Deactivation of vibrationally excited ozone by O(3P) atoms

Using laser-induced fluorescence of ozone (to measure the rate of disappearance of O₃²) and NO₂ titration (to determine O atom concentrations), we have determined bimolecular rate constants for the deactivation by O(³P atoms) of ozone in excited stretching and bending modes. These experiments do not distinguish between deactivation by (a) the exchange of vibrational and translational energy or (b) the chemical reaction O₃ + O → 2O₂. If the non-reactive pathway (a) is assumed to dominate, then O(³P) is 150 times more effective than O₂ in deactivating O²₃. If chemical reaction (b) is dominant, the bimolecular rate constant for O²₃ + O(³P) is larger by a factor of 150–1500 than that for ground-state ozone.     

The ring-opening reaction of chromenes: a photochemical mode-dependent transformation

The efficiency of the photochemical ring-opening of chromenes (or benzopyrans) depends on the vibronic transition selected by the chosen excitation wavelength. In the present work, ab initio CASPT2//CASSCF calculations are used to determine the excited-state ring-opening reaction coordinate for 2H-chromene (C) and 2,2-diethyl-2H-chromene (DEC) and provide an explanation for such an unusual mode-dependent behavior. It is shown that excited-state relaxation and decay occur via a multimodal and barrierless (or nearly barrierless) reaction coordinate. In particular, the relaxation out of the Franck-Condon involves a combination of in-plane skeletal stretching and out-of-plane modes, while the second part of the reaction coordinate is dominated exclusively by a different out-of-plane mode. Population of this last mode is shown to be preparatory with respect to both C-O bond breaking and decay via an S(1)/S(0) conical intersection. The observed mode-dependent ring-opening efficiency is explained by showing that the vibrational mode corresponding to the most efficient vibronic transition has the largest projection onto the out-of-plane mode of the reaction coordinate. To support the computationally derived mechanism, we provide experimental evidence that the photochemical ring-opening reaction of 2,2-dimethyl-7,8-benzo(2H)chromene, that similarly to DEC exhibits a mode-dependent photoreaction, has a low ( approximately 1 kcal mol(-1)) activation energy barrier.     

INVESTIGATION INTO THE SPECTROSCOPY AND PHOTOISOMERIZATION OF A SERIES OF POLY (ETHYLENE GLYCOL) PEPTIDE SCHIFF BASES OF 11-cis RETINAL

Abstract— The 11-cis and all-trans isomers of a series of poly(ethylene glycol)-oligopeptide - Schiff bases as models for rhodopsin were synthesized and studied. Absorption data for certain of the PEG-peptide Schiff bases demonstrated that no intramolecular hydrogen-bonding (or protonation) occurs between the Schiff base and an acidic amino acid residue, as was previously thought. Photoisomerization of the 11-cis protonated and unprotonated Schiff bases were examined using both steady state and laser flash techniques. Also with 355 nm excitation (and additionally 532 nm in one case), an approximate 40% increase in quantum yield of isomerization (φ) occurred for all protonated PEG-peptide Schiff bases compared to the H⁺-n-butylamine counterparts (in methanol). In one case, a > 100% increase in φ was found in dichloromethane. These data show that PEG-oligopeptide Schiff bases are still further improved models for rhodopsin compared to their n-butylamine analogs.     

Investigations of thermal polymerization in the stable free‐radical polymerization of 2‐vinylnaphthalene

The feasibility of utilizing stable free‐radical polymerization (SFRP) in the synthesis of well‐defined poly(2‐vinylnaphthalene) homopolymers has been investigated. Efforts to control molecular weight by manipulating initiator concentration while maintaining a 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy (TEMPO):benzoyl peroxide (BPO) molar ratio of 1.2:1 proved unsuccessful. In addition, systematic variations of the TEMPO: BPO molar ratio did not result in narrow molecular weight distributions. In situ Fourier transform infrared spectroscopy (FTIR) indicated that the rate of monomer disappearance under SFRP and thermal conditions were identical. This observation indicated a lack of control in the presence of the stable free radical, TEMPO. The similarities in chemical structure between styrene and 2‐vinylnaphthalene suggested thermally initiated polymerization occurred via the Mayo mechanism. A kinetic analysis of the thermal polymerization of styrene and 2‐vinylnaphthalene suggested that the additional fused ring in 2‐vinylnaphthalene increased the propensity for thermal polymerization. The observed rate constant for thermal polymerization of 2‐vinylnaphthalene was determined using in situ FTIR spectroscopy and was one order of magnitude greater than styrene, assuming pseudo‐first‐order kinetics. Also, an Arrhenius analysis indicated that the activation energy for the thermal polymerization of 2‐vinylnaphthalene was 30 kJ/mol less than styrene. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 583–590, 2002; DOI 10.1002/pola.10131     

Congruence modularity implies the Arguesian identity

It is shown that if is any variety of algebras all of whose congruence lattices are modular, then the congruence lattice of every algebra in satisfies the Arguesian law.     

