Measurements and automated mechanism generation modeling of OH production in photolytically initiated oxidation of the neopentyl radical

Production of OH in the reaction of the neopentyl radical with O2 has been measured by a laser photolysis/cw absorption method for various pressures and oxygen concentrations at 673, 700, and 725 K. The MIT Reaction Mechanism Generator (RMG) was used to automatically generate a model for this system, and the predicted OH concentration profiles are compared to present and literature experimental results. Several reactions significantly affect the OH profile. The experimental data provide useful constraints on the rate coefficient for the formally direct chemical activation reaction of neopentyl radical with O2 to form OH (CH3)3CCH2 + O2 --> OH + 3,3-dimethyloxetane (Rxn 1) At 673 K and 60 Torr, log k(1) (cm(3) molecule(-1) s(-1)) = -13.7 +/- 0.5. Absolute absorbance measurements on OH and I indicate that the branching ratio for R + O2 to OH is about 0.03 under these conditions. The data suggest that the ab initio neopentyl + O2 potential energy surface of Sun and Bozzelli is accurate to within 2 kcal mol(-1).     

New Freeze-Dried Andean Blueberry Juice Powders for Potential Application as Functional Food Ingredients: Effect of Maltodextrin on Bioactive and Morphological Features

Andean blueberry (Vaccinium meridionale Swartz) fruits are an underutilized source of anthocyanins and other valuable bioactive phytochemicals. The purpose of this work was to obtain Andean blueberry juice powders via freeze-drying processing and evaluate the effect of maltodextrin as a drying aid on their physicochemical, technological, microstructural, and bioactive characteristics. Andean blueberry juices were mixed with variable proportions of maltodextrin (20–50%); freeze-dried; and characterized in terms of their tristimulus color, Fourier transform infrared spectra (FTIR), moisture content, water activity, morphology, water solubility, flow properties, total polyphenols and anthocyanins content, and DPPH^•-scavenging capacity. The powders obtained presented suitable characteristics in terms of their water activity (<0.5), solubility (>90%), and bioactive compound recovery (>70% for total phenolics, and >60% for total monomeric anthocyanins), with antioxidant activities up to 4 mg equivalent of gallic acid/g of dry matter. Although an increased content of maltodextrin resulted in lower concentrations of phytochemicals, as expected, it also favored an increased % recovery (over 90% of total phenolics at the highest maltodextrin proportion) and improved their flow properties. Freeze-dried juice powders are a potential alternative for the stabilization and value addition of this fruit as a new source of functionality for processed foods.     

Measurements and modeling of DO2 formation in the reactions of C2D5 and C3D7 radicals with O2

Time-resolved production of HO2 and DO2 from the reactions of nondeuterated and deuterated ethyl and propyl radicals with O2 are measured as a function of temperature and pressure in the "transition region" between 623 and 748 K using the technique of laser photolysis/long path frequency modulation spectroscopy. Experimental measurements, using both pulsed-photolytic Cl-atom-initiated oxidation of ethane and propane and direct photolysis of ethyl, n-propyl, and isopropyl iodides, are compared to kinetic models based on the results of time-dependent master equation calculations with ab initio characterization of stationary points. The formation of DO2 and HO2 from the subsequent reaction of the alkyl radicals with O2 is followed by infrared frequency modulation spectroscopy. The concentration of I atoms is simultaneously monitored by direct absorption of a second laser probe on the spin-orbit transition. The kinetic models accurately describe the time scale and amplitude of the DO2 and HO2 formation resulting from C2D5 + O2, n-C3D7 + O2, i-C3D7 + O2, and i-C3H7 + O2. Overall, a very good level of agreement is found between theory and experiments over a wide range of temperatures, pressures, and O2 concentrations. Good agreement is also found between previous literature studies and the theory presented in this work except in the case of the high-temperature rate coefficients for the reaction of i-C3H7 + O2 to form propene. A reinvestigation of the high-temperature kinetics of the i-C3H7 + O2 reaction appears warranted. The results from the present work suggest that the theory for formation of HO2 from the reactions of ethyl and both isomeric forms of propyl radicals with O2 are very well established at this time. It is hoped that these reactions can now form the groundwork for the study and interpretation of larger and more complex R + O2 systems.     

Counting the Clicks in Fluorescent Polymer Networks

We introduce a fluorescence‐based methodology enabling the quantification of ligation points in photochemically prepared polymer networks. Well‐defined α,ω‐tetrazole‐capped polymer strands prepared via RAFT polymerization are crosslinked under UV irradiation by a trimaleimide via nitrile imine mediated tetrazole–ene cycloaddition. Thus, for each linkage point a fluorescent pyrazoline ring is formed, resulting in fluorescent networks, which are degradable by aminolysis of the trithiocarbonate functionalities, leading to soluble fragments. The fluorescence emission of the soluble network fragments correlates directly with the number of pyrazoline moieties originally present in the network, thus providing a direct measure of the number of ligation points constituting the network. The herein introduced strategy based on a fluorescence readout is a powerful yet simple approach to quantify network formation processes applicable to a wide class of polymers accessible via RAFT.     

Measurements and modeling of HO2 formation in the reactions of n-C3H7 and i-C3H7 radicals with O2

The formation of HO(2) in the reactions of C(2)H(5), n-C(3)H(7), and i-C(3)H(7) radicals with O(2) is investigated using the technique of laser photolysis/long-path frequency-modulation spectroscopy. The alkyl radicals are formed by 266 nm photolysis of alkyl iodides. The formation of HO(2) from the subsequent reaction of the alkyl radicals with O(2) is followed by infrared frequency-modulation spectroscopy. The concentration of I atoms is simultaneously monitored by direct absorption of a second laser probe on the spin-orbit transition. The measured profiles are compared to a kinetic model taken from time-resolved master-equation results based on previously published ab initio characterizations of the relevant stationary points on the potential-energy surface. The ab initio energies are adjusted to produce agreement with the present experimental data and with available literature studies. The isomer specificity of the present results enables refinement of the model for i-C(3)H(7) + O(2) and improved agreement with experimental measurements of HO(2) production in propane oxidation.     

Stoichiometry analysis of titanium oxide coating by LIBS

In this work, laser induced breakdown spectroscopy (LIBS) is used to determine the composition of titanium oxide film produced by anodized of Ti6Al4V alloy. We have used Ti lines in the spectral region between 470–520 nm to determine temperature of the plasma generated on anodized surface of Ti6Al4V alloy for temperature determination by Boltzmann plot method. In order to measure the content of oxygen and titanium ratio on the surface the alloy, we have used the oxygen lines 777.194, 777.417 and 777.539 nm, and titanium lines 780.597 and 782.491 nm observed in an ambient of argon. Finally, we report the possibilities for the determination of the coating chemical composition using LIBS.