- Catalytic antioxidant activity of bis-aniline-derived diselenides as GPx mimics
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Herein, we describe a simple and efficient route to access aniline-derived diselenides and evaluate their antioxidant/GPx-mimetic properties. The diselenides were obtained in good yields via ipso-substitution/reduction from the readily available 2-nitroaromatic halides (Cl, Br, I). These diselenides present GPx-mimetic properties, showing better antioxidant activity than the standard GPx-mimetic compounds, ebselen and diphenyl diselenide. DFT analysis demonstrated that the electronic properties of the substituents determine the charge delocalization and the partial charge on selenium, which correlate with the catalytic performances. The amino group concurs in the stabilization of the selenolate intermediate through a hydrogen bond with the selenium.
- Barbosa, Flavio A. R.,Bettanin, Luana,Botteselle, Giancarlo V.,Braga, Antonio L.,Canto, R?mulo F. S.,Ciancaleoni, Gianluca,Domingos, Josiel B.,Elias, Welman C.,Gallardo, Hugo,Rafique, Jamal,Saba, Sumbal,Salin, Drielly N. O.
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supporting information
(2021/08/06)
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- Naphthalimide derivative containing selenoheterocycle, and preparation method and antiviral application thereof (by machine translation)
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The invention discloses a selenoheterocycle-containing naphthalimide derivative and a preparation method and an antiviral application thereof, wherein the naphthalimide derivative is 1. H, 3H-selenium xanthene [2, 1, 9 -]Def] Isoquinoline -1, 3 (2)HThe diketone derivative hydrochloride has a structural formula shown in the formula (1 - 7) as shown in the specification. The compound 1 - 7 disclosed by the invention is used for inducing a human host cell II type serine protease TMPMPMPRSS2 promoter region to be rich in guanine DNA sequences to induce formation G - four-chain bodies. The conjugated mother ring structure in compound 1 - 7 can interact with G - four split formed in the research target in π -pi stacking mode through computer molecule simulation experiment, and the side chain can be well combined with the groove structure G - four-chain body. The invention plays an important role in developing clinical medicine development of the naphthalimide derivative containing the selenium heterocycle, and especially has an important value for finding a new antiviral small molecule medicine. (by machine translation)
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Paragraph 0022; 0053
(2020/07/12)
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- Mechanistic Studies on the Anodic Functionalization of Alkenes Catalyzed by Diselenides
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Herein, we present a detailed kinetic and thermodynamic analysis of the anodic allylic esterification of alkenes as well as the bulk application of the anodic amination and esterification of nonactivated alkenes catalyzed by diselenides. The electrochemical study led to a comprehensive picture of the coupled electrochemical and chemical reaction steps. Cyclic voltammetry measurements are consistent with a bimolecular step after initial electrochemical 1e- oxidation of the diphenyl diselenide catalyst, 1a, and therefore we postulate a dimerization of the cation, which reacts very rapidly with the alkene, forming the addition product, i.e. the selenolactone 2a. Subsequent electrochemical oxidation of 2a occurs at a slightly higher potential than initial oxidation of 1a. The second oxidation is also followed by a bimolecular process and we hypothesize a dimerization of the cation, which finally eliminates 1a and protons in the rate-determining step, forming the product. Electrochemical analysis of various catalysts, i.e. nonsterically demanding diaryl diselenides with electron withdrawing and donating substituents, revealed that the oxidation potential of the catalyst and the intermediate can be readily tuned by the substituents, thus, prospectively allowing for a wide application of olefinic and nucleophilic substrates. The substituent pattern at the alkene has a smaller influence on the redox potential of the adduct. Controlled potential electrolysis experiments employing different nucleophiles proved that the reaction can be run electrochemically. The functionalization of unactivated alkenes with N- and O-nucleophiles was successfully demonstrated in several bulk electrolysis experiments, and the products were isolated in good yields.
- Wilken, Mona,Ortgies, Stefan,Breder, Alexander,Siewert, Inke
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p. 10901 - 10912
(2018/11/02)
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- Selenols are resistant to irreversible modification by HNO
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The discovery of nitric oxide (NO) as an endogenously generated signaling species in mammalian cells has spawned a vast interest in the study of the chemical biology of nitrogen oxides. Of these, nitroxyl (azanone, HNO) has gained much attention for its potential role as a therapeutic for cardiovascular disease. Known targets of HNO include hemes/heme proteins and thiols/thiol-containing proteins. Recently, due to their roles in redox signaling and cellular defense, selenols and selenoproteins have also been speculated to be additional potential targets of HNO. Indeed, as determined in the current work, selenols are targeted by HNO. Such reactions appear to result only in formation of diselenide products, which can be easily reverted back to the free selenol. This characteristic is distinct from the reaction of HNO with thiols/thiolproteins. These findings suggest that, unlike thiolproteins, selenoproteins are resistant to irreversible oxidative modification, support that Nature may have chosen to use selenium instead of sulfur in certain biological systems for its enhanced resistance to electrophilic and oxidative modification.
