77826-55-2Relevant articles and documents
Characterization of (Boc-Cys/Sec-NHMe)2 and (Boc-Cys/Sec-OMe)2: Evidence of local conformational difference between disulfide and diselenide
Dolle, Ashwini,Reddy, K. Kasi Amarnath,Gunaga, Shubha Shridhar,Krishnamurthy, Kiran,Senapati, Dillip Kumar,Rana, Abhijit,Sindogi, Kishorkumar,Biswal, Himansu S.,Raghothama, Srinivasarao,Gowd, Konkallu Hanumae
, (2020)
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.
Palladium-Catalyzed Carbonylative Synthesis of Aryl Selenoesters Using Formic Acid as an Ex Situ CO Source
Yano De Albuquerque, Danilo,Teixeira, Wystan K. O.,Sacramento, Manoela Do,Alves, Diego,Santi, Claudio,Schwab, Ricardo S.
supporting information, p. 595 - 605 (2022/01/12)
A new catalytic protocol for the synthesis of selenoesters from aryl iodides and diaryl diselenides has been developed, where formic acid was employed as an efficient, low-cost, and safe substitute for toxic and gaseous CO. This protocol presents a high functional group tolerance, providing access to a large family of selenoesters in high yields (up to 97%) while operating under mild reaction conditions, and avoids the use of selenol which is difficult to manipulate, easily oxidizes, and has a bad odor. Additionally, this method can be efficiently extended to the synthesis of thioesters with moderate-to-excellent yields, by employing for the first time diorganyl disulfides as precursors.
Pyridazine N-Oxides as Photoactivatable Surrogates for Reactive Oxygen Species
Basistyi, Vitalii S.,Frederich, James H.
supporting information, p. 1907 - 1912 (2022/03/27)
A method for the photoinduced evolution of atomic oxygen from pyridazine N-oxides was developed. This underexplored oxygen allotrope mediates arene C-H oxidation within complex, polyfunctional molecules. A water-soluble pyridazine N-oxide was also developed and shown to promote photoinduced DNA cleavage in aqueous solution. Taken together, these studies highlight the utility of pyridazine N-oxides as photoactivatable O(3P) precursors for applications in organic synthesis and chemical biology.
A green disulfide synthesis method
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Paragraph 0052-0054, (2022/01/08)
The present invention discloses a green disulfide synthesis method, belonging to the field of green chemical and organic synthesis technology. Under room temperature, open, neutral conditions, rapid preparation of parent nuclei is alkanes, olefins, aromatic hydrocarbons, oxazole, thiazole, pyrazole, imidazole, etc. and their derivatives of symmetrical disulfide, the catalyst is MBrx(M is Fe2+,Fe3+,Ce3+, etc., x is 2-3), the only oxidant isH2O2. The present invention is reacted by using commercially available and low-cost reagents (e.g., FeBr2,CeBr3 andH2O2,etc.) and common organic solvents, the steps are concise, the operation is convenient, the reaction is rapid, the reaction conditions are mild, the room temperature is open, and no further purification can be obtained pure disulfide, more advantageous than all previous methods, is expected to be in organic synthesis, medicine, Pesticides and electronics and other industries are widely used.
Expressed Protein Ligation without Intein
Kratch, Kaci C.,Leeuwon, Sunshine Z.,Liu, Wenshe Ray,Morse, Jared S.,Qiao, Yuchen,Wang, Wesley Wei,Wang, Xiaoyan Aria,Xu, Shiqing,Yu, Ge
supporting information, p. 7047 - 7054 (2020/05/14)
Proteins with a functionalized C-terminus such as a C-terminal thioester are key to the synthesis of larger proteins via expressed protein ligation. They are usually made by recombinant fusion to intein. Although powerful, the intein fusion approach suffe
Scalable synthesis of orthogonally protected β-methyllanthionines by indium(III)-mediated ring opening of aziridines
Li, Ziran,Gentry, Zachary,Murphy, Brennan,Vannieuwenhze, Michael S.
supporting information, p. 2200 - 2203 (2019/03/26)
Lantibiotics are a class of peptide antibiotics with activity against most Gram-positive bacteria. Lanthionine (Lan) and β-MeLan are unusual thioether-bridged, non-proteinogenic amino acids, which are characteristic features of lantibiotics. In this paper, we report the facile stereoselective synthesis of β-methyllanthionines with orthogonal protection by nucleophilic ring opening of aziridines. This method leads to an expedient access to β-methyllanthionines and allows production of over 30 g of β-methyllanthionine in a single batch.
Modulating Thiol p Ka Promotes Disulfide Formation at Physiological pH: An Elegant Strategy to Design Disulfide Cross-Linked Hyaluronic Acid Hydrogels
Bermejo-Velasco, Daniel,Azémar, Alice,Oommen, Oommen P.,Hilborn, J?ns,Varghese, Oommen P.
