Optimal Dynamic Discrimination Research Articles

Photonic reagents for concentration measurement of flu-orescent proteins with overlapping spectra.

By exploiting photonic reagents (i.e., coherent control by shaped laser pulses), we employ Optimal Dynamic Discrimination (ODD) as a novel means for quantitatively characterizing mixtures of fluorescent proteins with a large spectral overlap. To illustrate ODD, we simultaneously measured concentrations of in vitro mixtures of Enhanced Blue Fluorescent Protein (EBFP) and Enhanced Cyan Fluorescent Protein (ECFP). Building on this foundational study, the ultimate goal is to exploit the capabilities of ODD for parallel monitoring of genetic and protein circuits by suppressing the spectral cross-talk among multiple fluorescent reporters.

Discriminability of tryptophan containing dipeptides using quantum control

We show that the coherent manipulation of molecular wavepackets in the excited states of trp-containing dipeptides allows efficient discrimination among them. Optimal dynamic discrimination fails, however, for some dipeptide couples. When considering the limited spectral resources at play (3 nm bandwidth at 266 nm), we discuss the concept of discriminability, which appears uncorrelated to both static spectra and relaxation lifetimes.

Optimal Dynamic Discrimination in Tryptophan-Containing Dipeptides

Optimal Dynamic Discrimination based on the phase-shaping of deep ultraviolet femtosecond pulses was applied to selectively modulate the time-resolved fluorescence depletion of pairs of tryptophan-containing dipeptides. Our results indicate that phase-sensitive excitation allows their differential identification, beyond the limits of linear and time-resolved spectroscopy.

Control of nitromethane photoionization efficiency with shaped femtosecond pulses

The applicability of adaptive femtosecond pulse shaping is studied for achieving selectivity in the photoionization of low-density polyatomic targets. In particular, optimal dynamic discrimination (ODD) techniques exploit intermediate molecular electronic resonances that allow a significant increase in the photoionization efficiency of nitromethane with shaped near-infrared femtosecond pulses. The intensity bias typical of high-photon number, nonresonant ionization is accounted for by reference to a strictly intensity-dependent process. Closed-loop adaptive learning is then able to discover a pulse form that increases the ionization efficiency of nitromethane by ∼150%. The optimally induced molecular dynamics result from entry into a region of parameter space inaccessible with intensity-only control. Finally, the discovered pulse shape is demonstrated to interact with the molecular system in a coherent fashion as assessed from the asymmetry between the response to the optimal field and its time-reversed counterpart.

Resolution of strongly competitive product channels with optimal dynamic discrimination: Application to flavins

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 ∼16σ. 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.

Quantum Control of Tightly Competitive Product Channels

Fundamental selectivity limits of quantum control are pushed by introducing laser driven optimal dynamic discrimination to create distinguishing excitations on two nearly identical flavin molecules. Even with modest spectral resources, significant specificity is achieved with optimal pulse shapes, which amplify small molecular differences to create distinct, identifying signals. Rather than being a hindrance, system complexity appears to aid the control process and augments control field capability, which bodes well for implementation of quantum control in a variety of demanding applications.

Exploring the capabilities of quantum optimal dynamic discrimination

Optimal dynamic discrimination (ODD) uses closed-loop learning control techniques to discriminate between similar quantum systems. ODD achieves discrimination by employing a shaped control (laser) pulse to simultaneously exploit the unique quantum dynamics particular to each system, even when they are quite similar. In this work, ODD is viewed in the context of multiobjective optimization, where the competing objectives are the degree of similarity of the quantum systems and the level of controlled discrimination that can be achieved. To facilitate this study, the D-MORPH gradient algorithm is extended to handle multiple quantum systems and multiple objectives. This work explores the trade-off between laser resources (e.g., the length of the pulse, fluence, etc.) and ODD's ability to discriminate between similar systems. A mechanism analysis is performed to identify the dominant pathways utilized to achieve discrimination between similar systems.

Publisher’s Note: “Optimal dynamic discrimination of similar quantum systems in the presence of decoherence” [J. Chem. Phys. 124, 024101 (2006)

Publisher’s Note: “Optimal dynamic discrimination of similar quantum systems in the presence of decoherence” [J. Chem. Phys. 124, 024101 (2006)

Optimal dynamic discrimination of similara quantum systems in the presence of decoherence

Optimal dynamic discrimination (ODD) of a mixture of similar quantum systems with time series signals enables the extraction of the associated concentrations with reasonable levels of laser-pulse noise, signal detection errors, and imperfect signal detector resolution [Li et al., J. Chem. Phys. 122, 154103 (2005)]. The ODD paradigm is reexpressed in the density-matrix formulation to allow for the consideration of environmental decoherence on the quality of the extracted concentrations, along with the above listed factors. Simulations show that although starting in a thermally mixed state along with decoherence can be detrimental to discrimination, these effects can be counteracted by seeking a suitable optimal control pulse. Additional sampling of the temporal data also aids in extracting more information to better implement ODD.

Optimal dynamic discrimination of similar quantum systems with time series data

Optimal dynamic discrimination (ODD) was proposed [Li et al., J. Phys. Chem. B 106, 8125 (2002)] as a paradigm for discriminating noninteracting similar quantum systems in a mixture. This paper extends the ODD concept to optimize a laser control pulse for guiding similar quantum systems such that each exhibits a distinct time series signal for maximum discrimination. The use of temporal data addresses various experimental difficulties, including noise in the laser pulse, signal detection errors, and finite time resolution in the signal. Simulations of ODD with time series data are presented to explore these effects. It is found that the use of an optimally chosen control pulse can significantly enhance the discrimination quality. The ODD technique is also adapted to the case where the sample contains an unknown background species.

Mechanistic Analysis of Optimal Dynamic Discrimination of Similar Quantum Systems

Optimal dynamic discrimination (ODD) was recently introduced as a technique for maximally drawing out and detecting the differences between similar quantum systems by exploiting their controllable dynamical properties. As a simulation of ODD, optimal fields were found that successfully discriminated among similar species, but the underlying mechanisms of the process remained obscure. Hamiltonian encoding (HE) has been introduced as a technique for identifying the mechanisms of controlled quantum dynamics. The results of a HE based simulation analysis of ODD are presented in this paper. Different types and degrees of constructive and destructive interference are shown to underly the controlled discrimination processes. In general, it is found that successful discrimination relies on more complex interfering pathways for increasingly similar systems or increasing numbers of similar quantum systems.

Optimal Dynamic Discrimination of Similar Molecules through Quantum Learning Control

A paradigm for discriminating similar quantum systems in the laboratory is presented based on optimal control principles with the aid of closed loop learning algorithms. The optimal dynamic discrimination (ODD) process is simulated for a noninteracting mixture of up to three similar finite-dimensional quantum systems. The optimal control field giving rise to species discrimination, that considers the presence of field and observation noise, is deduced with a genetic algorithm (GA). The similar quantum systems yield distinct dynamics and detection signals, although influenced by the same control laser pulse. The ODD process is shown to operate by drawing on constructive and destructive interference effects to simultaneously maximize or minimize the signals from each of the species in the mixture. The ODD technique may have applications to the analysis and separation of possibly even complex chemical species.