TY - JOUR
T1 - Resolution of strongly competitive product channels with optimal dynamic discrimination
T2 - Application to flavins
AU - Roslund, Jonathan
AU - Roth, Matthias
AU - Guyon, Laurent
AU - Boutou, Véronique
AU - Courvoisier, Francois
AU - Wolf, Jean Pierre
AU - Rabitz, Herschel
N1 - Funding Information:
J.-P.W. and F.C. acknowledge support from the Swiss National Science Foundation. H.R. acknowledges support from DHS, ONR, and ARO.
PY - 2011/1/21
Y1 - 2011/1/21
N2 - Fundamental molecular selectivity limits are probed by exploiting laser-controlled quantum interferences for the creation of distinct spectral signatures in two flavin molecules, erstwhile nearly indistinguishable via steady-state methods. Optimal dynamic discrimination (ODD) uses optimally shaped laser fields to transiently amplify minute molecular variations that would otherwise go unnoticed with linear absorption and fluorescence techniques. ODD is experimentally demonstrated by combining an optimally shaped UV pump pulse with a time-delayed, fluorescence-depleting IR pulse for discrimination amongst riboflavin and flavin mononucleotide in aqueous solution, which are structurally and spectroscopically very similar. Closed-loop, adaptive pulse shaping discovers a set of UV pulses that induce disparate responses from the two flavins and allows for concomitant flavin discrimination of ∼16. Additionally, attainment of ODD permits quantitative, analytical detection of the individual constituents in a flavin mixture. The successful implementation of ODD on quantum systems of such high complexity bodes well for the future development of the field and the use of ODD techniques in a variety of demanding practical applications.
AB - Fundamental molecular selectivity limits are probed by exploiting laser-controlled quantum interferences for the creation of distinct spectral signatures in two flavin molecules, erstwhile nearly indistinguishable via steady-state methods. Optimal dynamic discrimination (ODD) uses optimally shaped laser fields to transiently amplify minute molecular variations that would otherwise go unnoticed with linear absorption and fluorescence techniques. ODD is experimentally demonstrated by combining an optimally shaped UV pump pulse with a time-delayed, fluorescence-depleting IR pulse for discrimination amongst riboflavin and flavin mononucleotide in aqueous solution, which are structurally and spectroscopically very similar. Closed-loop, adaptive pulse shaping discovers a set of UV pulses that induce disparate responses from the two flavins and allows for concomitant flavin discrimination of ∼16. Additionally, attainment of ODD permits quantitative, analytical detection of the individual constituents in a flavin mixture. The successful implementation of ODD on quantum systems of such high complexity bodes well for the future development of the field and the use of ODD techniques in a variety of demanding practical applications.
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U2 - 10.1063/1.3518751
DO - 10.1063/1.3518751
M3 - Article
C2 - 21261372
AN - SCOPUS:79551624293
SN - 0021-9606
VL - 134
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 3
M1 - 034511
ER -