14193-38-5Relevant academic research and scientific papers
The Reaction of Superoxide Radical Anion with Dithiothreitol: A Chain Process
Zhang, Nan,Schuchmann, Heinz-Peter,Sonntag, Clemens von
, p. 4718 - 4722 (1991)
The radical-induced oxidation of dithiothreitiol (DTT) by O2 to 4,5-dihydroxy-1,2-dithiane (ox-DTT) in aqueous solutions of pH 8.7 proceeds via a chain reaction.Radicals such as OH generated by the radiolysis of N2O/O2-saturated aqueous solutions abstract an H atom from DTT.The resulting DTT(-H). radicals cyclize and deprotonate, yielding the disulfide radical anion ox-DTT.-.The latter reacts with O2 (k = 7.1 x 108 dm3 mol-1 s-1) giving rise to ox-DTT and O2.-.The G value of ox-DTT formation increases with decreasing dose rate, displaying a linear yield vs (dose rate)1/2 relationship indicative of a chain reaction.The chain is inhibited by superoxide dismutase, showing that 02.- is a chain carrier.Hydrogen peroxide is not a chain product, from which it is concluded that O2.- does not abstract hydrogen from DTT but rather forms a short lived complex with the DTT anion which then predominantly decomposes into an RSO. radical and an OH- ion, (and to a lesser extent into an OH radical and an RSO- ion).In a second step, the RSO. radical reacts with DTT (probably the anionic form DTT-), thus regenerating DTT(-H)..The resulting sulfenic acid eliminates water and yields the chain product ox-DTT.An overall propagation rate constant of 35 dm3 mol-1 s-1 has been estimated.
dl-biTOT - A novel building block for electroactive oligomers and polymers in semiconductor applications
Von Kieseritzky, Fredrik,Hellberg, Jonas
, p. 1004 - 1006 (2002)
The title compound dl-biTOT (1, dl-2,2′,3,3′-tetrahydro2,2′-bithieno[3,2-b][1,4]oxathiine) was prepared in a five-step synthesis using cheap and readily available starting materials, with an overall yield of 50%. Compound 1 is believed to display interesting and unique properties as a building block in oligomer and polymer applications in the rapidly growing field of organic semiconductors. A new and superior method to oxidize dithiothreitol (Cleland's reagent), that operates rapidly and cleanly on a multigram scale is also reported.
Silica phosphoric acid/NaNO2 as a novel heterogeneous system for the coupling of thiols to their corresponding disulfides
Zolfigol, Mohammad Ali,Shirini, Farhad,Zamani, Khosrow,Ghofrani, Efat,Ebrahimi, Satar
, p. 2177 - 2182 (2004)
Silica phosphoric acid was prepared via reaction of silica chloride (I) and phosphoric acid. Thiols can be readily converted to their corresponding thionitrites with a combination of silica phosphoric acid (II), wet SiO 2, 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.
Radical-induced oxidation of dithiothreitol in acidic oxygenated aqueous solution: A chain reaction
Lal, Manohar,Rao, Raghavendra,Fang, Xingwang,Schuchmann, Heinz-Peter,Von Sonntag, Clemens
, p. 5735 - 5739 (1997)
Sulfur-centered radicals derived from dithiothreitol (DTT) have been generated radiolytically in aqueous solution in the neutral to acid pH range. In the presence of O2, these are eventually transformed by a chain reaction into dihydroxydithiane (ox-DTT) and H2O2. In acid solution, the chain character of the reaction becomes more pronounced with decreasing pH. The radiolytic yield of the products (G value) also depends on the DTT concentration and the dose rate. The HO2· radical carries the chain, abstracting an H atom from the DTT molecule (k = 120 dm3 mol-1 s-1), while its conjugated base, the O2·- radical (pK(a)(HO2·) = 4.8), does not react with DTT. The chain is continued when the DTT-derived radicals react with O2, yielding ox-DTT and HO2· radicals. The self-termination of the HO2·/O2·- radicals breaks the chain.
Selective, Modular Probes for Thioredoxins Enabled by Rational Tuning of a Unique Disulfide Structure Motif
Becker, Katja,Busker, Sander,Felber, Jan G.,Maier, Martin S.,Poczka, Lena,Scholzen, Karoline,Theisen, Ulrike,Thorn-Seshold, Julia,Thorn-Seshold, Oliver,Zeisel, Lukas,Arnér, Elias S. J.,Brandst?dter, Christina
supporting information, p. 8791 - 8803 (2021/06/27)
Specialized cellular networks of oxidoreductases coordinate the dithiol/disulfide-exchange reactions that control metabolism, protein regulation, and redox homeostasis. For probes to be selective for redox enzymes and effector proteins (nM to μM concentrations), they must also be able to resist non-specific triggering by the ca. 50 mM background of non-catalytic cellular monothiols. However, no such selective reduction-sensing systems have yet been established. Here, we used rational structural design to independently vary thermodynamic and kinetic aspects of disulfide stability, creating a series of unusual disulfide reduction trigger units designed for stability to monothiols. We integrated the motifs into modular series of fluorogenic probes that release and activate an arbitrary chemical cargo upon reduction, and compared their performance to that of the literature-known disulfides. The probes were comprehensively screened for biological stability and selectivity against a range of redox effector proteins and enzymes. This design process delivered the first disulfide probes with excellent stability to monothiols yet high selectivity for the key redox-Active protein effector, thioredoxin. We anticipate that further applications of these novel disulfide triggers will deliver unique probes targeting cellular thioredoxins. We also anticipate that further tuning following this design paradigm will enable redox probes for other important dithiol-manifold redox proteins, that will be useful in revealing the hitherto hidden dynamics of endogenous cellular redox systems.
