Crystal structure of seleno-<scp>L</scp>-cystine dihydrochloride

Görbitz, Carl Henrik; Levchenko, V. E.; Semjonovs, Jevgenijs; Sharif, Mohamed Yusuf

doi:10.1107/s205698901501021x

Cited by 8 publications

(8 citation statements)

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“…These interactions occur in crystalline cystine and selenocystine, two naturally occurring amino acids (Figure ). , The biological relevance of these compounds and of some others discussed above (Figure ) suggests that the ChB donor ability of the moieties discussed in this paragraph may have a nonminor biological importance. Dicyanodiselenide functions as a tetradentate ChB donor consistent with the computed presence of two σ-holes on any selenium atom (Figure ).…”

Section: Sulfides Disulfides and Selenium And Tellurium Analoguesmentioning

confidence: 99%

The Chalcogen Bond in Crystalline Solids: A World Parallel to Halogen Bond

2019

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Conspectus The distribution of the electron density around covalently bonded atoms is anisotropic, and this determines the presence, on atoms surface, of areas of higher and lower electron density where the electrostatic potential is frequently negative and positive, respectively. The ability of positive areas on atoms to form attractive interactions with electron rich sites became recently the subject of a flurry of papers. The halogen bond (HaB), the attractive interaction formed by halogens with nucleophiles, emerged as a quite common and dependable tool for controlling phenomena as diverse as the binding of small molecules to proteinaceous targets or the organization of molecular functional materials. The mindset developed in relation to the halogen bond prompted the interest in the tendency of elements of groups 13–16 of the periodic table to form analogous attractive interactions with nucleophiles. This Account addresses the chalcogen bond (ChB), the attractive interaction formed by group 16 elements with nucleophiles, by adopting a crystallographic point of view. Structures of organic derivatives are considered where chalcogen atoms form close contacts with nucleophiles in the geometry typical for chalcogen bonds. It is shown how sulfur, selenium, and tellurium can all form chalcogen bonds, the tendency to give rise to close contacts with nucleophiles increasing with the polarizability of the element. Also oxygen, when conveniently substituted, can form ChBs in crystalline solids. Chalcogen bonds can be strong enough to allow for the interaction to function as an effective and robust tool in crystal engineering. It is presented how chalcogen containing heteroaromatics, sulfides, disulfides, and selenium and tellurium analogues as well as some other molecular moieties can afford dependable chalcogen bond based supramolecular synthons. Particular attention is given to chalcogen containing azoles and their derivatives due to the relevance of these moieties in biosystems and molecular materials. It is shown how the interaction pattern around electrophilic chalcogen atoms frequently recalls the pattern around analogous halogen, pnictogen, and tetrel derivatives. For instance, directionalities of chalcogen bonds around sulfur and selenium in some thiazolium and selenazolium derivatives are similar to directionalities of halogen bonds around bromine and iodine in bromonium and iodonium compounds. This gives experimental evidence that similarities in the anisotropic distribution of the electron density in covalently bonded atoms translates in similarities in their recognition and self-assembly behavior. For instance, the analogies in interaction patterns of carbonitrile substituted elements of groups 17, 16, 15, and 14 will be presented. While the extensive experimental and theoretical data available in the literature prove that HaB and ChB form twin supramolecular synthons in the solid, more experimental information has to become available before such a statement can be safely extended to interactions wherein ele...

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Section: Sulfides Disulfides and Selenium And Tellurium Analoguesmentioning

confidence: 99%

The Chalcogen Bond in Crystalline Solids: A World Parallel to Halogen Bond

2019

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“…A comparative study of the bond length C−Se and torsion angle, τ (SeC β C α C) (Table ) for the molecular structure of seleno‐ l ‐cystine dihydrochloride 5 , selenocysteic acid 9 , unnatural selenocystine containing peptide, l ‐selenocystine mutated Sec‐PnIA and GPx enzyme is shown in Table . Selenocysteic acid 9 has a slightly shorter C−Se bond than selenocystine hydrochloride because of the presence of electronegative atoms.…”

Section: Resultsmentioning

confidence: 99%

“…[33] In the crystal packing of two units, the significant intramolecular and intermolecular interactions between the two units are Se1=O5···N1, distance 2.762 andS e1=O3···N1,d istance 2.740 . Ac omparatives tudy of the bond length CÀSe and torsion angle, t(SeC b C a C) (Table 1) for the molecular structure of seleno-l-cystine dihydrochloride 5, [34] selenocysteic acid 9,u nnatural selenocystine containing peptide, [35] l-selenocystine mutated Sec-PnIA [36] and GPx enzyme [37] is shown in Table 2. Selenocysteic acid 9 has as lightly shorter CÀSe bond than selenocystine hydrochloride because of the presence of electronegative atoms.…”

Section: Molecular Structures Of 9a Nd 13mentioning

confidence: 99%

Reactivity of Selenocystine and Tellurocystine: Structure and Antioxidant Activity of the Derivatives

