A Reinvestigation of the Effect of Pressure on the Reaction of Fe(III) with Thiocyanate Ions in Aqueous Solution

Doss, R.; Eldik, Rudi van; Kelm, H.

doi:10.1002/bbpc.19820861011

Cited by 16 publications

(1 citation statement)

References 15 publications

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“…We chose to obtain the value of k by measuring the increase in time of the maximum product concentration and comparing the numerics and experiments. This fit (shown in the Supporting Information) yields k ∼ 3 × 10 4 M −3 ·s −1 , with an uncertainty of 20%. − This value of k is used to calculate the variables τ = 200 μs and L = 0.5 μm, in order to rescale the dimensionless solution onto dimensional variables and compare with the experimentally measured profiles. This comparison is shown in Figure , where the theoretical and experimental concentration profiles are superimposed for four discrete times.…”

Section: Resultsmentioning

confidence: 99%

Monitoring a Reaction at Submillisecond Resolution in Picoliter Volumes

et al. 2011

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Well-established rapid mixing techniques such as stopped-flow have been used to push the dead time for kinetic experiments down to a few milliseconds. However, very fast reactions are difficult to resolve below this limit. We now outline an approach that provides access to ultrafast kinetics but does not rely on active mixing at all. Here, the reagents are compartmentalized into water-in-oil emulsion microdroplets (diameter ∼50 μm) that are statically arrayed in pairs, resting side-by-side in a well feature of a poly(dimethylsiloxane) (PDMS) device. A reaction between the contents of two droplets arrayed in such a holding trap is initiated by droplet fusion that is brought about by electrocoalescence and known to occur on a time scale of about 100 μs. A reaction between the reactants (Fe(3+) and SCN(-)) is monitored by image analysis measuring the product formation in the newly merged drop in both space and time, by use of a fast camera. A comparison of the concentration field of the reaction product with the output of a reaction-diffusion system of equations yields a rate constant k ∼ 3 × 10(4) M(-3)·s(-1). Since reaction and diffusion are formally included in the mathematical model, measurements can proceed immediately after the drop fusion, removing the need to allow time for mixing. This approach is different from existing methodologies, for example, experiments in a conventional stopped-flow apparatus but also electrofusion of moving droplets where contents are mixed by chaotic advection before a reaction is monitored. Our analysis makes kinetics accessible that are several times faster than techniques that have to allow time for mixing.

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Section: Resultsmentioning

confidence: 99%

Monitoring a Reaction at Submillisecond Resolution in Picoliter Volumes

et al. 2011

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Umwandlung von η¹‐Nitrosyl‐in η²‐Hydroxylaminyl‐Liganden bei der Reduktion von [Mo(NO)₂(‘S₄’)] zu [Mo(η²‐NH₂O)(NO)(‘S₄’)]: Eine Modellreaktion für einen Teilschritt der enzymatischen [NO → NH₃]‐Konversion

et al. 1988

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GmbH. D-75 14 Eggenstein-Leopoldshafen 2, unter Angabe der Hinterlegungsnummer CSD-52985, der Autoren und des Zeitschriftenzitates angeforden werden. 161 a) R. Appel, J. Kochta, F. Knoch, Chem. Ber. 120 (1987) 131; b) J. Fink, W. Rosch, U.-J. Vogelbacher, M. Regitz, Angew. Chem. 98 (1987) 265: Angew. Chem. Inr. Ed. Engl. 26 (1987) 280. 171 Spektroskopische Daten von 4 (Bezifferung wie in Abb. I ) : "P-NMR (81.0 MHz. H,PO, ext.): 6-494.3 (JRh.,,=45.7. Jpl.p2=24.6. J,,.,,= 18.2

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Transformation of η¹‐Nitrosyl to η²‐Hydroxylaminyl Ligands in the Reduction of [Mo(NO)₂(‘S₄’)] to [Mo(η²‐NH₂O)(NO)(‘S₄’)]: A Model Reaction for a Partial Step in the Enzymatic NO→NH₃ Conversion

Sellmann

Seubert

Moll

et al. 1988

Angew. Chem. Int. Ed. Engl.

