High-temperature measurements of the reactions of OH with toluene and acetone

The reaction of hydroxyl [OH] radicals with toluene [C6H5CH3] was studied at temperatures between 911 and 1389 K behind reflected shock waves at pressures of approximately 2.25 atm. OH radicals were generated by rapid thermal decomposition of shock-heated tert-butyl hydroperoxide [(CH3)3-CO-OH], and monitored by narrow-line width ring dye laser absorption of the well-characterized R1(5) line of the OH A-X (0,0) band near 306.7 nm. OH time histories were modeled by using a comprehensive toluene oxidation mechanism. Rate constants for the reaction of C6H5CH3 with OH were extracted by matching modeled and measured OH concentration time histories in the reflected shock region. Detailed error analyses yielded an uncertainty estimate of +/-30% at 1115 K for the rate coefficient of this reaction. The current high-temperature data were fit with the lower temperature measurements of Tully et al. [J. Phys. Chem. 1981, 85, 2262-2269] to the following two-parameter form, applicable over 570-1389 K: k3 = (1.62 x 10(13)) exp(-1394/T [K]) [cm3 mol(-1) s(-1)]. The reaction between OH radicals and acetone [CH3COCH3] was one of the secondary reactions encountered in the toluene + OH experiments. Direct high-temperature measurements of this reaction were carried out at temperatures ranging from 982 to 1300 K in reflected shock wave experiments at an average total pressure of 1.65 atm. Uncertainty limits were estimated to be +/-25% at 1159 K. A two-parameter fit of the current data yields the following rate expression: k6 = (2.95 x 10(13)) exp(-2297/T [K]) [cm3 mol(-1) s(-1)].     

Enhanced deterministic phase retrieval using a partially developed speckle field

A technique for enhanced deterministic phase retrieval using a partially developed speckle field (PDSF) and a spatial light modulator (SLM) is demonstrated experimentally. A smooth test wavefront impinges on a phase diffuser, forming a PDSF that is directed to a 4f setup. Two defocused speckle intensity measurements are recorded at the output plane corresponding to axially-propagated representations of the PDSF in the input plane. The speckle intensity measurements are then used in a conventional transport of intensity equation (TIE) to reconstruct directly the test wavefront. The PDSF in our technique increases the dynamic range of the axial intensity derivative for smooth phase objects, resulting in a more robust solution to the TIE. The SLM setup enables a fast and accurate recording of speckle intensity. Experimental results are in good agreement with those obtained using the iterative phase retrieval and digital holographic methods of wavefront reconstruction.     

Divalent activation in temporary phosphate tethers: highly selective cuprate displacement reactions

Desymmetrization of a readily derived pseudo-C(2)-symmetric monocyclic phosphate via highly diastereoselective anti-S(N)2' allylic displacement reactions is reported. This method utilizes of a wide variety of zinc-derived organocuprates to afford E-1,2-syn-configured phosphate acid building blocks. Extension of this protocol to unsymmetric monocyclic phosphates exclusively yields 1,2-anti-configured products. Within this study, stereoelectronic factors, coupled with allylic strain, ultimately govern regio- and diastereoselective cuprate reactions, further substantiating the Corey mechanism for organocuprate additions into allylic esters. [reaction: see text]     

The role of botrydienediol in the biodegradation of the sesquiterpenoid phytotoxin botrydial by Botrytis cinerea

The biotransformation of botrydienediol (6) labelled with deuterium on carbons C-10 and C-15 has been studied. This has led to modification of some previous assumptions about the biodegradative route of botrydial. The [10-²H,15-²H]-botry-1(9)-4-diendiol (12) was transformed into dehydrobotrydienediol derivatives 13-15 but it was not incorporated into secobotryane skeleton (7). In addition, three new sesquiterpenoids have been isolated, which shed further light on the secondary metabolites of Botrytis cinerea. From the point of view of persistence of these toxins in the food chain, the easy biotransformation and different biodegradative routes of botrydial (1), seem to indicate that the toxin may not persist in the plant for a long time as it will be metabolized by the fungi and the plant.     

High-temperature measurements of the reactions of OH with a series of ketones: acetone, 2-butanone, 3-pentanone, and 2-pentanone

The overall rate constants for the reactions of hydroxyl radicals (OH) with a series of ketones, namely, acetone (CH(3)COCH(3)), 2-butanone (C(2)H(5)COCH(3)), 3-pentanone (C(2)H(5)COC(2)H(5)), and 2-pentanone (C(3)H(7)COCH(3)), were studied behind reflected shock waves over the temperature range of 870-1360 K at pressures of 1-2 atm. OH radicals were produced by rapid thermal decomposition of the OH precursor tert-butyl hydroperoxide (TBHP) and were monitored by the narrow line width ring dye laser absorption of the well-characterized R(1)(5) line in the OH A-X (0, 0) band near 306.69 nm. The overall rate constants were inferred by comparing the measured OH time histories with the simulated profiles from the detailed mechanisms of Pichon et al. (2009) and Serinyel et al. (2010). These measured values can be expressed in Arrhenius form as k(CH3COCH3+OH) = 3.30 × 10(13) exp(-2437/T) cm(3) mol(-1) s(-1), k(C2H5COCH3+OH )= 6.35 × 10(13) exp(-2270/T) cm(3) mol(-1) s(-1), k(C2H5COC2H5+OH) = 9.29 × 10(13) exp(-2361/T) cm(3) mol(-1) s(-1), and k(C3H7COCH3+OH) = 7.06 × 10(13) exp(-2020/T) cm(3) mol(-1) s(-1). The measured rate constant for the acetone + OH reaction from the current study is consistent with three previous experimental studies from Bott and Cohen (1991), Vasudevan et al. (2005), and Srinivasan et al. (2007), within ±20%. Here, we also present the first direct high-temperature rate constant measurements of 2-butanone + OH, 3-pentanone + OH, and 2-pentanone + OH reactions. The measured values for the 2-butanone + OH reaction are in close accord with the theoretical calculation from Zhou et al. (2011), and the measured values for the 3-pentanone + OH reaction are in excellent agreement with the estimates (by analogy with the H-atom abstraction rate constants from alkanes) from Serinyel et al. Finally, the structure-activity relationship from Kwok and Atkinson (1995) was used to estimate these four rate constants, and the estimated values from this group-additivity model show good agreement with the measurements (within ~25%) at the present experimental conditions.     

