Calculation of Heartbeat Rate and SpO2 Parameters Using a Smartphone Camera: Analysis and Testing.

Mathematical and signal-processing methods were used to obtain reliable measurements of the heartbeat pulse rate and information on oxygen concentration in the blood using short video recordings of the index finger attached to a smartphone built-in camera. Various types of smartphones were used with different operating systems (e.g., iOS, Android) and capabilities. A range of processing algorithms were applied to the red-green-blue (RGB) component signals, including mean intensity calculation, moving average smoothing, and quadratic filtering based on the Savitzky-Golay filter. Two approaches-gradient and local maximum methods-were used to determine the pulse rate, which provided similar results. A fast Fourier transform was applied to the signal to correlate the signal's frequency components with the pulse rate. We resolved the signal into its DC and AC components to calculate the ratio-of-ratios of the AC and DC components of the red and green signals, a method which is often used to estimate the oxygen concentration in blood. A series of measurements were performed on healthy human subjects, producing reliable data that compared favorably to benchmark data obtained by commercial and medically approved oximeters. Furthermore, the effect of the video recording duration on the accuracy of the results was investigated.

Quantum interferences among Dexter energy transfer pathways.

Dexter energy transfer in chemical systems moves an exciton (i.e., an electron-hole pair) from a donor chromophore to an acceptor chromophore through a bridge by a combination of bonded and non-bonded interactions. The transition is enabled by both one-electron/one-particle and two-electron/two-particle interaction mechanisms. Assuming that there is no real intermediate state population of an electron, hole, or exciton in the bridge, the transport involves two states that are coupled non-adiabatically. As such, coherent quantum interferences arise among the Dexter energy coupling pathways. These interferences, while related to well understood interferences in single-electron transfer, are much richer because of their two particle nature: the transfer of a triplet exciton involves the net transfer of both an electron and a hole. Despite this additional complexity, simple rules can govern Dexter coupling pathway interferences in special cases. As in the case of single-electron transfer, identical parallel coupling pathways can be constructively interfering and may enhance the Dexter transfer rate. Because of the virtual particle combinatorics associated with two-particle superexchange, two parallel Dexter coupling routes may be expected to enhance Dexter couplings by more than a factor of two. We explore Dexter coupling pathway interferences in non-covalent assemblies, employing a method that enables the assessment of Dexter coupling pathway strengths and interferences, in the context of one-particle and two-particle coupling interactions.

Dexter energy transfer pathways.

Energy transfer with an associated spin change of the donor and acceptor, Dexter energy transfer, is critically important in solar energy harvesting assemblies, damage protection schemes of photobiology, and organometallic opto-electronic materials. Dexter transfer between chemically linked donors and acceptors is bridge mediated, presenting an enticing analogy with bridge-mediated electron and hole transfer. However, Dexter coupling pathways must convey both an electron and a hole from donor to acceptor, and this adds considerable richness to the mediation process. We dissect the bridge-mediated Dexter coupling mechanisms and formulate a theory for triplet energy transfer coupling pathways. Virtual donor-acceptor charge-transfer exciton intermediates dominate at shorter distances or higher tunneling energy gaps, whereas virtual intermediates with an electron and a hole both on the bridge (virtual bridge excitons) dominate for longer distances or lower energy gaps. The effects of virtual bridge excitons were neglected in earlier treatments. The two-particle pathway framework developed here shows how Dexter energy-transfer rates depend on donor, bridge, and acceptor energetics, as well as on orbital symmetry and quantum interference among pathways.

A Nonequilibrium Molecular Dynamics Study of Infrared Perturbed Electron Transfer.

Infrared (IR) excitation is known to change electron-transfer kinetics in molecules. We use nonequilibrium molecular dynamics (NEqMD) simulations to explore the molecular underpinnings of how vibrational excitation may influence nonadiabatic electron-transfer. NEqMD combines classical molecular dynamics simulations with nonequilibrium semiclassical initial conditions to simulate the dynamics of vibrationally excited molecules. We combine NEqMD with electronic structure computations to probe IR effects on electron transfer rates in two molecular species, dimethylaniline-guanosine-cytidine-anthracene (DMA-GC-Anth) and 4-(pyrrolidin-1-yl)phenyl-2,6,7-triazabicyclo[2.2.2]octatriene-10-cyanoanthracen-9-yl (PP-BCN-CA). In DMA-GC-Anth, the simulations find that IR excitation of the NH2 scissoring motion and the subsequent intramolecular vibrational energy redistribution (IVR) do not significantly alter the mean-squared donor-acceptor (DA) coupling interaction. This finding is consistent with earlier computational analysis of static systems. In PP-BCN-CA, IR excitation of the bridging C═N bond changes the bridge-mediated coupling for charge separation and recombination by ∼30-40%. The methods described here enable detailed explorations of how IR excitation may perturb charge-transfer processes at the molecular scale.

How can infra-red excitation both accelerate and slow charge transfer in the same molecule?

A UV-IR-Vis 3-pulse study of infra-red induced changes to electron transfer (ET) rates in a donor-bridge-acceptor species finds that charge-separation rates are slowed, while charge-recombination rates are accelerated as a result of IR excitation during the reaction. We explore the underpinning mechanisms for this behavior, studying IR-induced changes to the donor-acceptor coupling, to the validity of the Condon approximation, and to the reaction coordinate distribution. We find that the dominant IR-induced rate effects in the species studied arise from changes to the density of states in the Marcus curve crossing region. That is, IR perturbation changes the probability of accessing the activated complex for the ET reactions. IR excitation diminishes the population of the activated complex for forward (activationless) ET, thus slowing the rate. However, IR excitation increases the population of the activated complex for (highly activated) charge recombination ET, thus accelerating the charge recombination rate.