Evaluation of Redox Activity of Human Myocardium‐derived Mesenchymal Stem Cells by Scanning Electrochemical Microscopy

In this study the redox activity of human myocardium‐derived mesenchymal stem cells (hmMSC) were investigated by redox‐competition (RC‐SECM) and generation‐collection (GC‐SECM) modes of scanning electrochemical microscopy (SECM), using 2‐methylnaphthalene‐1,4‐dione (menadione, MD) as a redox mediator. The redox activity of human healthy and dilated hmMSCs was evaluated by measuring reduction of MD. Measurements were performed by approaching and retracting the UME from the surface of growing hmMSC cells. The current study shows that the RC‐SECM mode can be applied to investigate integrity of cell membranes, whereas the most promising results were observed by using the GC‐SECM mode and applying the Hill's equation for the calculation/fitting of dependencies of electrical current vs menadione concentration. The calculated apparent Michaelis constant (K_M) for the production of menadiol (MDH₂) in the pathological hmMSC cells was 14.4 folds higher compared to that of the healthy hmMSC revealing the lover redox activity of pathological cells. Moreover, the calculated Hill's coefficient n shows a negative cooperative binding between MD and healthy hmMSC and positive cooperative binding between MD and pathological hmMSC. It means that healthy hmMSC is of lower affinity to MD, which is also related to the better membrane integrity of healthy cells. Data of this study demonstrate that SECM can be applied to investigate intracellular redox and membrane changes ongoing in human dilated myocardium‐derived hmMSC in order to improve their functioning and further regenerative potential.     

Bloch cavity solitons in nonlinear resonators with intracavity photonic crystals

We predict a novel type of cavity solitons, Bloch cavity solitons, existing in nonlinear resonators with the refractive index modulated in both longitudinal and transverse directions and for both focusing (at normal diffraction) and defocusing (at anomalous diffraction) nonlinearities. We develop a modified mean-field theory and analyze the properties of these novel cavity solitons demonstrating, in particular, their substantial narrowing in the zero-diffraction regime.     

Broad angle phase matching in subdiffractive photonic crystals

We show that photonic crystals made of materials with normal dispersion allow broad angular range phase matching in nonlinear wave mixing processes if tuned to the subdiffractive (or equivalently self-collimated) beam propagation regimes for the frequencies of both interacting waves. This allows efficient parametric mixing of narrow beams. We demonstrate this idea by numerical simulation of the second harmonic generation in two-dimensional photonic crystal in particular nonlinear material (AlGaAs) in planar waveguide geometry.     

Computation of phase response curves via a direct method adapted to infinitesimal perturbations

A new numerical algorithm for computation of phase response curves of stable limit cycle oscillators is proposed. The idea of the algorithm originates from a direct method that is based on computation of the oscillator response to short finite pulses delivered at different phases of oscillations. Here we adapt the direct method to the case of infinitesimal perturbations and compare our algorithm with the standard algorithm based on the backward integration of the adjoint equations. In contrast to the standard algorithm, our algorithm does not require any backward integration and it is easier to program since a necessity of numerical interpolation for the Jacobian matrix is avoided. In addition, we demonstrate by examples that our algorithm is faster than the standard algorithm and this advantage is especially notable for weakly stable limit cycle oscillators.     

NMR spin-spin coupling constants in polymethine dyes as polarity indicators

Herein, we explore the use of spin-spin coupling constants (SSCCs) in merocyanine (MCYNE) dyes as indicators of polarity. For this purpose, we use Car-Parrinello hybrid quantum mechanics/molecular mechanics (QM/MM) to determine the structures of MCYNE in solvents of different polarity, followed by computations of the SSCCs by using QM/MM linear-response theory. The molecular geometry of MCYNE switches between neutral, cyanine-like, and zwitterionic depending on the polarity of the solvent. This structural variation is clearly reflected in the proton SSCCs in the polymethine backbone, which are highly sensitive to the dielectric nature of the environment; this mechanism can be used as a "polarity indicator" for different microenvironments. This result is highlighted by computing the SSCCs of the MCYNE probe in the cavity of the beta-lactoglobulin protein. The computed SSCCs clearly indicate a non-polar hydrophobic dielectric nature of this cavity.     

Continuous pole placement method for time-delayed feedback controlled systems

Continuous pole placement method is adapted to time-periodic states of systems with timedelay. The method is applied for finding an optimal control matrix in the problem ofstabilization of unstable periodic orbits of dynamical systems via time-delayed feedbackcontrol algorithm. The optimal control matrix ensures the fastest approach of a perturbedsystem to the stabilized orbit. An application of the pole placement method to systemswith time delay meets a fundamental problem, since the number of the Floquet exponents isinfinity, while the number of control parameters is finite. Nevertheless, we show thatseveral leading Floquet exponents can be efficiently controlled. The method is numericallydemonstrated for the Lorenz system, which until recently has been considered as a systeminaccessible for the standard time-delayed feedback control due to the odd-numberlimitation. The proposed optimization method is also adapted for an extended time-delayedfeedback control algorithm and numerically demonstrated for the Rössler system.     

Global properties in an experimental realization of time-delayed feedback control with an unstable control loop

We demonstrate by electronic circuit experiments the feasibility of an unstable control loop to stabilize torsion-free orbits by time-delayed feedback control. Corresponding analytical normal form calculations and numerical simulations reveal a severe dependence of the basin of attraction on the particular coupling scheme of the control force. Such theoretical predictions are confirmed by the experiments and emphasize the importance of the coupling scheme for the global control performance.     

1H NMR and DFT study of proton exchange in heterogeneous structures of pyridine-N-oxide/HCl/DCl/H2O

Moderately narrow 1H NMR signals were observed in the solid-phase obtained from pyridine-N-oxide (PyO)...HCl solutions in acetonitrile/H2O after heterogeneous phase separation. High-resolution 1H NMR spectra are compared with those of crystalline PyO...HCl and PyO...DCl. It is concluded that partially resolved peaks in 1H NMR spectra of solids are related with heterogeneity of the spin system and the presence of different mobile H-bond clusters containing PyO, HCl, DCl and water molecules. Some part of non-bonded water or HCl molecules is captured in the cavities of crystalline samples. The attribution of the 1H NMR signals was based on the density functional theory calculation of proton magnetic screening tensor of the most expected H-bond structures in the 6-311G** basis taking into account the solvent effect by the polarized continuum model.