- Bianco, Christopher L.,Moore, Cathy D.,Fukuto, Jon M.,Toscano, John P.
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- Compound for treatment or prevention of breast cancer
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The invention discloses a compound for treatment or prevention of breast cancer, specifically a 2-phenyl benzoselenazole compound, its pharmaceutically acceptable salt and easily hydrolysable prodrug. The invention further discloses a pharmaceutical composition containing the compounds and use of the compound in preparation of drugs for treatment or prevention of breast cancer in mammals. The compound involved in the invention can effectively inhibit or reduce mammalian breast cancer cell growth or proliferation, at the same time, the compound has no inhibiting effect on the growth of partial test cells except for breast cancer cells and has good selectivity. The compound shows more obvious efficacy, high selectivity, low toxicity and small side effect. (formula of the compound).
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Paragraph 0059; 0060; 0063
(2018/02/04)
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- Aldehyde capture ligation for synthesis of native peptide bonds
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Chemoselective reactions for amide bond formation have transformed the ability to access synthetic proteins and other bioconjugates through ligation of fragments. In these ligations, amide bond formation is accelerated by transient enforcement of an intramolecular reaction between the carboxyl and the amine termini of two fragments. Building on this principle, we introduce an aldehyde capture ligation that parlays the high chemoselective reactivity of aldehydes and amines to enforce amide bond formation between amino acid residues and peptides that are difficult to ligate by existing technologies.
- Raj, Monika,Wu, Huabin,Blosser, Sarah L.,Vittoria, Marc A.,Arora, Paramjit S.
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supporting information
p. 6932 - 6940
(2015/06/16)
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- Synthesis of disulfides and diselenides by copper-catalyzed coupling reactions in water
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A simple and efficient protocol for copper-catalyzed coupling reactions between aryl halides and elemental sulfur or selenium has been developed. A variety of disulfides and diselenides can be obtained in moderate to excellent yields up to 96%. The Royal Society of Chemistry 2013.
- Li, Zhengkai,Ke, Fang,Deng, Hang,Xu, Hualong,Xiang, Haifeng,Zhou, Xiangge
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supporting information
p. 2943 - 2946
(2013/07/25)
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- Sensitive near-infrared fluorescent probes for thiols based on Se-N bond cleavage: Imaging in living cells and tissues
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Cy-NiSe and Cy-TfSe were designed and synthesized as sensitive near-infrared (NIR) fluorescent probes for detecting thiols on the basis of Se-N bond cleavage both in cells and in tissues. Since a donor-excited photoinduced electron transfer (d-PET) process occurs between the modulator and the fluorophore, Cy-NiSe and Cy-TfSe have weak fluorescence. On titration with glutathione, the free dye exhibits significant fluorescence enhancement. The two probes are sensitive and selective for thiols over other relevant biological species. They can function rapidly at pH 7.4, and their emission lies in the NIR region. Confocal imaging confirms that Cy-NiSe and Cy-TfSe can be used for detecting thiols in living cells and tissues. Turn-on fluorescent probes Cy-NiSe and Cy-TfSe, which show weak fluorescence due to donor-excited photoinduced electron transfer, release near-infrared fluorescent dye Cy7-MeAm on cleavage of the Se-N bond by thiols. Thus, they can be used for real-time imaging of thiols such as glutathione in living cells and tissue (see figure). Copyright
- Wang, Rui,Chen, Lingxin,Liu, Ping,Wang, Yunqing,Zhang, Qin
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supporting information
p. 11343 - 11349,7
(2012/12/12)
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- Bis(2-aminophenyl) diselenide derivatives with amino acids moieties as potential antivirals and antimicrobials
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The seleno-organic compounds based on bis(2-aminophenyl) diselenide-1 are potential antiviral, antibacterial and antifungal agents.1 In this work, we reported synthesis of bis(2-aminophenyl) diselenide derivatives 2, 3 having amino acid and dipeptide moieties. This process was realized by acylation of amine groups in 1 with N-blocked amino acids, using the active esters method (with DCC and HOBT). After removing protective groups successive N-blocked amino acids were added the same way as previously. All compounds have been tested against broad spectrum of pathogenic microorganisms (Staphylococcus aureus, Staphylococcus simulans, Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, Candida albicans, Aspergillus niger) and viruses (HSV-1, EMCV, VSV), in vitro. Most of them exhibited high activity against EMCV. Some of tested compounds were active against gram-positive bacteria species (Staphylococcus aureus, Staphylococcus simulans) and yeast Candida albicans.
