NQR Studies of the chloro(amino)cyclotriphosphazenes,N3P3(NHCH2·CH2NH)Cl4, N3P3(NHBut)4Cl4 and N3P3(NHBut)4Cl2

The frequencies and variable-temperature behaviour of ³⁵Cl nuclear quadrupole resonance in three aminocyclophosphazene derivatives are reported. The observed frequencies and multiplicity are correlated with the disposition of the substituents and the crystal structure. The temperature-dependence data are discussed in the framework of Bayer-Kushida-Brown equations and low-lying torsional (librational) frequencies and their average temperature coefficients are estimated. Brown's parabolic equation provides a good fit to the experimental data. Variable-temperature proton FT-NMR measurements (at 270 MHz) have also been carried out. The results are consistent with the NQR data and indicate the presence of two-site chemical exchange of the -NH protons and hydrogen bonding.     

A simple and inexpensive two channel boxcar integrator

It is shown that the inclusion of a small amount of primary ionisation makes the solution to the discharge equilibrium problem single valued.     

Electronegativities in the calculation of diatomic molecular parameters (Hydrides of some transition elements)

The force constants for diatomic molecules and isolated bonds may be expressed by using equalized electro-negativities, bond orders, bond strengths and interatomicdistances. We have studied Mn¹H, Mn²H, Co²H, Ni¹H, Ni²H, Cu¹H, Cu²H, Ag¹H, and Ag²H and have determined the proportionality constant d, as well as the Lennard-Jones parameters a and b, for the potential energy functions used by Szöke and calculated the anharmonicity ω_eξ_e and the rotational-vibrational coupling constant α_e. The relation between electronegativity and ionization potential has been verified and the variations of molecular parameters with atomic number Z have been studied.     

Ultrafast dynamics and excited state deactivation of [Ru(bpy)2Sq]+ and its derivatives

Femtosecond transient absorption spectroscopy has been employed to understand the excited state dynamics of [Ru(bpy)(2)Sq](+) (I; bpy is 2,2'-bipyridyl, and Sq is the deprotonated species of the semiquinone form of 1,2-dihydroxy benzene) and its derivatives, a widely studied near-infrared (NIR) active electrochromic dye. Apart from the well-defined dpi(Ru) --> pi(bpy)-based metal-to-ligand charge transfer (MLCT) transition bands at approximately 480 nm, this class of molecules generally shows another dpi(Ru) --> pi(Sq)(SOMO)-based intense MLCT band at around 900 nm, which is known to be redox active and bleaches reversibly upon a change in the oxidation state of the coordinated dioxolene moiety. To have better insight into the photoinduced electron transfer dynamics associated with this MLCT transition, detailed investigations have been carried out on exciting this MLCT band at 800 nm. Immediately after photoexcitation, bleach at 900 nm has been observed, whose recovery is found to follow a triexponential function with major contribution from the ultrafast component. This ultrafast component of approximately 220 fs has been ascribed to the S(1) to S(0) internal conversion process. In addition to the bleach, we have detected two transient species absorbing at 730 and 1000 nm with a formation time approximately 220 fs for both species. The excited state lifetimes for these two transient species have been measured to be 1.5 and 11 ps and have been attributed to excited singlet ((1)MLCT) and triplet ((3)MLCT) states, respectively. Transient measurements carried out on the different but analogous derivatives (II and III) have also shown similar recovery dynamics except that the rate for the internal conversion process has increased with the decrease in the S(1) to S(0) energy gap. The observed results are consistent with the energy gap law for nonradiative decay from S(1) to S(0).     

Universal occurrence of the phase-flip bifurcation in time-delay coupled systems

Recently, the phase-flip bifurcation has been described as a fundamental transition in time-delay coupled, phase-synchronized nonlinear dynamical systems. The bifurcation is characterized by a change of the synchronized dynamics from being in-phase to antiphase, or vice versa; the phase-difference between the oscillators undergoes a jump of pi as a function of the coupling strength or the time delay. This phase-flip is accompanied by discontinuous changes in the frequency of the synchronized oscillators, and in the largest negative Lyapunov exponent or its derivative. Here we illustrate the phenomenology of the bifurcation for several classes of nonlinear oscillators, in the regimes of both periodic and chaotic dynamics. We present extensive numerical simulations and compute the oscillation frequencies and the Lyapunov spectra as a function of the coupling strength. In particular, our simulations provide clear evidence of the phase-flip bifurcation in excitable laser and Fitzhugh-Nagumo neuronal models, and in diffusively coupled predator-prey models with either limit cycle or chaotic dynamics. Our analysis demonstrates marked jumps of the time-delayed and instantaneous fluxes between the two interacting oscillators across the bifurcation; this has strong implications for the performance of the system as well as for practical applications. We further construct an electronic circuit consisting of two coupled Chua oscillators and provide the first formal experimental demonstration of the bifurcation. In totality, our study demonstrates that the phase-flip phenomenon is of broad relevance and importance for a wide range of physical and natural systems.     

Spectroscopic labeling of A, S/T in the 1H-15N HSQC spectrum of uniformly (15N-13C) labeled proteins

A new triple resonance two-dimensional experiment, termed (HC)NH, has been described to generate specific labels on the peaks of alanines and serines/threonines, separately, in the ¹H–¹⁵N HSQC spectrum of a protein. The performance of the pulse sequence has been demonstrated with a 151 residue protein. The method permits the investigation of local environments around those specific residues without actually having to obtain complete resonance assignments for the entire protein. With this one can envisage use of the technique for studying large protein systems from different points of view.     

The Kirkendall Effect for Engineering Oxygen Vacancy of Hollow Co3O4 Nanoparticles toward High‐Performance Portable Zinc–Air Batteries

Structure and defect control are widely accepted effective strategies to manipulate the activity and stability of catalysts. On a freestanding hierarchically porous carbon microstructure, the tuning of oxygen vacancy in the embedded hollow cobaltosic oxide (Co₃O₄) nanoparticles is demonstrated through the regulation of nanoscale Kirkendall effect. Starting with the embedded cobalt nanoparticles, the concentration of oxygen‐vacancy defect can vary with the degree of Kirkendall oxidation, thus regulating the number of active sites and the catalytic performances. The optimized freestanding catalyst shows among the smallest reversible oxygen overpotential of 0.74 V for catalyzing oxygen reduction/evolution reactions in 0.1 m KOH. Moreover, the catalyst shows promise for substitution of noble metals to boost cathodic oxygen reactions in portable zinc–air batteries. This work provides a strategy to explore catalysts with controllable vacancy defects and desired nano‐/microstructures.