Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane

Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2′-yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive ‘mixed’ state of 1-(pyren-2′-yl)-o-carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium.

Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium between LE and CT states by time-resolved and temperature-dependent fluorescence, fs- and ns-transient absorption, and LR-TDDFT calculations.     

Anti-Inflammatory and Antinociceptive Activities of the Essential Oil of Tagetes parryi A. Gray (Asteraceae) and Verbenone

Tagetes parryi is a plant empirically used to treat gastrointestinal and inflammatory diseases, its essential oil (EOTP) was obtained from the aerial parts, and the composition was elucidated by GC-MS. The in vivo and in vitro anti-inflammatory activities and the antinociceptive activity of EOTP and (1S)-(-)-verbenone (VERB) were assessed. The major compounds identified for EOTP were verbenone (33.39%), dihydrotagetone (26.88%), and tagetone (20.8%). EOTP and VERB diminished the ear oedema induced with TPA by 93.77 % and 81.13 %, respectively. EOTP and VERB decreased inflammation in a 12-O-tetradecanoylphorbol-13-acetate (TPA) chronic model with ED₅₀ = 54.95 mg/kg and 45.24 mg/kg, respectively. EOTP (15 µg/mL) inhibited the in vitro production of the pro-inflammatory mediators NO (67.02%), TNF-α (69.21%), and IL-6 (58.44%) in LPS-stimulated macrophages. In the acetic induced writhing test, EOTP and VERB showed antinociceptive effects with ED₅₀ = 84.93 mg/kg and ED₅₀ = 45.24 mg/kg, respectively. In phase 1 of the formalin test, EOTP and VERB showed no antinociceptive effects, whereas in phase 2, EOTP (ED₅₀ = 35.45 mg/kg) and VERB (ED₅₀ = 24.84 mg/kg) showed antinociceptive effects. The antinociceptive actions of ETOP and VERB were blocked with the co-administration of L-NAME. This study suggests that EOTP and VERB might be used in the treatment of pain and inflammatory problems.     

Detection of unexploded ordnance by PGNAA based borehole-logging

The performance of a borehole-logging system, based on prompt-gamma-neutron-activation-analysis (PGNAA), for explosive detection was studied by Monte-Carlo simulations. The prompt gamma of nitrogen, which is a constituent of common explosive, was used to identify the unexploded ordnance (UXO). Our results show that the minimum counting time depends on the soil moisture, the cladding thickness and the explosive composition. In conjunction with the standard detection by magnetometry, the PGNAA is a promising analytical technique for definitive identification of deep buried UXOs.     

Flexible electronics: Prediction of substrate deformation during different steps of the lithography process

A numerical model was developed to simulate the micro-deformations of a polymeric substrate due to lithographic processing of different layers of a transistor-like structure. The results of the model were validated with the results from experiments. The model, a mechanical-thermal-hygroscopic model, takes into account the dimensional effects of temperature, moisture and stresses. It also includes the temperature dependent visco-elastic behaviour of the polymer substrate. The model can be used to predict overlay accuracies between different functional layers introduced by the lithographic process. It can also be used to understand the underlying processes such that it provides a tool to improve the overlay accuracy during actual processing.     

A corresponding states principle-based equation for the surface tension of Alkenes

This study presents a new formula for the surface tension prediction of alkenes. As a first step, an analysis of the available data of the experimental surface tension data for alkenes was performed. The experimental data were collected, after a careful literature survey, for the following pure fluids: propene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, and 1-pentadecene. Then, the experimental data were regressed with the most reliable semi-empirical correlating methods based on the corresponding state theory existing in the literature. As a final step, an analysis of the available data of the experimental surface tension data for alkenes was performed starting from the two recently proposed equations for the prediction of the surface tension of refrigerants based on the corresponding states principle. To minimize the deviation between the predicted data and the experimental data and to find the optimal equation coefficients for experimental data regression, a (μ + λ)-evolution strategy was adopted. The analysis showed that the equation that gave the best results for the prediction of the surface tension of alkenes was the one with a very limited number of parameters. The finally proposed equation is very simple and gives a noticeable improvement with respect to the existing equations. It is based on the corresponding state principle, containing the acentric factor, the critical temperature, and pressure.     

Synchronization and Non-Smooth Dynamical Systems

In this article we establish an interaction between non-smooth systems, geometric singular perturbation theory and synchronization phenomena. We find conditions for a non-smooth vector fields be locally synchronized. Moreover its regularization provide a singular perturbation problem with attracting critical manifold. We also state a result about the synchronization which occurs in the regularization of the fold-fold case. We restrict ourselves to the 3-dimensional systems (ℓ = 3) and consider the case known as a T-singularity.     

Emergent biaxiality in nematic microflows illuminated by a laser beam

Anisotropic fluids (e.g. liquid crystals) offer a remarkable promise as optofluidic materials owing to the directional, tunable, and coupled interactions between the material, flow, and the optical fields. Here we present a comprehensive in silico treatment of this anisotropic interaction by performing nonequilibrium molecular dynamics simulations. We quantify the response of a nematic liquid crystal (NLC) undergoing a Poiseuille flow in the Stokes regime, while being illuminated by a laser beam incident perpendicular to the flow direction. We adopt a minimalistic model to capture the interactions, accounting for two features: first, the laser heats up the NLC locally; and second, the laser polarises the NLC and exerts an optical torque that tends to reorient molecules of the nematic phase. Because of this reorientation the liquid crystal exhibits small regions of biaxiality, where the nematic director is one symmetry axis and the axis of rotation for the reorientation of the molecules is the other one. We find that the relative strength of the viscous and the optical torques mediates the flow-induced response of the biaxial regions, thereby tuning the emergence, shape and location of the regions of enhanced biaxiality. The mechanistic framework presented here promises experimentally tractable routes toward novel optofluidic applications based on material-flow-light interactions.     

Information-theoretic differential geometry of quantum phase transitions

The manifold of coupling constants parametrizing a quantum Hamiltonian is equipped with a natural Riemannian metric with an operational distinguishability content. We argue that the singularities of this metric are in correspondence with the quantum phase transitions featured by the corresponding system. This approach provides a universal conceptual framework to study quantum critical phenomena which is differential geometric and information theoretic at the same time.