- Dbrowska, Ewa,Ptka-Ottlik, Magdalena,Palus, Jerzy
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experimental part
p. 1082 - 1086
(2009/04/10)
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- Functionalized alkyl and aryl diselenides as antimicrobial and antiviral agents: Synthesis and properties
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The different dialkyl and diaryl diselenides with carbamoyl and sulfamoyl moieties 2, 3, 5 and other substituents in the ortho position of benzene ring 4, 7, 8 as well as derivatives of 1,2,4-benzoselenadiazine (6) were designed as antiviral and antimicrobial agents and synthesized. Some of them, particularly 8a and 8b, were found in the antiviral assay in vitro to be strong inhibitors of cytopathic activity encephalomyocarditis virus (EMCV). The compound 4a and 8a were found to have a broad spectrum of acivity against bacteria, yeasts and pathogenic fungi in vitro.
- Wojtowicz,Chojnacka,Mlochowski,Palus,Syper,Hudecova,Uher,Piasecki,Rybka
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p. 1235 - 1242
(2007/10/03)
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- New heterocyclic selenenamides: 1,2,4-benzoselenadiazin-3(4H)-ones and 1,3,2-benzodiselenazoles
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Two groups of selenium-containing heterocycles having new, unique 1,2,4-benzoselenadiazine and 1,3,2-diselenazole ring systems with an endocyclic selenenamide C-N moiety are presented. The first type was obtained by oxidative cyclization of 2,2′-diselenobis(phenylureas) and the second type by the reaction of 1,2-di(bromoseleno)benzene with primary amines.
- Kloc, Krystian,M?ochowski, Jacek,Osajda, Karol,Syper, Ludwik,Wójtowicz, Halina
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p. 4071 - 4074
(2007/10/03)
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- Synthesis of diselenadiazafulvalenes and influence of steric strain on their anodic behavior
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A novel family of π-donor molecules, the diselenadiazafulvalenes (DSeDAFs), is presented. The synthetic approach to these donors, from o-nitroaniline, allows the formation of N,N′-dimethyldibenzo DSeDAF and N,N′-ethylenedibenzo DSeDAF. Comparative electrochemical study of these π-donor molecules demonstrates their excellent donor ability and the stabilizing effect of the ethylene bridge on the cation radical species.
- Casar, Zdenko,Leban, Ivan,Marechal, Alenka Majcen-Le,Lorcy, Dominique
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p. 1568 - 1573
(2007/10/03)
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- Synthesis of organic diselenide using zinc powder
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A new synthetic method of diselenide by reducing element selenium with zinc powder in basic environment, and then reacting with electrophiles is described. Nine diselenides are synthesized with yields between 52-90%.
- Ping,Xunjun
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p. 1721 - 1725
(2007/10/02)
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- ELECTROCHEMICAL SYNTHESIS OF SELENO AND TELLURO DERIVATIVES IN MeCN
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Large-scale electrolysis with concurrent sonication in MeCN allows for the synthesis of a large variety of seleno and telluro derivatives.Aliphatic chalcogenides REER or RER (E = Se, Te) can be prepared by reduction of E powder to E2(2-) or E(2-), followed by addition of an alkyl halide RX.Depending upon R, substitution can compete with homogeneous electron or H+ transfers.RE+ can be prepared by anodic oxidation of REER, and trapped by nucleophiles and olefins.The synthesis of aromatic chalcogenides ArEAr'can be carried out by electrochemically inducedSRN1 substitution.The yields are improved by redox catalysis.Under such conditions, the synthesis of PhEAr (Ar = NCC6H4, PhCOC6H4) proceeds in good yields.ArEEAr and ArEAr can be prepared by cathodic reduction of PhEAr.
- Degrand, Chantal,Prest, Rita,Nour, Mohamed
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p. 201 - 210
(2007/10/02)
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- LITHIUM DISELENIDE IN APROTIC MEDIUM - A CONVENIENT REAGENT FOR SYNTHESIS OF ORGANIC DISELENIDES
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The reduction of selenium with lithium in THF in the presence of diphenylacetylene as a catalyst afforded lithium diselenide, which reacted with electrophiles giving alkyl or aryl diselenides 1 - 3 and selenides 4, as by-products.The useful method for preparation of diselenides based on this reaction was elaborated.
