Cycloparaphenylene (CPP) series are molecular models for graphene armchair edges: trends in their aromaticity and cyclic conjugation are evaluated

Cycloparaphenylene ([r]CPP) and cyclacene ([r]CA) series are models for short carbon nanotubes. It is shown that armchair edges in model cycloparaphenylenes possess greater aromaticity and cyclic conjugation than do zigzag edges in model cyclacenes. According to Aihara’s bond resonance energy (BRE) and Bosanac and Gutman energy effect (ef) measurements, cycloparaphenylenes are twice as aromatic as cyclacenes. The general solution of all eigenvalues of all members of the cycloparaphenylene series is given. The origin of the recurrence of some eigenvalues are determined.     

Measurement of multi-exponential optical decay processes by?phase-shift cavity ring-down

Multi-exponential decay waveforms are common occurrences in cavity ring-down spectroscopy and the respective ring-down times are typically obtained by fitting the ring-down waveform to the sum of exponential decay functions. In phase-shift cavity ring-down (CRD) spectroscopy the measurement of a single phase angle will not provide sufficient information and needs to be complemented by either intensity measurements or phase angle measurements at different modulation frequencies. Here, a formalism analogous to that developed for fluorescence lifetime spectroscopy is adapted to the phase-shift CRD technique and is tested for two types of waveguide CRD systems: (1) a single-mode fiber cavity in which light is confined by two identical Fiber Bragg Gratings and (2) a multimode fiber loop. By measuring the phase angle at different modulation frequencies, lifetimes for up to three different decay processes were obtained.     

A genetic algorithm with neural network fitness function evaluation for IMRT beam angle optimization

Intensity Modulated Radiotherapy Treatment (IMRT) is a technique used in the treatment of cancer, where the radiation beams are modulated by a multileaf collimator allowing the irradiation of the patient using non-uniform radiation fields from selected angles. Beam angle optimization consists in trying to find the best set of angles that should be used in IMRT planning. The choice of this set of angles is patient and pathology dependent and, in clinical practice, most of the times it is made using a trial and error procedure or simply using equidistantly distributed angles. In this paper we propose a genetic algorithm that aims at calculating good sets of angles in an automated way, given a predetermined number of angles. We consider the discretization of all possible angles in the interval [0 \(^{\circ }\) , 360 \(^{\circ }\) ], and each individual is represented by a chromosome with 360 binary genes. As the calculation of a given individual’s fitness is very expensive in terms of computational time, the genetic algorithm uses a neural network as a surrogate model to calculate the fitness of most of the individuals in the population. To explicitly consider the estimation error that can result from the use of this surrogate model, the fitness of each individual is represented by an interval of values and not by a single crisp value. The genetic algorithm is capable of finding improved solutions, when compared to the usual equidistant solution applied in clinical practice. The genetic algorithm will be described and computational results will be shown.     

Critical exponents for Fréedericskz transition in nematics between concentric cylinders

The equilibrium tilt angle profile in a cell limited by two concentric cylinders filled with nematic liquid crystals is determined for strong homeotropic anchoring at the surfaces. The anchoring condition is such that the nematic director is perpendicular to the cylinder axes and a radial nonuniform electric field is applied to investigate a Fréedericksz transition. The distortions induced by the field remain in the plane perpendicular to the cylinder axes, and a threshold field is analytically determined indicating a transition from a pure splay to a splay-bend conformation of the director. It is shown that this transition can be induced by the thickness of the region between the two cylinders, and can be detected even in the absence of an external field. If the maximum value of the tilt angle is assumed as an order parameter, its behavior near to the transition can be used to obtain the critical exponent, which is the same as the one obtained in the mean field approximation. These results are indications that nontrivial consequences may occur when complex fluids are subject to non-planar geometries.     

Intertrimer and intratrimer metallophilic and excimeric bonding in the ground and phosphorescent States of trinuclear coinage metal pyrazolates: a computational study

The interactions present in cyclic trinuclear coinage metal pyrazolates were studied computationally. Cuprophilic interaction was found to bind the singlet ground state of the dimer of trimers [[Cu(Pz)](3)](2), overcoming electrostatic repulsion. The large variation in intertrimer separations found in the literature for coinage metal pyrazolates is consistent with the relatively weak metallophilic interaction. The emissive triplet excited-state geometry of [[M(Pz)](3)](2) is predicted by density functional calculations to show major geometric distortion caused by Jahn-Teller instability and excimeric M-M bonding. Large calculated Stokes' shifts, which are also observed for experimental models, are consistent with significant excited-state distortions for these materials. The major finding derived from the present study is that the intertrimer M...M contraction in the emissive T(1) state is much more than the intratrimer contraction in all [[M(Pz)](3)](2) models, giving rise to a lower T(1) --> S(0) phosphorescence energy in these models than in analogous monomer-of-trimer models. The observations made here point to a great potential for rationally tuning the emission properties of trinuclear coinage metal complexes through choice of the metal and ligands.     

Synthesis and comparative spectroscopic analysis of two chenodeoxycholic acid (CDCA) derivatives with closely related 7α-ester moieties

3α-Hydroxyl-7α-(4-pentenoyloxy)-5β-cholanoic acid (5) has been synthesized in four step reactions starting from CDCA. The serendipitous synthesis of methyl 3α-(ethoxycarbonyloxy)-7α-(allyloxycarbonyloxy)-5β-cholanoate (7) has led us to compare the spectroscopic difference of the 7α-(allyloxycarbonyloxy) group versus the 7α-(4-pentenoyloxy) group. The molecular structures of these compounds were confirmed by X-ray crystallography. Methyl 3α-(ethoxycarbonyloxy)-7α-(allyloxycarbonyloxy)-5β-cholanoate was obtained by a method, which may prove useful in the synthesis of ¹⁴C-labeled derivatives for metabolic studies.     

Synthesis and characterization of cellulose acetate from cellophane industry residues. Application as acetaminophen controlled-release membranes

Journal of Thermal Analysis and Calorimetry - Cellophane film production generates cellulosic residues from scraps, edges, and low-quality films. In this work, cellophane was used as a raw material...     

Fingerprinting pre-historical symbolic artefacts by a non-destructive methodological approach

Journal of Radioanalytical and Nuclear Chemistry - A contribution to the discussion about Vila Nova de São Pedro (VNSP) as a production centre of symbolic lithic artefacts, the origin of raw...     

Modern Synthetic Strategies with Organoselenium Reagents: A Focus on Vinyl Selenones

In recent years, vinyl selenones were rediscovered as useful building blocks for new synthetic transformations. This review will highlight these advances in the field of multiple-bond-forming reactions, one-pot synthesis of carbo- and heterocycles, enantioselective construction of densely functionalized molecules, and total synthesis of natural products.