Protein dielectrophoresis: Key dielectric parameters and evolving theory

Globular proteins exhibit dielectrophoresis (DEP) responses in experiments where the applied field gradient factor ∇E² appears far too small, according to standard DEP theory, to overcome dispersive forces associated with the thermal energy kT of disorder. To address this a DEP force equation is proposed that replaces a previous empirical relationship between the macroscopic and microscopic forms of the Clausius–Mossotti factor. This equation relates the DEP response of a protein directly to the dielectric increment δε⁺ and decrement δε⁻ that characterize its β-dispersion at radio frequencies, and also indirectly to its intrinsic dipole moment by way of providing a measure of the protein's effective volume. A parameter Γ_pw, taken as a measure of cross-correlated dipole interactions between the protein and its water molecules of hydration, is included in this equation. For 9 of the 12 proteins, for which an evaluation can presently be made, Γ_pw has a value of ≈4600 ± 120. These conclusions follow an analysis of the failure of macroscopic dielectric mixture (effective medium) theories to predict the dielectric properties of solvated proteins. The implication of a polarizability greatly exceeding the intrinsic value for a protein might reflect the formation of relaxor ferroelectric nanodomains in its hydration shell.     

Exhaled breath condensate: Determination of non-volatile compounds and their potential for clinical diagnosis and monitoring. A review

Exhaled breath condensate is a promising, non-invasive, diagnostic sample obtained by condensation of exhaled breath. Starting from a historical perspective of early attempts of breath testing towards the contemporary state-of-the-art breath analysis, this review article focuses mainly on the progress in determination of non-volatile compounds in exhaled breath condensate. The mechanisms by which the aerosols/droplets of non-volatile compounds are formed in the airways are discussed with methodological consequences for sampling. Dilution of respiratory droplets is a major problem for correct clinical interpretation of the measured data and there is an urgent need for standardization of EBC. This applies also for collection instrumentation and therefore various commercial and in-house built devices are described and compared with regard to their design, function and collection parameters. The analytical techniques and methods for determination of non-volatile compounds as potential markers of oxidative stress and lung inflammation are scrutinized with an emphasis on method suitability, sensitivity and appropriateness. The relevance of clinical findings for each group of possible non-volatile markers of selected pulmonary diseases and methodological recommendations with emphasis on interdisciplinary collaboration that is essential for future development into a fully validated clinical diagnostic tool are given.     

Numerical and experimental characterization of antenna positioning in a dual-radio mesh router

This paper investigates the influence of the position of the antennas in a dual-radio mesh router by characterizing the router components from an electromagnetic point of view. Since the behavior of a wireless router equipped with multiple devices and antennas can be affected by mutual coupling among several close conducting bodies, numerical and experimental tests are carried out to provide some suggestions for an accurate positioning of the antennas. A reference configuration is implemented in an electromagnetic Computer-Aided Design (CAD) simulator. The most significant numerical results are validated by performing a campaign of measurements in anechoic chamber and deploying a testbed for the derivation of the experimental values of throughput, return loss, power density, and directivity.     

An investigation of preservice teachers’ use of guess and check in solving a semi open-ended mathematics problem

Open-ended problems have been regarded as powerful tools for teaching mathematics. This study examined the problem solving of eight mathematics/science middle-school teachers. A semi-structured interview was conducted with (PTs) after completing an open-ended triangle task with four unique solutions. Of particular emphasis was how the PTs used a specific heuristic strategy. The results showed that the primary strategy PTs employed in attempting to solve the triangle problem task was guess and check; however, from the PTs’ reflections, we found there existed misapplications of guess and check as a systematic problem-solving strategy. In order to prepare prospective teachers to effectively teach, teacher educators should pay more attention to the mathematical proficiency of PTs, particularly their abilities to systematically and efficiently use guess and check while solving problems and explain their solutions and reasoning to middle-school students.