- Syper, Ludwik,Mlochowski, Jacek
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p. 6119 - 6130
(2007/10/02)
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- Rates of Oxidation of o-Nitrobenzeneselenenyl Compounds by m-Chloroperoxybenzoic Acid and the Rate of Reaction of o-Nitrobenzeneselenol with o-Nitrobenzeneselenenic Acid
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Rate constants for the oxidation of a series of o-nitrobenzeneselenenyl derivatives (Ar = o-O2NC6H4) by m-chloroperoxybenzoic acid (MCPBA) have been measured at 25 deg C in ethanol (compound, kPA (M-1s-1)): ArSeH, 1.1 * 104; ArSeOH, 80; ArSeOSeAr, 12; ArSeOEt, 4; ArSeSeAr, 0.15.The rate constant (kArSeH = 1.0 * 102 M-1s-1) for the reaction of ArSeH with ArSeOH to give ArSeSeAr (eq 3), which is pH independent in acid solution, has also been determined.Significant practical consequences of these and related results include the following: (a) the rate of oxidation of selenol (ArSeH) to selenenic acid (ArSeOH) is enough faster than either the oxidation of ArSeOH to seleninic acid (ArSeO2H) or eq 3 so that oxidation of the selenol with 1 molar equiv of MCPBA gives ArSeOH in high yield; (b) with a weaker oxidant, hydrogen peroxide, the rate of oxidation of the selenol is enough slower than the rate of eq 3 that the diselenide (ArSeSeAr) becomes the almost exclusive product; (c) the rate of oxidation of the diselenide is so much smaller than that of any of the other compounds that its initial oxidation to ArSeOSeAr is far and away the slowest step in its overall oxidation to seleninic acid by excess peracid.
- Kice, John L.,Chiou, Shishue
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p. 290 - 294
(2007/10/02)
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- COMPARATIVE REACTIVITIES OF SELENOSULFATES AND SELENENYLTHIOSULFATES WITH THIOLS
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Nitroaryl selenosulfates (1) and selenenylthiosulfates (2) reacted instantaneously with a thiol, N-succinylcysteamine, in water at pH 4.6 to give an insoluble selenenyl sulfide and diselenide.The selenenyl sulfide was the major product from the 2-nitro compounds whereas the diselenide was the major (almost exclusive) product from the 4-nitro compounds.However when the 4-nitro compounds reacted with N-succinylcysteamine in dimethylformamide the selenenyl sulfide was the major and the diselenide the minor product indicating the formation of selenenyl sulfide preceded that of diselenide.Also in the dimethylformamide reactions a short-lived, light-sensitive, purple intermediate was formed which was identified as 4-nitroselenophenol.It was impossible to compare reactivities of selenosulfates and selenenylthiosulfates in water since all reacted immediately to form insoluble products.However, when formation of the purple complex of 4-nitroselenophenol in dimethylformamide was used as an indicator, Se-(4-nitrophenyl) selenenylthiosulfate reacted significantly faster with N-succinylcysteamine than did Se-(4-nitrophenyl) selenosulfate thus correlating with previously observed rates of inactivation of the enzyme papain by these compounds.
- Patarasakulchai, Nuansri,Southwell-Keely, Peter T.
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p. 277 - 282
(2007/10/02)
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- STUDIES ON LONG-RANGE COUPLINGS BETWEEN 77Se AND 13C IN SOME ARYL SELENIDES, DICHLORIDES, AND SELENOXIDES. THE INVERSE EFFECT ON COUPLINGS IN THE SELENOXIDE FORMATION.
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Long-range coupling constants between **7**7Se and **1**3C in selenoanisole, diphenyl selenide, diphenyl diselenide, and their 2-mono- and 2,2 prime -disubstituted derivatives, selenoxanthone, selenanthrene, dichlorides, and selenoxides were measured to disclose predominant factors governing the magnitude of the coupling. Extraordinary large values for two- and three-bond couplings are found in selenoxanthone. Three factors are operative: the orientational effect, the coordination number, and the effect of ring formation. The last factor accompanies a stronger inverse effect on the coupling of selenoxides than on that of selenides.
- Nakanishi,Ikeda
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p. 1661 - 1664
(2007/10/02)
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- Electrochemical Preparation of Organic Diselenides
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By the method of electrosynthesis a number of organic diselenides can be prepared simply and without danger.The cathodic polarisation of a special selenium electrode in aprotic solutions gives rise to polyselenideanions, which react with electrophilic compounds to the corresponding diselenides of the general formula RSeSeR (2a-e) with R = benzyl, 2-nitrophenyl, cyclohexyl, isopropyl, 4-cyanophenyl.
- Jeroschewski, P.,Ruth, W,,Struebing, B.,Berge, H.
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p. 787 - 792
(2007/10/02)
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