Abstract:Thioamides are used as potential surrogates of amides to study the structure and dynamics of proteins and nucleic acids. However, incorporation of thioamides in biomolecules leads to changes in their structures and conformations mostly attributed to the strength of the amide-N-H···S═C hydrogen bond. In most cases, it is considered weak owing to the small electronegativity of sulfur, and in some cases, it is as strong as conventional H-bonds. Herein, adopting PDB structure analysis, NMR spectroscopy, and quantu… Show more
“…25 Studies on small peptide systems have revealed that backbone-backbone H-bonding interactions may exist in thioamides. 26,27 Nonetheless, it was generally assumed for some time that a side-chain thioether was a poor H-bond acceptor and that N-H/S interactions between amide backbones and the sulfur atom of methionine were weak and of little signicance. 28,29 Recent observations on model systems have challenged this credo, however.…”
In addition to the classical N–H···O=C non-covalent interaction, less conventional types of hydrogen bonding, such as N–H···S, may play a key role in determining the molecular structure. In this work,...
“…25 Studies on small peptide systems have revealed that backbone-backbone H-bonding interactions may exist in thioamides. 26,27 Nonetheless, it was generally assumed for some time that a side-chain thioether was a poor H-bond acceptor and that N-H/S interactions between amide backbones and the sulfur atom of methionine were weak and of little signicance. 28,29 Recent observations on model systems have challenged this credo, however.…”
In addition to the classical N–H···O=C non-covalent interaction, less conventional types of hydrogen bonding, such as N–H···S, may play a key role in determining the molecular structure. In this work,...
“…16 Recently, it has become evident that the replacement of oxygen in amide bonds by other chalcogens such as sulphur and selenium retains the ability of the resulting thio-and selenoamides to engage in hydrogen bonding interactions. [17][18][19][20] In addition, it has been observed both theoretically and experimentally that NHÁ Á ÁS or NHÁ Á ÁSe hydrogen bonds can be as strong as those of NHÁ Á ÁO, despite the lower electronegativity of S and Se. 21,22 In proteins and peptides, the introduction of thioamide or selenoamide bonds has allowed to tune their structure, stability, and -in case of enzymes -activity.…”
mentioning
confidence: 99%
“…Here, we disclose the synthesis (reported in the ESI †) and selfassembly of the chiral, C 3 -symmetrical benzene-tricarboselenoamide c-SeBTA (Scheme 1). We compare its self-assembly behavior to that of OBTA/c-OBTA 20 and SBTA/c-SBTA. 21 The different nature of the selenoamide hydrogen bond is illustrated by our finding that c-SeBTA polymers have an increased stability towards thermal denaturation yet enhanced lability towards polar solventsinduced denaturation.…”
Selenoamide moieties introduced into C3-symmetrical molecules enhance supramolecular interactions and confer a remarkable thermal stability to the supramolecular polymers.
“…The substitution of O with S provides a greater contact surface area between the peptide and the receptor, which leads to improved van der Waals interactions mediated by the C S group compared to the C O group. 10 Although we did not notice any direct hydrogen bonds between the protein and S atom, 31 we cannot fully negate the possibility of any water mediated hydrogen bonding between the S atom and the receptor. 32 …”
Thioamide substitution into macrocyclic peptides increases the conformational rigidity of the backbone resulting in enhanced biological activity and metabolic stability.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.