Oxidative Formation of Disulfide Bonds by a Chemiluminescent 1,2-Dioxetane under Mild Conditions
Sauer, Caroline S.,K?ckenberger, Johannes,Heinrich, Markus R.
, p. 9331 - 9338 (2020/08/14)
The oxidation of alkyl thiols to disulfides has been achieved under mild conditions using a chemiluminescent 1,2-dioxetane as a stoichiometric oxidant. Besides the mild and biocompatible reaction conditions, this approach offers the possibility to monitor the presence of thiols through oxidation and chemiluminescence of the remaining dioxetane.
Syntheses of prodrug-type phosphotriester oligonucleotides responsive to intracellular reducing environment for improvement of cell membrane permeability and nuclease resistance
Hayashi, Junsuke,Samezawa, Yusuke,Ochi, Yosuke,Wada, Shun-ichi,Urata, Hidehito
, p. 3135 - 3138 (2017/06/13)
We synthesized prodrug-type phosphotriester (PTE) oligonucleotides containing the six-membered cyclic disulfide moiety by using phosphoramidite chemistry. Prodrug-type oligonucleotides named “Reducing-Environment-Dependent Uncatalyzed Chemical Transforming (REDUCT) PTE oligonucleotides” were converted into natural oligonucleotides under cytosol-mimetic reductive condition. Furthermore, the REDUCT PTE oligonucleotides were robust to nuclease digestion and exhibited good cell membrane permeability.
Hydrogen Bonding-Assisted Enhancement of the Reaction Rate and Selectivity in the Kinetic Resolution of d,l-1,2-Diols with Chiral Nucleophilic Catalysts
Fujii, Kazuki,Mitsudo, Koichi,Mandai, Hiroki,Suga, Seiji
supporting information, p. 2778 - 2788 (2017/08/23)
An extremely efficient acylative kinetic resolution of d,l-1,2-diols in the presence of only 0.5 mol% of binaphthyl-based chiral N,N-4-dimethylaminopyridine was developed (selectivity factor of up to 180). Several key experiments revealed that hydrogen bonding between the tert-alcohol unit(s) of the catalyst and the 1,2-diol unit of the substrate is critical for accelerating the rate of monoacylation and achieving high enantioselectivity. This catalytic system can be applied to a wide range of substrates involving racemic acyclic and cyclic 1,2-diols with high selectivity factors. The kinetic resolution of d,l-hydrobenzoin and trans-1,2-cyclohexanediol on a multigram scale (10 g) also proceeded with high selectivity and under moderate reaction conditions: (i) very low catalyst loading (0.1 mol%); (ii) an easily achievable low reaction temperature (0 °C); (iii) high substrate concentration (1.0 M); and (iv) short reaction time (30 min). (Figure presented.).
Tris(3-hydroxypropyl)phosphine (THPP): A mild, air-stable reagent for the rapid, reductive cleavage of small-molecule disulfides
McNulty, James,Krishnamoorthy, Venkatesan,Amoroso, Dino,Moser, Michael
supporting information, p. 4114 - 4117 (2015/11/03)
Tris(3-hydroxypropyl)phosphine (THPP) is demonstrated to be a versatile, water-soluble and air-stable reducing agent, allowing for the rapid, irreversible reductive cleavage of disulfide bonds in both aqueous and buffered aqueous-organic media. The reagent shows exceptional stability at biological pH under which condition it permits the rapid reduction of a wide range of differentially functionalized small-molecule disulfides.
A potent, versatile disulfide-reducing agent from aspartic acid
Lukesh III, John C.,Palte, Michael J.,Raines, Ronald T.
supporting information; experimental part, p. 4057 - 4059 (2012/04/10)
Dithiothreitol (DTT) is the standard reagent for reducing disulfide bonds between and within biological molecules. At neutral pH, however, >99% of DTT thiol groups are protonated and thus unreactive. Herein, we report on (2S)-2-amino-1,4-dimercaptobutane (dithiobutylamine or DTBA), a dithiol that can be synthesized from l-aspartic acid in a few high-yielding steps that are amenable to a large-scale process. DTBA has thiol pKa values that are ～1 unit lower than those of DTT and forms a disulfide with a similar E o′ value. DTBA reduces disulfide bonds in both small molecules and proteins faster than does DTT. The amino group of DTBA enables its isolation by cation-exchange and facilitates its conjugation. These attributes indicate that DTBA is a superior reagent for reducing disulfide bonds in aqueous solution.
