PMID- 21244017 OWN - NLM STAT- MEDLINE DCOM- 20110603 LR - 20131121 IS - 1520-6882 (Electronic) IS - 0003-2700 (Linking) VI - 83 IP - 4 DP - 2011 Feb 15 TI - Monitoring a reaction at submillisecond resolution in picoliter volumes. PG - 1462-8 LID - 10.1021/ac103234a [doi] AB - 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 approximately 50 mum) 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 mus. 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 approximately 3 x 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. FAU - Huebner, Ansgar M AU - Huebner AM AD - Department of Biochemistry, University of Cambridge, Cambridge, United Kingdom. FAU - Abell, Chris AU - Abell C FAU - Huck, Wilhelm T S AU - Huck WT FAU - Baroud, Charles N AU - Baroud CN FAU - Hollfelder, Florian AU - Hollfelder F LA - eng PT - Journal Article PT - Research Support, Non-U.S. Gov't DEP - 20110118 PL - United States TA - Anal Chem JT - Analytical chemistry JID - 0370536 RN - 0 (Dimethylpolysiloxanes) RN - 0 (Oils) RN - 059QF0KO0R (Water) RN - 63148-62-9 (baysilon) SB - IM MH - Diffusion MH - Dimethylpolysiloxanes/chemistry MH - Equipment Design MH - Hydrodynamics MH - Kinetics MH - Microarray Analysis/instrumentation/*methods MH - Oils/chemistry MH - Water/chemistry EDAT- 2011/01/20 06:00 MHDA- 2011/06/04 06:00 CRDT- 2011/01/20 06:00 PHST- 2011/01/20 06:00 [entrez] PHST- 2011/01/20 06:00 [pubmed] PHST- 2011/06/04 06:00 [medline] AID - 10.1021/ac103234a [doi] PST - ppublish SO - Anal Chem. 2011 Feb 15;83(4):1462-8. doi: 10.1021/ac103234a. Epub 2011 Jan 18.