The Significance of Induced Circular Dichroism

Gawroński, Jacek; Grajewski, Jakub

doi:10.1021/ol0352456

Cited by 47 publications

(36 citation statements)

References 13 publications

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“…4(a) show the typical CD spectrum of HSA with the minimums at 208 and 222 nm. 13 Obviously, this finding is an additional and unequivocal confirmation that diapocynin was complexed with HSA. The near-UV CD spectrum of HSA in the presence or absence of diapocynin was also studied.…”

Section: Interaction Of Diapocynin With Hsa: Induced Circular Dichroimentioning

confidence: 59%

“…To perform that, HSA has binding sites, which are cavities in the protein where the drugs are bound. 13 The appearance of ICD is a quite specific property, since it depends on effective binding between the ligand and the protein and also of a specific alteration in its molecular structure, leading to the conversion of its achiral to chiral conformation, in other words, from an optically inactive to active compound. 11 Diapocynin has a 2,2'-disubstituted-biphenyl moiety; hence, any energy barrier that impedes free rotation around the central single bond between the phenyl rings could provoke the appearance of chirality in this molecule, specifically, axial chirality.…”

Section: Introductionmentioning

confidence: 99%

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Experimental, DFT and docking simulations of the binding of diapocynin to human serum albumin: induced circular dichroism

et al. 2015

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Diapocynin has been regarded as the active principle of apocynin, which is the most used inhibitor of NADPH oxidase. Here we performed a comprehensive study of the interaction of diapocynin with human serum albumin (HSA). We found that diapocynin binds with higher efficacy to site I of HSA and its binding constant (8.5x10 5 mol -1 L) was almost 100-fold higher compared to apocynin. By interacting with this chiral cavity of the protein, diapocynin became a chiral molecule, which was evidenced by its induced circular dichroism spectrum.The axial chirality was theoretically confirmed by searching the most stable conformations adopted by diapocynin using the Density Function Theory (DFT). The four minimum energy conformers, which presented dihedral angles of 58.00° and 302.00° (syn-aS and syn-aR enantiomers pair bearing 2,2'-dihydroxyl groups at the same side) and 132.86° and 227.14° (anti-aS and anti-aR enantiomers pair bearing 2,2'-dihydroxyl groups at opposite sides) were used as initial conformations for the docking simulations. The highest scored docking pose was obtained for site 1 and the dihedral angle resulted in 106.44°, i.e., an anti-aS chiral conformer. In conclusion, diapocynin is a strong ligand of HSA. An unprecedented combination of DFT calculation and docking simulation was used to explain the acquired chirality of diapocynin when bound to HSA.

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Section: Interaction Of Diapocynin With Hsa: Induced Circular Dichroimentioning

confidence: 59%

Section: Introductionmentioning

confidence: 99%

Experimental, DFT and docking simulations of the binding of diapocynin to human serum albumin: induced circular dichroism

et al. 2015

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“…It is known as induced chirality and is experimentally detected by the appearance of a new circular dichroism signal, which originally was not present in the protein or in the free ligand [17]. How proposed by Gawronski and Grajewski there are two different conditions for induction of chirality: induction of a dominating chiral structure of the achiral molecule or induction of a chiral arrangement of the electric dipole transition moments between the relevant chromophores of the achiral (guest) and chiral (host) molecules [26]. Regardless its origin, the induction of chirality by host-guest interaction leads to a new circular dichroism signal, which is known as induced circular dichroism (ICD) and can be useful for studying the interaction between proteins and ligands.…”

Section: Introductionmentioning

confidence: 99%

“…In this case, the use of drugs that are well-stablished ligands of site I or II and susceptible to ICD are used to evaluate the effect of the competitor studied compound. For instance, phenylbutazone, diazepam and bilirubin as site markers for site I, II and III, respectively [17, 26, 27] and dansylglycine for site II [28] are all susceptible to ICD. For these reasons, here we aimed to study the features of divanillin as a ligand of bovine serum albumin (BSA).…”

Section: Introductionmentioning

confidence: 99%

Induction of axial chirality in divanillin by interaction with bovine serum albumin

et al. 2017

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Vanillin is a plant secondary metabolite and has numerous beneficial health applications. Divanillin is the homodimer of vanillin and used as a taste enhancer compound and also a promissory anticancer drug. Here, divanillin was synthesized and studied in the context of its interaction with bovine serum albumin (BSA). We found that divanillin acquires axial chirality when complexed with BSA. This chiroptical property was demonstrated by a strong induced circular dichroism (ICD) signal. In agreement with this finding, the association constant between BSA and divanillin (3.3 x 105 mol-1L) was higher compared to its precursor vanillin (7.3 x 104 mol-1L). The ICD signal was used for evaluation of the association constant, demonstration of the reversibility of the interaction and determination of the binding site, revealing that divanillin has preference for Sudlow’s site I in BSA. This property was confirmed by displacement of the fluorescent markers warfarin (site I) and dansyl-L-proline (site II). Molecular docking simulation confirmed the higher affinity of divanillin to site I. The highest scored conformation obtained by docking (dihedral angle 242°) was used for calculation of the circular dichroism spectrum of divanillin using Time-Dependent Density Functional Theory (TDDFT). The theoretical spectrum showed good similarity with the experimental ICD. In summary, we have demonstrated that by interacting with the chiral cavities in BSA, divanillin became a atropos biphenyl, i.e., the free rotation around the single bound that links the aromatic rings was impeded. This phenomenon can be explained considering the interactions of divanillin with amino acid residues in the binding site of the protein. This chiroptical property can be very useful for studying the effects of divanillin in biological systems. Considering the potential pharmacological application of divanillin, these findings will be helpful for researchers interested in the pharmacological properties of this compound.

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“…1 Induced circular dichroism (ICD) is observed when covalent or noncovalent association between a chiral substrate and a UV active, stereodynamic probe favors population of a chiral conformation or configuration of the latter, thus causing a distinct CD output. [2][3][4] The development of conformationally flexible receptors capable of reporting a molecular recognition event upon binding to a substrate provides new avenues for chiroptical analysis. [5][6][7][8][9][10] For example, Rosini and Toniolo demonstrated that the absolute configuration of chiral amino acids, carboxylic acids, and alcohols can be correlated to the ICD output of a covalently linked stereodynamic biphenyl reporter unit.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective sensing of chiral amino alcohols with a stereodynamic arylacetylene‐based probe

2012

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Enantioselective induced circular dichroism analysis of amino alcohols has been accomplished using a conformationally flexible arylacetylene-based probe exhibiting two terminal aldehyde groups. The chirality of the amino alcohol substrates is imprinted on the stereodynamic receptor upon [1 + 2] condensation, which ultimately generates a strong chiroptical response. The distinct induced circular dichroism effects of the diimines obtained can be used for enantioselective sensing and enantiomeric excess determination of a wide range of substrates.

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The Significance of Induced Circular Dichroism

Cited by 47 publications

References 13 publications

Experimental, DFT and docking simulations of the binding of diapocynin to human serum albumin: induced circular dichroism

Experimental, DFT and docking simulations of the binding of diapocynin to human serum albumin: induced circular dichroism

Induction of axial chirality in divanillin by interaction with bovine serum albumin

Enantioselective sensing of chiral amino alcohols with a stereodynamic arylacetylene‐based probe

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