Electron spin relaxation and frequency-dependent lineshape analysis of the 5′—ATP—Mn(II)—Trp system

A frequency-dependent lineshape analysis of the ESR spectra of ternary systems in solution has been carried out. The 5′-ATP—Mn(II)—Trp complex has been chosen as a model system. The analysis points out the presence of inverted spectra at both X- and Q-bands. The lineshape is described by a distribution of configurational sites, Y^l(ω) = Σ_kP_kY_k(H). The temperature dependence of the ESR linewidth has also been investigated and is discussed in terms of chemical equilibria and correlation times.     

Primary methods for the measurement of electrolytic conductivity

This paper surveys the state of the art for primary methods for the evaluation of electrolytic conductivity in aqueous solutions as they are currently carried out in several national metrological institutes (NMIs). The theoretical and practical basic knowledge of this measurement is described. Analysis of and comments on the different approaches are offered to give emphasis to technical difficulties and possible solutions. Further development is foreseeable, ensuring a common effort for the sharing of expertise that has been undertaken at the NMIs. In particular, improvements are expected towards traceable measurements of solutions with conductivity values lower than those actually standardized, down to the level of ultrapure water.     

Travelling Randomly on the Poincaré Half-Plane with a Pythagorean Compass

A random motion on the Poincaré half-plane is studied. A particle runs on the geodesic lines changing direction at Poisson-paced times. The hyperbolic distance is analyzed, also in the case where returns to the starting point are admitted. The main results concern the mean hyperbolic distance (and also the conditional mean distance) in all versions of the motion envisaged. Also an analogous motion on orthogonal circles of the sphere is examined and the evolution of the mean distance from the starting point is investigated.     

Net,excess and absolute adsorption in mixed gas adsorption

The formulation of a thermodynamic framework for mixtures based on absolute, excess or net adsorption is discussed and the qualitative dependence with pressure and fugacity is used to highlight a practical issue that arises when extending the formulations to mixtures and to the Ideal Adsorbed Solution Theory (IAST). Two important conclusions are derived: the correct fundamental thermodynamic variable is the absolute adsorbed amount; there is only one possible definition of the ideal adsorbed solution and whichever starting point is used the same final IAST equations are obtained, contrary to what has been reported in the literature.     

One- and two-photon absorption and emission properties of a Zn(II) chemosensor

This paper presents the synthesis and two photon-induced absorption (TPA) properties of a functionalized distyrylbenzene (DSB) 1 containing a tetra-azacyclododecane (cyclen) receptor for Zn(II). The influence of Zn(II) on one- and two-photon absorption characteristics of 1 has been investigated in dimethyl sulfoxide. The experiments show that the TPA action spectrum of uncomplexed 1, at 750 nm employing nanosecond-long excitation pulses, is 5 times more intense than that of the complexed form. This moderate contrast between the bound and unbound species confirms, however, the potential of this design scheme for the development of molecular structures with enhanced sensitivity and contrast to be used as Zn(II) sensors through TPA-induced fluorescence microscopy.     

A R2/R1 ratiometric procedure for a concentration-independent, pH-responsive, Gd(III)-based MRI agent

A novel procedure for making the pH responsiveness of a Gd-based probe independent of its concentration has been developed. The method is based on a ratiometric approach and requires the measurement, at magnetic fields higher than 1 T, of the paramagnetic contribution to the longitudinal and the transverse NMR relaxation rates of water protons in the presence of a Gd-based probe with a rotational mobility in the nanosecond time scale. The method has been tested and validated in vitro by using a macromolecular adduct based on the polyornithine backbone, whose rotational mobility is pH dependent. The results reported in this communication improve substantially the diagnostic potential of MRI responsive agents.     

Mechanism of angular momentum exchange between molecules and Laguerre-Gaussian beams

We derive the interaction Hamiltonian between a diatomic molecule and a Laguerre-Gaussian beam under the assumption of a small spread of the center of mass wave function of the molecule in comparison with the beam waist. Considering the dynamical variables of the center of mass, vibrational, rotational, and electronic motion, we show that, within the electronic dipole approximation, the orbital angular momentum of the field couples with the rotational and electronic motion. The changes in the transition probabilities and selection rules induced by the field orbital angular momentum and the applicability of the derived interaction mechanisms for polyatomic molecules are discussed.