1119-62-6Relevant articles and documents
Vis/NIR light driven mild and clean synthesis of disulfides in the presence of Cu2(OH)PO4 under aerobic conditions
Shah, Sk. Sheriff,Karthik,Singh, N. D. Pradeep
, p. 45416 - 45419 (2015)
A highly efficient one-pot strategy has been developed for the synthesis of disulfide in the presence of air under the irradiation of Vis/NIR light. Copper hydroxyphosphate (CHP) Cu2(OH)PO4, has been used as a Vis/NIR active photocatalyst. Disulfide forms on the surface of the catalyst by a radical mechanism. The protocol is useful for solvent free disulfide synthesis from a variety of thiols. This journal is
Efficient and selective oxidation of thiols to disulfides by 1,4-diazabicyclo[2.2.2]octane-di-N-oxide-diperhydrate under neutral and heterogeneous conditions
Salehi, Peyman,Zolfigol, Mohammad Ali,Tolami, Leila Bazaz
, p. 1777 - 1781 (2004)
1,4-Diazabicyclo[2.2.2]octane-di-N-oxide-di-perhydrate selectively oxidizes thiols to disulfides in acetonitrile in good yields. The method is generally useful for a wide variety of thiols.
Photocatalytic transformation of organic and water-soluble thiols into disulfides and hydrogen under aerobic conditions using Mn(CO)5Br
Tan, Kheng Yee Desmond,Teng, Guan Foo,Fan, Wai Yip
, p. 4136 - 4143 (2011)
The photolysis of Mn(CO)5Br with thiols under aerobic conditions at room temperature produces the corresponding disulfides in high yields, accompanied by the evolution of hydrogen as the only other product. This transformation is a greener route toward the synthesis of disulfides and exhibits 100% atom economy. The catalytic system possesses high chemoselectivity, as evidenced by high disulfide yields even in the presence of numerous functional groups. A mechanism has been proposed to involve free radical species and is based on fac-Mn(CO)3(RSH)2Br being an important catalytic intermediate. Mn(CO)5Br is also able to catalyze the conversion of naturally occurring water-soluble thiols such as cysteine and glutathione. Coupled with suitable enzymes that regenerate thiols from disulfides using proton sources, it is possible to envisage a combined catalytic cycle that is able to reduce protons to hydrogen efficiently.
SULFUR-CONTAINING HETEROCYCLES 7. NEW METHOD FOR PREPARATION OF 1,2-DITHIOLAN-3-ONES
Vasil'eva, T. P.,Lin'kova, M. G.,Kil'disheva, O. V.,Knunyants, I. L.
, p. 1507 - 1510 (1980)
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Silica chloride/NaNO2 as a novel heterogeneous system for production of thionitrites and disulfides under mild conditions
Zolfigol, Mohammad Ali,Shirini, Farhad,Choghamarani, Arash Ghorbani,Ghofrani, Efat
, p. 1477 - 1481 (2003)
Thiols can be readily converted to their corresponding thionitrites with a combination of silica chloride (I), wet SiO2 and sodium nitrite in dichloromethane at room temperature. Disulfides result from the homolytic cleavage of the sulfur-nitrogen bond of the unstable thionitrite and subsequent coupling of the resultant thiyl radicals.
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Fernando,Freiser
, p. 4928,4929 (1958)
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Bohning,Weiss
, p. 4724,4728 (1960)
SERS surfaces modified with a 4-(2-pyridylazo)resorcinol disulfide derivative: Detection of copper, lead, and cadmium
Gayle Crane,Wang, DaoXin,Sears, Malia,Heyns, Bernard,Carron, Keith
, p. 360 - 364 (1995)
We have developed a surface-enhanced Raman spectroscopic technique for the determination of Pb2+, Cd2+, and Cu2+ concentration using a 4-(2-pyridylazo)resorcinol (PAR) coating modified with a disulfide. The disulfide provided a strong anchor to a roughened silver substrate. Atomic specificity was demonstrated by the distinct spectral changes that occurred through the interaction of Pb2+, Cd2+, and Cu2+ ions with the indicator. The absorption of these metals by the coating was followed with SERS and could be fit to a Frumkin isotherm. Langmuirian behavior was not observed; this is most likely due to the electrostatic repulsions as the metal cations are absorbed. The detection limits at pH 6 for Pb2+, Cd2+, and Cu2+ were 522, 50.3, and 1.49 ppb, respectively. Flow experiments using an optical fiber probe indicated instantaneous response to changes in metal concentration.