The Palo Verde reactor neutrino experiment a test for long baseline neutrino oscillations

Our collaboration has installed a long baseline neutrino oscillation experiment at the Palo Verde Nuclear Generating Station in Arizona. 12 tons of Gd loaded liquid scintillator, in a segmented detector, are used to search for oscillations at 740 m distance to three reactors. The anti-neutrino capture on the proton serves as detection reaction. The experiment is expected to reach a sensitivity of Δm² > 1.3 · 10⁻³ eV² and sin²2Θ > 0.1. Our range of sensitivity is tuned to test the ν_μ ↔ ν_e solution of the atmospheric neutrino anomaly.     

Effects of simulated source of tremor on acoustic and airflow voice measures

To test the effects of different sources of tremor on the voice, tremor was simulated by external rhythmic perturbation of structures at the subglottal, glottal, and supraglottal levels in 10 healthy subjects. The acoustic and airflow signals simultaneously recorded during sustained phonation in the normal and the 3 simulated tremor conditions were analyzed and compared. Voice measures included: fundamental frequency, 2 short-term perturbation measures (jitter and shimmer), and 3 long-term tremor measures (prominence ratios of the spectral peaks of the acoustic frequency contour, acoustic amplitude contour, and airflow contour). Measures of fundamental frequency and percent shimmer were not significantly affected by the simulated tremors. Measures of percent jitter and the amplitudes of the long-term frequency and amplitude modulations were most prominently increased when respiratory drive was perturbed by simulated tremor. Spectral analysis of the acoustic amplitude contour was most useful in distinguishing the 3 sites of simulated tremor.     

Studies of the dynamics of autoignition assisted outwardly propagating spherical cool and double flames under shock-tube conditions

The initiation, propagation, and transition of the autoignition assisted spherical cool flame and double flame are studied numerically and experimentally using n-heptane/air/He mixtures under shock-tube experimental conditions over a wide range of temperatures. The primary goal of the current study is to understand the effects of the ignition Damkohler number, ignition energy, flame curvature, and autoignition-induced flow compression on the propagation of spherical flames to ensure the proper interpretation of shock-tube flame speed measurements at engine-relevant conditions. The results show that at high ignition Damkohler number, there are three different flame regimes, cool flame, double flame, and hot flame. The cool flame speed accelerates dramatically with the increase of ignition Damkohler number. In addition, it is found that the change of flame regime, low-temperature autoignition, flame stretch, and autoignition-induced flow compression result in a complicated non-linear dependence of flame speed on stretch. The results also reveal that the spherical cool flame has much lower Markstein length compared to the hot flame at T > 600 K. Moreover, it is found that both the autoignition assisted cool flame and the trailing hot flame front in the double flame can propagate much faster that the hot flame alone at the same mixture conditions, leading to a nonlinear dependence of flame speed on the mixture initial temperature. The simulated flame trajectories and the flame speed dependence on temperature agree qualitatively well with the shock-tube experiments. A quantitative criterion to ensure the accurate speed measurement of the cool and hot flame is proposed. The present study provides important physical insight and guidance for the flame speed measurement using a shock-tube at engine relevant conditions.     

Thermal decomposition of toluene: Overall rate and branching ratio

The two-channel thermal decomposition of toluene, C₆H₅CH₃ → C₆H₅CH₂ + H (1) and C₆H₅CH₃ → C₆H₅ + CH₃ (2), was investigated in shock tube experiments over the temperature range of 1400-1780 K at a pressure of 1.5 (±0.1) bar. Rate coefficients for reactions (1) and (2) were determined by monitoring benzyl radical (C₆H₅CH₂) absorption at 266 nm during the decomposition of toluene diluted in argon and modeling the temporal behavior of the benzyl concentration with a kinetic model. The first-order rate coefficients determined at a pressure of 1.5 bar are expressed by k₁(T) = 2.09 × 10¹⁵ exp (−87510 [cal/mol]/RT) [s⁻¹] and k₂(T) = 2.66 × 10¹⁶ exp (−97880 [cal/mol]/RT) [s⁻¹]. The resulting branching ratio, k₁/(k₁ + k₂), ranges from 0.8 at 1350 K to 0.6 at 1800 K.     

Phenalenannulations: Three‐Point Double Annulation Reactions that Convert Benzenes into Pyrenes

3‐Point annulations, or phenalenannulations, transform a benzene ring directly into a substituted pyrene by “wrapping” two new cycles around the perimeter of the central ring at three consecutive carbon atoms. This efficient, modular, and general method for π‐extension opens access to non‐symmetric pyrenes and their expanded analogues. Potentially, this approach can convert any aromatic ring bearing a ‐CH₂Br or a ‐CHO group into a pyrene moiety. Depending upon the workup choices, the process can be directed towards either tin‐ or iodo‐substituted product formation, giving complementary choices for further various cross‐coupling reactions. The two‐directional bis‐double annulation adds two new polyaromatic extensions with a total of six new aromatic rings at a central core.