A DFT study on the recognition of α-amino acid derivatives by chiral uranyl–salen

Forte, Giuseppe; Sfrazzetto, Giuseppe Trusso; Pappalardo, Andrea

doi:10.1016/j.comptc.2015.06.007

Cited by 4 publications

(2 citation statements)

References 54 publications

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“…具有氢键供体 NH 基团的大环化合物合成及其在主客体识别和超分子化学研究领域一直是研究的热点, 含脲基 [1][2] 、酰亚胺基 [3][4][5][6][7] 的大环合成、组装及阴离子识别研究方面不断取得进展, 但迄今报道的含 NH 功能基的人工大环受体中, 绝大多数大环结构本身没有手性特征, 一定程度上限制了含 NH 基团结构的大环在生物分子或药物分子识别及探针方面的性质考察 [8][9][10] . 我们知道, 手性化合物广泛存在于具有生物活性的天然产物以及药物分子中 [11][12] , 大多数药物分子是手性的, 其中不同构型的手性分子往往表现出不同甚至截然相反的生理活性, 针对药物手性对映体分析与分离, 及其药理、毒性方面的研究一直受到关注 [13][14][15][16][17][18][19][20][21][22] . 青霉胺 (Penicillamine)是一种常见的手性药物, 研究表明它的两种对映体(D-和 L-Pen)生理药效显著差异, D-Pen 可用于治疗胱氨酸尿症和类风湿性关节炎, 而 L-Pen 则是有毒的, 针对青霉胺对映体检测、探针及分离研究一直受到研究者的青睐 [23][24][25][26][27][28] , 如十多年来, 蒲林课题组 [29][30][31] 设计合成含双联萘基的手性衍生物, 对氨基酸对映体识别作用进行了系统深入的研究.…”

Section: 引言unclassified

Enantiomers Identification of Penicillamine by Chiral Mono-Schiff Base Macrocycles

Tian¹,

Lin²,

Han³

et al. 2023

Acta Chimica Sinica

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A large number of chiral drug molecules have a chiral structure containing both D-and L-enantiomers, leading to the mirror image arrangements of the two forms eliciting quite different physiological responses. Penicillamine (Pen) is a common chiral drug that is obtained from penicillin, and researchers have been making continuous efforts to achieve rigorous analysis and discrimination of the two enantiomers. Based on chiral Schiff base macrocycles containing NH functionalities have the advantages of mild synthesis conditions and convergence of structural arrangement. Here we report two enantiomers of the mono-Schiff base macrocycle containing chiral NH moiety in the cyclic structure (CR and CS), and the binding affinity and enantioselectivity of the cyclic enantiomers toward small molecules penicillamine (D-Pen and L-Pen). The crystal structures of the mono-Schiff base cyclic enantiomers were determined by X-ray diffraction analysis, and the results show that the two cyclic enantiomers exhibit twisted non-planar conformation, in which the chiral NH proton points to the inside of the ring cavity. The interactions between different enantiomers of the chiral macrocycle and penicillamine were investigated by ultraviolet visible (UV-Vis) and hydrogen nuclear magnetic resonance ( 1 H NMR) titration, and the results show that the chiral macrocycle binds with the enantiomers of penicillamine with a bonding ratio of 1∶1, binding constants around 10 7 L•mol −1 , and the complexes of [C-Pen＋H] ＋ can be easily formed and detected by electrospray ionization-mass spectrometry (ESI-MS). The interactions between different enantiomers of the chiral macrocycle and penicillamine are attributed to the intermolecular hydrogen bonding of enantiomers by the asymmetrical chiral NH moiety in the mono-Schiff base macrocycle. Comparison of bonding constants based on the chiral macrocycle binds with the enantiomers of penicillamine, the results show that the chiral CR exhibits higher enantioselectivity for L-Pen, while CS exhibits the higher enantioselectivity for D-Pen, with a binding constant ratio around 2, respectively. Further, investigation of circular dichroism (CD) spectroscopic titration indicate that the penicillamine with the same chirality as the host macrocycle binds stronger with the host than its enantiomer with the host.

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Section: 引言unclassified

Enantiomers Identification of Penicillamine by Chiral Mono-Schiff Base Macrocycles

Tian¹,

Lin²,

Han³

et al. 2023

Acta Chimica Sinica

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“…While the SEGWE method was explicitly designed for small molecules, containing only lighter atoms such as C, H, and O, this has not stopped its use in the analysis of compounds and complexes containing aluminium [254][255][256], cobalt [257], copper [258,259], gold [260], heavy alkaline earth elements [261], all heavier Group 14 elements [262], iridium [263], nickel [264], palladium [236,265,266], samarium [267], selenium [268], silver [269,270], titanium [271], uranium [272], yttrium [273,274], and zinc [275,276]. While caution might be well advised in the extrapolated use of an effective density optimised using a training set consisting solely of small, organic molecules, it was noted in [259] that for the species studied therein, the ligand units used made up the bulk of the molecular weight, 540 g mol −1 , compared with the heavier Cu (64 g mol −1 ) atom and halides (35 g mol −1 for Cl, 127 g mol −1 for I).…”

Section: Stokes-einstein-gierer-wirtz Estimation -Examples and Applicationsmentioning

confidence: 99%

The interpretation of small molecule diffusion coefficients: Quantitative use of diffusion-ordered NMR spectroscopy

Evans

2020

Progress in Nuclear Magnetic Resonance Spectroscopy

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This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Structures, bonding and thermodynamics of extracting U(VI) from aqueous nitric acid solutions with N-methyl-N-decyl-octanamide and its amide derivatives: An M06-2X investigation

Cheng

2019

The Journal of Chemical Thermodynamics

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A DFT study on the recognition of α-amino acid derivatives by chiral uranyl–salen

Cited by 4 publications

References 54 publications

Enantiomers Identification of Penicillamine by Chiral Mono-Schiff Base Macrocycles

Enantiomers Identification of Penicillamine by Chiral Mono-Schiff Base Macrocycles

The interpretation of small molecule diffusion coefficients: Quantitative use of diffusion-ordered NMR spectroscopy

Structures, bonding and thermodynamics of extracting U(VI) from aqueous nitric acid solutions with N-methyl-N-decyl-octanamide and its amide derivatives: An M06-2X investigation

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