Thiol-based michael-type addition. A systematic evaluation of its controlling factors
Francini, Nora,Gennari, Arianna,Lallana, Enrique,Tirelli, Nicola,Wedgwood, Jennifer
, (2020)
This paper is about the factors controlling kinetics and product stability of this popular bioconjugation reaction. We demonstrate that a) thiol pKa, i.e. the amount of thiolates, is the only determinant of the reaction kinetics for the nucleophile; b) product degradation occurs primarily via hydrolysis (not thiol exchange), and is more prominent for the most rapidly reacting electrophiles. In terms of molecular design, acrylamides and low pKa thiols appear as the reaction partners that provide the best compromise for stability and reaction rate.
Polydopamine as a Catalyst for Thiol Coupling
Du, Yong,Yang, Hao-Cheng,Xu, Xiao-Ling,Wu, Jian,Xu, Zhi-Kang
, p. 3822 - 3825 (2015)
In biological systems, disulfide bonds are formed efficiently under mild conditions without the release of harmful byproducts. Inspired by nature, we report a biomimetic polydopamine (PDA) catalyst for oxidative thiol coupling. This reaction was accelerated with only a small amount of PDA particles in neutral, weakly alkaline, and even weakly acidic aqueous media at room temperature under an air atmosphere. The catalytic particles were facilely separated and were reused without a decrease in activity. The entire process is totally biofriendly, including the synthesis of the PDA particles. This route is especially useful for the synthesis of pharmaceutical molecules. S-imulating nature: Inspired by disulfide bond formation mechanisms in nature, we demonstrate that polydopamine particles can be used as a promising biomimetic catalyst for the thiol coupling reaction in aqueous media under mild conditions. This approach involves no harmful chemicals and produces no waste products except for water.
Danehy,Kreuz
, p. 1109,1111 (1961)
Reactivity and O2 Formation by Mn(IV)- and Mn(V)-Hydroxo Species Stabilized within a Polyfluoroxometalate Framework
Schreiber, Roy E.,Cohen, Hagai,Leitus, Gregory,Wolf, Sharon G.,Zhou, Ang,Que, Lawrence,Neumann, Ronny
, p. 8738 - 8748 (2015)
Manganese(IV,V)-hydroxo and oxo complexes are often implicated in both catalytic oxygenation and water oxidation reactions. Much of the research in this area is designed to structurally and/or functionally mimic enzymes. On the other hand, the tendency of such mimics to decompose under strong oxidizing conditions makes the use of molecular inorganic oxide clusters an enticing alternative for practical applications. In this context it is important to understand the reactivity of conceivable reactive intermediates in such an oxide-based chemical environment. Herein, a polyfluoroxometalate (PFOM) monosubstituted with manganese, [NaH2(Mn-L)W17F6O55]q-, has allowed the isolation of a series of compounds, Mn(II, III, IV and V), within the PFOM framework. Magnetic susceptibility measurements show that all the compounds are high spin. XPS and XANES measurements confirmed the assigned oxidation states. EXAFS measurements indicate that Mn(II)PFOM and Mn(III)PFOM have terminal aqua ligands and Mn(V)PFOM has a terminal hydroxo ligand. The data are more ambiguous for Mn(IV)PFOM where both terminal aqua and hydroxo ligands can be rationalized, but the reactivity observed more likely supports a formulation of Mn(IV)PFOM as having a terminal hydroxo ligand. Reactivity studies in water showed unexpectedly that both Mn(IV)-OH-PFOM and Mn(V)-OH-PFOM are very poor oxygen-atom donors; however, both are highly reactive in electron transfer oxidations such as the oxidation of 3-mercaptopropionic acid to the corresponding disulfide. The Mn(IV)-OH-PFOM compound reacted in water to form O2, while Mn(V)-OH-PFOM was surprisingly indefinitely stable. It was observed that addition of alkali cations (K+, Rb+, and Cs+) led to the aggregation of Mn(IV)-OH-PFOM as analyzed by electron microscopy and DOSY NMR, while addition of Li+ and Na+ did not lead to aggregates. Aggregation leads to a lowering of the entropic barrier of the reaction without changing the free energy barrier. The observation that O2 formation is fastest in the presence of Cs+ and ～fourth order in Mn(IV)-OH-PFOM supports a notion of a tetramolecular Mn(IV)-hydroxo intermediate that is viable for O2 formation in an oxide-based chemical environment. A bimolecular reaction mechanism involving a Mn(IV)-hydroxo based intermediate appears to be slower for O2 formation.
