Spin dynamics in a dissipative environment: from quantal to classical

We address the problem of spin dynamics in the presence of a thermal bath, by solving exactly the appropriate quantum master equations with continued-fraction methods. The crossover region between the quantum and classical domains is studied by increasing the spin value , and the asymptote for the classical absorption spectra is eventually recovered. Along with the recognized relevance of the coupling strength, we show the critical role played by the structure of the system-environment interaction in the emergence of classical phenomenology.     

Dual Functioning Thieno‐Pyrrole Fused BODIPY Dyes for NIR Optical Imaging and Photodynamic Therapy: Singlet Oxygen Generation without Heavy Halogen Atom Assistance

We discovered a rare phenomenon wherein a thieno‐pyrrole fused BODIPY dye (SBDPiR690) generates singlet oxygen without heavy halogen atom substituents. SBDPiR690 generates both singlet oxygen and fluorescence. To our knowledge, this is the first example of such a finding. To establish a structure–photophysical property relationship, we prepared SBDPiR analogs with electron‐withdrawing groups at the para‐position of the phenyl groups. The electron‐withdrawing groups increased the HOMO–LUMO energy gap and singlet oxygen generation. Among the analogs, SBDPiR688, a CF₃ analog, had an excellent dual functionality of brightness (82290 m ^?1 cm^?1) and phototoxic power (99170 m ^?1 cm^?1) comparable to those of Pc 4, due to a high extinction coefficient (211 000 m ^?1 cm^?1) and balanced decay (Φ_flu=0.39 and Φ_Δ=0.47). The dual functionality of the lead compound SBDPiR690 was successfully applied to preclinical optical imaging and for PDT to effectively control a subcutaneous tumor.     

Synthesis of 3-Substituted Pyrazole Derivatives by Mixed Anhydride Method and Study of Their Antibacterial Activities

A convenient synthesis of 3-substituted pyrazole derivatives by a mixed anhydride method using i-butylchloroformate and N-methylmorpholine at ?20 °C in tetrahydrofuran and study of in vitro antibacterial activities of the prepared compounds against Staphylococcus epidermidis, Bacillus subtilis, Pseudomonas aeruginosa, and Proteus valguris by agar-diffusion method were carried out. The results suggested that the products 4a, 4b, and 4c exhibited moderate to feeble inhibition against all test bacteria at greater concentration but 4d was best against Staphylococcus epidermidis (22 mm) and worst against Pseudomonas aeruginosa (16 mm) at the greatest concentration (2.5 mg/ml), and the activities decreased with decrease in concentration.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Particle deposition onto Janus and patchy spherical collectors

An Eulerian model (convection-diffusion-migration equation) is presented to study colloid deposition behavior on Janus and patchy spherical collectors using Happel cell geometry. The model aims to capture the effect of the collector surface charge heterogeneity on the particle deposition rate. Two separate cases of surface charge distribution are presented. In the first case, the surface heterogeneity is modeled as half the collector favoring deposition and the other half hindering it (Janus collectors). For the second case, the surface heterogeneity is modeled as alternate stripes of attractive and repulsive regions on the collector (patchy collectors). The model also considers fluid flow approaching the collector at different angles in addition to the standard gravity assisted and gravity hindered flow conditions to analyze the effect of the collector orientation on the deposition. It was observed that particles tend to deposit at the edges of the favorable stripes and the extent of this preferential accumulation varies along the tangential position of the collector due to the nonuniform nature of the collector. The predicted deposition behavior is compared to the patchwise heterogeneity model. The study brings to fore how recent developments in synthesis of chemically heterogeneous particles and beads can be used for improved particle capture in porous media and for designing filter beds with enhanced life.     

GeneralizedM-diffusion model of molecular rotations

The widely usedM-model of rotational diffusion of molecules in fluid phases is generalized. The ordinaryM-model assumes that intermolecular collisions causeinstantaneous changes in the orientation of an otherwise free rotor. The present scheme takes cognizance of the ubiquitous intermolecular torques which should make the molecular orientation a continuously variable random function of time. It is assumed here that the component of the angular velocity, which is conjugate to the angle specifying the orientation of the molecule, is a stationary Gaussian-Markov process. The ordinaryM-model emerges then as a special case of the more general treatment presented here. The results derived for the dipole correlation function of a linear rotor on the basis of the generalized scheme are applied to a series of infrared data. The observed agreement is highly satisfactory. The present analysis affords a justification for the Gordon scheme which generalizes theM-model by assigning to the mean rate of collision anad-hoc dependence on the angular speed of the rotor. It is argued also that the model treated here incorporates certain memory effects which are ignored in the ordinaryM-model, and may yield, in some cases, results which are similar to those based on certain memory function formalisms.     

Self-interstitials trapped at Co impurities in electron-irradiated Al: Theoretical study of the effects of static and dynamic quadrupolar interactions on Mössbauer line shape

The Mössbauer effect in electron-irradiated Al—Co alloy, in which the thermally activated reorientations of the impurity-defect dumbbells lead to fluctuating nuclear quadrupole interactions, is studied. A theory is presented which treats the simultaneous effects of quadrupolar relaxations and the diffusion broadening on the resonance line. The derived expressions of the line shape are discussed in light of the recent work by Vogl, Mansel and Dederichs.     

Localization of spin and charge in phenalenyl-based neutral radical conductors

We report the development of an experimentally based structural analysis to examine the degree of localization of the spin and charge in the phenalenyl-based neutral radical molecular conductors--the results motivate a reinterpretation of the electronic structure of a number of the radicals that we have reported over the past 10 years. The analysis is based on the well-known relationship between bond order and bond length and makes use of the experimental bond distance deviations between the molecular structure of the radical and its corresponding cation. We determined the single crystal X-ray structure of the ethyl radical (1) at 11 temperatures between 90 K and room temperature so that we could follow the evolution of the structure and the electron density distribution through the magnetic phase transition that occurs in the vicinity of 140 K. We show that the enhanced conductivity in the dimeric ethyl (1) and butyl (3) radicals at the magnetic phase transition results from the development of a complex, but highly delocalized electronic structure and not to the formation of a diamagnetic pi-dimer. We find that the monomeric radicals 4, 12, and 13 have an asymmetric electron density distribution in the crystal lattice whereas radical 11 is the only monomeric radical which remains fully delocalized. The pi-chain radicals (7, 8, 14, and 15) retain the strongly delocalized electronic structures expected for a resonating valence bond ground-state structure.