular dichroism (ECD) combined with IR and NMR spectroscopies were successfully used for the determination of the stereochemistry and 3D structure of all 4 stereoisomers of tadalafil in a solution. High-performance liquid chromatography, usually in tandem with mass spectrometry, is often considered to be the most important and commonly used method in pharmaceutical analysis, and the issue of PDE-5 inhibitors is not an exception.…”

Section: Introductionmentioning

confidence: 99%

“…20 Chiroptical spectroscopy, which is inherently sensitive to the 3D structure of chiral molecules, presents a powerful tool for the conformational analysis and determination of the absolute configuration. [21][22][23][24][25][26][27][28] Optical rotatory dispersion, vibrational circular dichroism (VCD), and electronic circular dichroism (ECD) combined with IR and NMR spectroscopies were successfully used for the determination of the stereochemistry and 3D structure of all 4 stereoisomers of tadalafil in a solution. 29 Another approach for the differentiation and quantitation of enantiomeric tadalafil isomers based on electrospray mass spectrometry was devised.…”

Section: Introductionmentioning

confidence: 99%

Chiroptical and vibrational spectroscopic study of genuine and counterfeit medicines containing tadalafil

et al. 2018

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The production and distribution of counterfeit pharmaceuticals present a serious problem worldwide. This is true especially in case of phosphodiesterase type 5 inhibitors for treating erectile dysfunction, where consumers often prefer buying them anonymously from unverified sources. In this study, genuine and counterfeit Cialis® 20 mg tablets were analyzed by electronic circular dichroism, vibrational circular dichroism, and infrared spectroscopy. The characteristic spectral patterns were identified by comparison with the spectra of tadalafil standard as an active pharmaceutical ingredient, and its presence was confirmed in all samples. The amount of tadalafil, however, was markedly lower in the case of counterfeit tablet as the observed band intensities were considerably lower. No other significant differences between the genuine and counterfeit tablets were revealed. Ab initio density functional theory calculations provided a detailed description of the stable conformers of tadalafil in a solution and enabled thorough interpretation of the experimental spectra.

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Cocaine Hydrochloride Structure in Solution Revealed by Three Chiroptical Methods

Cited by 17 publications

References 45 publications

Methylone and pentylone: structural analysis of new psychoactive substances

Methylone and pentylone: structural analysis of new psychoactive substances

Structure determination of butylone as a new psychoactive substance using chiroptical and vibrational spectroscopies

Chiroptical and vibrational spectroscopic study of genuine and counterfeit medicines containing tadalafil

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