, p. 1412 - 1420 (2019/03/02)
The disulfide bond plays a crucial role in protein biology and has been exploited by scientists to develop antibody-drug conjugates, sensors, and for the immobilization other biomolecules to materials surfaces. In spite of its versatile use, the disulfide chemistry suffers from some inevitable limitations such as the need for basic conditions (pH > 8.5), strong oxidants, and long reaction times. We demonstrate here that thiol-substrates containing electron-withdrawing groups at the β-position influence the deprotonation of the thiol group, which is the key reaction intermediate in the formation of disulfide bonds. Evaluation of reaction kinetics using small molecule substrate such as l-cysteine indicated disulfide formation at a 2.8-fold higher (k1 = 5.04 × 10-4 min-1) reaction rate as compared to the conventional thiol substrate, namely 3-mercaptopropionic acid (k1 = 1.80 × 10-4 min-1) at physiological pH (pH 7.4). Interestingly, the same effect could not be observed when N-acetyl-l-cysteine substrate (k1 = 0.51 × 10-4 min-1) was used. We further grafted such thiol-containing molecules (cysteine, N-acetyl-cysteine, and 3-mercaptopropionic acid) to a biopolymer namely hyaluronic acid (HA) and determined the pKa value of different thiol groups by spectrophotometric analysis. The electron-withdrawing group at the β-position reduced the pKa of the thiol group to 7.0 for HA-cysteine (HA-Cys); 7.4 for N-acetyl cysteine (HA-ActCys); and 8.1 for HA-thiol (HA-SH) derivatives, respectively. These experiments further confirmed that the concentration of thiolate (R-S-) ions could be increased with the presence of electron-withdrawing groups, which could facilitate disulfide cross-linked hydrogel formation at physiological pH. Indeed, HA grafted with cysteine or N-acetyl groups formed hydrogels within 3.5 min or 10 h, respectively, at pH 7.4. After completion of cross-linking reaction, both gels demonstrated a storage modulus G′ ≈ 3300-3500 Pa, which indicated comparable levels of cross-linking. The HA-SH gel, on the other hand, did not form any gel at pH 7.4 even after 24 h. Finally, we demonstrated that the newly prepared hydrogels exhibited excellent hydrolytic stability but can be degraded by cell-directed processes (enzymatic and reductive degradation). We believe our study provides a valuable insight on the factors governing the disulfide formation and our results are useful to develop strategies that would facilitate generation of stable thiol functionalized biomolecules or promote fast thiol oxidation according to the biomedical needs.
Cyclic telluride reagents with remarkable glutathione peroxidase-like activity for purification-free synthesis of highly pure organodisulfides
Arai, Kenta,Osaka, Yuui,Haneda, Masahiro,Sato, Yuumi
, p. 3647 - 3655 (2019/07/22)
Monoamino cyclic tellurides with a five- or six-membered ring structure and their derivatives were developed as a new class of catalyst for the oxidation of organothiols to organodisulfides in a glutathione peroxidase-like catalytic reaction. Quantitative conversion and high reaction rate were achieved by performing the reaction in an organic-aqueous segmented microflow system. Importantly, the process circumvented product purification, which is a major limitation of current organodisulfide synthetic methods.
COMPOUNDS AS L-CYSTINE CRYSTALLIZATION INHIBITORS AND USES THEREOF
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Paragraph 0314; 0316, (2018/11/21)
A method of preventing or inhibiting L-cystine crystallization is disclosed, using the compounds of formula I: [in-line-formulae]R1a—[O]v-(-A-L-)m-A-[O]v—R1b [/in-line-formulae] wherein A, L, R1a, R1b, m, and v are as described herein. The compounds may be prepared as pharmaceutical compositions, and may be used for the prevention and treatment of conditions that are causally related to L-cystine crystallization, such as comprising (but not limited to) kidney stones.
Cysteine-based silver nanoparticles as dual colorimetric sensors for cations and anions
Praveen Kumar,Kathuria, Lakshay,Haridas
supporting information, p. 8382 - 8389 (2016/10/11)
We report herein the synthesis of silver nanoparticles (Ag NPs), their characterization, and anion and cation sensing properties. Freshly prepared amide-triazole Ag NPs (3a-Ag NPs and 3b-Ag NPs) could detect fluoride and cations such as Hg2+ and Cd2+ in aqueous media with a color change from pink to brown. The cysteine-based Ag NPs 5b-Ag NPs showed a colorimetric response towards H2PO4-, whereas 6-Ag NPs showed a colorimetric response towards H2PO4- and HSO4- in aqueous media.
