- DIMETHYL TRISULFIDE AS A CYANIDE ANTIDOTE
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Dimethyl trisulfide (DMTS) antidote compositions may be used to as a cyanide poisoning antidote.
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Paragraph 0033
(2015/11/17)
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- Decoupling deprotonation from metalation: Thia-fries rearrangement
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(Chemical Equation Presented) Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible ortho deprotonation (see scheme; DIPA = diisopropylamine, LDA = lithium diisopropylamide). In contrast, ortho metalation results exclusively in the generation of a benzyne.
- Dyke, Alan M.,Gill, Duncan M.,Harvey, Jeremy N.,Hester, Alison J.,Lloyd-Jones, Guy C.,Munoz, M. Paz,Shepperson, Ian R.
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supporting information; experimental part
p. 5067 - 5070
(2009/03/11)
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- Complexation of phosphoryl-containing mono-, bi- and tri-podands with alkali cations in acetonitrile. Structure of the complexes and binding selectivity
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We present experimental and theoretical studies on new ionophores (L) which possess a high complexation ability for Li+or Na+cations. Four tri-podands(R1-O-C2H4-)3N[R 1 = -CH2-P(O)Ph2(P1), -C2H4-P(O)Ph2 (P2), -o-C6H4P(O)Ph2 (P3) and -o-C6H4-CH2-P(O)Ph2 (P4)], one bi-podand (R2-O-C2H4-)2N-CH3 [R2 = -o-C6H4-CH2-P(O)Ph2 (P5)] and one mono-podand [R2-O-(CH2-CH2-O)3R2 (P6)] containing phosphine oxide terminal groups have been synthesised. Stability constants, enthalpies and entropies of their complexation with lithium, sodium and potassium thiocyanates have been determined in acetonitrile at 298 K by a calorimetric titration technique. We find that tri-podands form a variety of complexes [(M+)3L, (M+)2L, M+L and M+L2)], whereas the bi- and mono-podand form only M+L complexes with Li+ and Na+, and M+L and M+L2 complexes with K+. Formation of poly-nuclear (M+)nL complexes of tri-podands in solution has been confirmed by electro-spray mass spectrometry. At relatively small concentrations of the ligand (CL0)S P1 binds Na+ much better than Li+, whereas P4 and P5 display a remarkable Li+/Na+ selectivity; at large CL0 the complexation selectivity decreases. X-Ray diffraction studies performed on monocrystals of complexes of NaNCS with tri-podands P2 and P3 show that Na+ is encapsulated inside a 'basket-like' pseudocavity, coordinating all donor atoms of the tri-podand. Molecular dynamics simulations on P2, P3 and P4 and on their 1:1 complexes with M+ in acetonitrile solution suggest that the structures of M+L complexes in solution are similar to those found for P2 and P3 complexes in the solid state.
- Solov'ev, Vitaly P.,Baulin, Vladimir E.,Strakhova, Nadezhda N.,Kazachenko, Vladimir P.,Belsky, Vitaly K.,Varnek, Alexandre A.,Volkova, Tatiana A.,Wipff, Georges
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p. 1489 - 1498
(2007/10/03)
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- Oscillations and Bistability in the Cu(II)-Catalyzed Reaction between H2O2 and KSCN
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The reaction between H2O2 and KSCN catalyzed by CuSO4 exhibits three different types of bistability as a function of flow rate in a continuous flow stirred tank reactor at 25 deg C.Two steady states and one oscillatory state are involved.The system is one of the few examples in which oscillations can appear in batch configuration as well.The color, the potential of a Pt electrode, and the rate of oxygen gas evolution oscillate for a wide range of reagent concentrations.The chemistry which accounts for the observed behavior is discussed briefly.
- Orban, Miklos
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p. 6893 - 6898
(2007/10/02)
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- Volume Change on Complex Formation Between Anions and Cyclodextrins in Aqueous Solution
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Partial molal volume changes during complex formation between SCN(1-), I(1-), and ClO4(1-) and α- and β-cyclodextrin have been determined by two independent methods of measurements; one based on density measurement and subsequent calculation of apparent molal volumes, the other on differentiating the association constants with respect to pressure.Results from the two methods are in good agreement.Negative volume changes were observed for complex formation between the anions and α-cyclodextrin while zero or slightly positive values were observed for complex formation with β-cyclodextrin.The result is consistent with the idea that the anions do not become dehydrated as they form complexes with cyclodextrins.
- Hoeiland, H.,Hald, L.H.,Kvammen, O.J.
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p. 775 - 784
(2007/10/02)
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