Macroporous p-type silicon Fabry-Perot layers. Fabrication, characterization, and applications in biosensing
Janshoff, Andreas,Dancil, Keiki-Pua S.,Steinem, Claudia,Greiner, Douglas P.,Lin, Victor S.-Y.,Gurtner, Christian,Motesharei, Kianoush,Sailor, Michael J.,Reza Ghadiri
, p. 12108 - 12116 (1998)
We present in this paper that porous silicon can be used as a large surface area matrix as well as the transducer of biomolecular interactions. We report the fabrication of heavily doped p-type porous silicon with pore diameters that can be tuned, depending on the etching condition, from approximately 5 to 1200 nm. The structure and porosity of the matrixes were characterized by scanning force microscopy (SFM) and scanning electron microscopy (SEM), Brunnauer-Emmett-Teller nitrogen adsorption isotherms, and reflectance interference spectroscopy. The thin porous silicon layers are transparent to the visible region of the reflectance spectra due to their high porosity (80-90%) and are smooth enough to produce Fabry-Perot fringe patterns upon white light illumination. Porous silicon matrixes were modified by ozone oxidation, functionalized in the presence of (2- pyridyldithiopropionamidobutyl)dimethylmethoxysilane, reduced to unmask the sulfhydryl functionalities, and coupled to biotin through a disulfide-bond- forming reaction. Such functionalized matrixes display considerable stability against oxidation and corrosion in aqueous media and were used to evaluate the utility of porous silicon in biosensing. The streptavidin-biotin interactions on the surface of porous silicon could be monitored by the changes in the effective optical thickness calculated from the observed shifts in the Fabry-Perot fringe pattern caused by the change in the refractive index of the medium upon protein-ligand binding. Porous silicon thus combines the properties of a mechanically and chemically stable high surface area matrix with the function of an optical transducer and as such may find utility in the fabrication of biosensor devices.
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Stout et al.
, p. 562 (1974)
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Photochemical metal-free aerobic oxidation of thiols to disulfides
Spiliopoulou, Nikoleta,Kokotos, Christoforos G.
supporting information, p. 546 - 551 (2021/01/28)
Thiol oxidation to disulfides is an area of great importance in organic synthesis, both for synthetic and biological purposes. Herein, we report a mild, inexpensive and green photochemical approach for the synthesis of both symmetrical and non-symmetrical disulfides, using metal-free and environmentally friendly conditions. Utilizing phenylglyoxylic acid as the photoinitiator, common household bulbs as the light source and a simple inorganic salt as the additive, a versatile oxidation of thiols leading to products in excellent yields is described. This journal is
Self pH regulated iron(II) catalyst for radical free oxidation of benzyl alcohols
Das, Biraj,Baruah, Manash J.,Sharma, Mukesh,Sarma, Bipul,Karunakar, Galla V.,Satyanarayana, Lanka,Roy, Subhasish,Bhattacharyya, Pradip K.,Borah, Kamala Kanta,Bania, Kusum K.
, (2019/11/14)
Selective oxidation of various aromatic benzyl alcohols to benzaldehydes was found to be catalyzed with 90% conversion and 99% selectivity by an iron (II) catalyst herein designated as Fe-DDPA [DDPA = 3′-disulfanediyldipropionic acid]. The Fe-DDPA catalyst was prepared by a small loading of FeCl2 into a 2D sheet formed by the supramolecular assembling of DDPA. From both solid and liquid state nuclear magnetic resonance (NMR) spectroscopic study it was evident for the stabilization of the Fe(II) center through Fe-S interaction with the disulfide (S-S) unit of DDPA. DDPA was found to serve as an excellent support to maintain a pH that was required for a radical free oxidation of benzyl alcohol to aldehydes. The catalytic oxidation of benzyl alcohols was found to occur with excellent conversion and selectivity in acetonitrile (CH3CN) solvent in comparison to various other solvents. From various spectroscopic studies viz UV-vis, FT-IR and ESI-MS it was ascertained that the CH3CN interacted with Fe-DDPA to form a [(DDPA)2Fe(CH3CN)2]2+ species which then reacted with H2O2 to form an intermediate Fe-hydroxoperoxo, FeIII-OOH species. The Fe-OOH further got oxidized to the active FeIV=O species and was responsible for bringing the high selectivity in the oxidation reaction. The generation of highly unstable Fe-OOH species was further confirmed by electrochemical study, UV–vis, Raman and ESR spectroscopic analysis.