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We thank a referee for bringing to our attention recent publications on other systematic investigations on the large effect of changes on hostguest complexes: a) F. Diederich, Angew. Chem. 100 (1988) 372 (especially p. 382); Angew. Chem. Int. Ed. Engl. 27 (1988) 362; b) T. J. Shepodd, M. A. Petti, D. A. Dougherty, J. Am. Chem. Soc llO(1988) 1983. 131 All new compounds gave satisfactory analytical data ( ' H and ''C NMR, elemental analyses) [4] H.-J. Schneider, R. Kramer, J. Pdhlmann, U. Schneider, J . Am. Chem. Soc. 110 (1988), in press. [5] H.-J. Schneider, R. Pohlmann, Bioorg. Chem. 15 (1987) 183. 161 Compare the hydrophobic increments of -NHCH3, whicheare roughly five orders of magnitude larger compared with those of -NMe, substituents: C. Hansch, A. Leo: Substituent Constants for Correlation Analysis in Chemistry and Biology, Wiley, New York 1979, p. 49ff. 0 VCH VerlagsgesellschaJi mbH, 0-6940 Weinheim, 1988 0570-0833/88/0909-1164 $ 02.50/0 Angew. Chem. Int. Ed. Engl. 27 11988) No. 9

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A Reinvestigation of the Effect of Pressure on the Reaction of Fe(III) with Thiocyanate Ions in Aqueous Solution

Cited by 16 publications

References 15 publications

Monitoring a Reaction at Submillisecond Resolution in Picoliter Volumes

Monitoring a Reaction at Submillisecond Resolution in Picoliter Volumes

Umwandlung von η¹‐Nitrosyl‐in η²‐Hydroxylaminyl‐Liganden bei der Reduktion von [Mo(NO)₂(‘S₄’)] zu [Mo(η²‐NH₂O)(NO)(‘S₄’)]: Eine Modellreaktion für einen Teilschritt der enzymatischen [NO → NH₃]‐Konversion

Transformation of η¹‐Nitrosyl to η²‐Hydroxylaminyl Ligands in the Reduction of [Mo(NO)₂(‘S₄’)] to [Mo(η²‐NH₂O)(NO)(‘S₄’)]: A Model Reaction for a Partial Step in the Enzymatic NO→NH₃ Conversion

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A Reinvestigation of the Effect of Pressure on the Reaction of Fe(III) with Thiocyanate Ions in Aqueous Solution

Cited by 16 publications

References 15 publications

Monitoring a Reaction at Submillisecond Resolution in Picoliter Volumes

Monitoring a Reaction at Submillisecond Resolution in Picoliter Volumes

Umwandlung von η1‐Nitrosyl‐in η2‐Hydroxylaminyl‐Liganden bei der Reduktion von [Mo(NO)2(‘S4’)] zu [Mo(η2‐NH2O)(NO)(‘S4’)]: Eine Modellreaktion für einen Teilschritt der enzymatischen [NO → NH3]‐Konversion

Transformation of η1‐Nitrosyl to η2‐Hydroxylaminyl Ligands in the Reduction of [Mo(NO)2(‘S4’)] to [Mo(η2‐NH2O)(NO)(‘S4’)]: A Model Reaction for a Partial Step in the Enzymatic NO→NH3 Conversion

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Umwandlung von η¹‐Nitrosyl‐in η²‐Hydroxylaminyl‐Liganden bei der Reduktion von [Mo(NO)₂(‘S₄’)] zu [Mo(η²‐NH₂O)(NO)(‘S₄’)]: Eine Modellreaktion für einen Teilschritt der enzymatischen [NO → NH₃]‐Konversion

Transformation of η¹‐Nitrosyl to η²‐Hydroxylaminyl Ligands in the Reduction of [Mo(NO)₂(‘S₄’)] to [Mo(η²‐NH₂O)(NO)(‘S₄’)]: A Model Reaction for a Partial Step in the Enzymatic NO→NH₃ Conversion