Satheeshkumar

Raju

Singh

et al. 2018

Chemistry A European J

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l-Selenocystine (5) and l-tellurocystine (6) have been prepared and the reactivity of these amino acids, i.e., oxidation of 5 and 6, has been performed at various pH values. Hydrogen peroxide was used as an oxidant and it was treated with 5 and 6 in excess in acidic and basic media. Compound 5, upon oxidation, afforded Se and Se products. Selenocysteic acid [HO SeCH CH(NH )COOH] 9, a novel Se compound, was isolated and characterised by single-crystal X-ray diffraction studies. In contrast, l-tellurocystine, upon oxidation with H O , afforded Te and Te products. Zwitterionic organotellurolate(IV), [TeCl CH CH(NH )COOH] 13, was isolated and characterised by NMR and IR spectroscopy, mass spectrometry and elemental analysis. Compound 13 crystallizes in an orthorhombic space group. l-Tellurocystine, when reduced with NaBH , produced the desired tellurolate intermediate, which was trapped with bromoacetic acid. Furthermore, l- and d-tellurocysteine derivatives, [(RTeCH CH(NH )COOH) R=phenyl, substituted phenyl and naphthyl (24-39)] were synthesised and evaluated for their glutathione peroxidase (GPx)-like activities. The results show that l-tellurocysteine derivatives have higher activity than their D-tellurocysteine analogues. DFT calculations for l-tellurocysteine derivatives provided information about the bond lengths and bond angles. This study reveals that the introduction of naphthyl substituents (35-38) leads to twisted conformation of the amino acid derivatives.

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“…Interestingly, the large deviations in the torsion angles between disulfide and diselenide are centered at χ 2 , χ 3 , and χ 2 ′ that describes rotations of planes about C β –S/Se, S/Se‐S/Se, and S/Se–C β bonds encompassing sulfur/selenium. In crystals of cystine/selenocystine (dihydrochloride form), the torsion angles are nearly the same between disulfide and diselenide, and the only obvious difference is increase in the length of the cell edge for selenocystine . However, inspection of structures in the unit cells have revealed for sulfur a 3.5 Å and for selenium a 3.6‐Å distance from chlorine, which corresponds to the sum of their Van der Waals radius.…”

Section: Discussionmentioning

confidence: 99%

Characterization of (Boc‐Cys/Sec‐NHMe)₂ and (Boc‐Cys/Sec‐OMe)₂: Evidence of local conformational difference between disulfide and diselenide

Dolle

Reddy

Gunaga

et al. 2020

Journal of Peptide Science

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Conformations of disulfide and diselenide were compared in (Boc‐Cys/Sec‐NHMe)2 and (Boc‐Cys/Sec‐OMe)2 using X‐ray crystallography, nuclear magnetic resonance (NMR) spectroscopy, density functional theory (DFT), and circular dichroism (CD) spectroscopy. Conformations of disulfide/diselenide in polypeptides are defined based on the sign of side chain torsion angle χ3 (–CH2–S/Se–S/Se–CH2–); negative indicates left‐handed and positive indicates right‐handed orientation. In the crystals of (Boc‐Cys‐OMe)2 and (Boc‐Sec‐OMe)2, the disulfide exhibits a left‐handed and the diselenide a right‐handed orientation. Characterization of cystine and selenocystine derivatives in solution using 1H‐NMR, natural abundant 77Se NMR, 2D‐ROESY, and chemical shift analysis coupled to DMSO titration has indicated the symmetrical nature and antiparallel orientation of Cys/Sec residues about the disulfide/diselenide bridges. Structural calculations of cystine and selenocystine derivatives using DFT further support the antiparallel orientation of Cys/Sec residues about disulfide/diselenide. The far‐ultraviolet (UV) region CD spectra of cystine and selenocystine derivatives have exhibited the negative Cotton effect (CE) for disulfide and positive for diselenide confirming the difference in the conformational preference of disulfide and diselenide. In the previously reported polymorphic structure of (Boc‐Sec‐OMe)2, the diselenide has right‐handed orientation. In the X‐ray structures of disulfide and diselenide analogues of Escherichia coli protein encoded by curli specific gene C (CgsC) retrieved from Protein Databank (PDB), disulfide has left‐handed and the diselenide right‐handed orientation. The current report provides the evidence for the local conformational difference between a disulfide and a diselenide group under unconstrained conditions, which may be useful for the rational replacement of disulfide by diselenide in polypeptide chains.

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Crystal structure of seleno-L-cystine dihydrochloride

Abstract: The crystal structure of seleno-l-cystine, in its hydrochloric acid salt, is isotypic with the common analogue with Se atoms replaced by sulfur, i.e. L-cystine hydrochloride.

Cited by 8 publications

References 11 publications

The Chalcogen Bond in Crystalline Solids: A World Parallel to Halogen Bond

The Chalcogen Bond in Crystalline Solids: A World Parallel to Halogen Bond

Reactivity of Selenocystine and Tellurocystine: Structure and Antioxidant Activity of the Derivatives

Characterization of (Boc‐Cys/Sec‐NHMe)₂ and (Boc‐Cys/Sec‐OMe)₂: Evidence of local conformational difference between disulfide and diselenide

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Crystal structure of seleno-L-cystine dihydrochloride

Abstract: The crystal structure of seleno-l-cystine, in its hydro­chloric acid salt, is isotypic with the common analogue with Se atoms replaced by sulfur, i.e. L-cystine hydro­chloride.

Cited by 8 publications

References 11 publications

The Chalcogen Bond in Crystalline Solids: A World Parallel to Halogen Bond

The Chalcogen Bond in Crystalline Solids: A World Parallel to Halogen Bond

Reactivity of Selenocystine and Tellurocystine: Structure and Antioxidant Activity of the Derivatives

Characterization of (Boc‐Cys/Sec‐NHMe)2 and (Boc‐Cys/Sec‐OMe)2: Evidence of local conformational difference between disulfide and diselenide

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Abstract: The crystal structure of seleno-l-cystine, in its hydrochloric acid salt, is isotypic with the common analogue with Se atoms replaced by sulfur, i.e. L-cystine hydrochloride.

Characterization of (Boc‐Cys/Sec‐NHMe)₂ and (Boc‐Cys/Sec‐OMe)₂: Evidence of local conformational difference between disulfide and diselenide