Mechanistic studies on the degradation of gasoline oxygenates by advanced oxidation technologies and the reaction of 4-methyl-1,2,4-triazoline-3,5-dione with tetracyclopropylethylene

Gasoline oxygenates (MTBE, methyl tert-butyl ether; DIPE, di-isopropyl ether; ETBE, ethyl tert-butyl ether; TAME, tert-amyl ether) are added to gasoline to boost octane and enhance combustion. The combination of large scale use, high water solubility and only minor biodegradability has now resulted in a significant gasoline oxygenate contamination occurring in surface, ground, and drinking water systems. Combination of hydroxyl radical formation and the pyrolytic environment generated by ultrasonic irradiation (665 kHz) leads to the rapid degradation of MTBE and other gasoline oxygenates in aqueous media. ^ The presence of oxygen promotes the degradation processes by rapid reaction with carbon centered radicals indicating radical processes involving O 2 are significant pathways. A number of the oxidation products were identified. The formation of products (alcohols, ketones, aldehydes, esters, peroxides, etc) could be rationalized by mechanisms which involve hydrogen abstraction by OH radical and/or pyrolysis to form carboncentered radicals which react with oxygen and follow standard oxidation chain processes. ^ The reactions of N-substituted R-triazolinediones (RTAD; R = CH 3 or phenyl) have attracted considerable interest because they exhibit a number of unusual mechanistic characteristics that are analogous to the reactions of singlet oxygen (1O2) and offer an easy way to provide C-N bond(s) formation. The reactions of triazolinedione with olefins have been widely studied and aziridinium imides are generally accepted to be the reactive intermediates. ^ We observed the rapid formation of an unusual intermediate upon mixing tetracyclopropylethylene with 4-methyl-1,2,4-triazoline-3,5-dione in CDCl 3. Detailed characterization by NMR (proton, 13C, 2-D NMRs) indicates the intermediate is 5,5,6,6-tetracyclopropyl-3-methyl-5,6-dihydro-oxazolo[3,2- b][1,2,4]-triazolium-2-olate. Such products are extremely rare and have not been studied. Upon warming the intermediate is converted to 2 + 2 diazetidine (major) and ene product (minor). ^ To further explore the kinetics and dynamics of the reaction activation energies were obtained using Arrhenius plots. Activation energies for the formation of the intermediate from reactants, and 2+2 adduct from the intermediate were determined as 7.48 kcal moll and 19.8 kcal mol−1 with their pre-exponential values of 2.24 × 105 dm 3 mol−1 sec−1 and 2.75 × 108 sec−1, respectively, meaning net slow reactions because of low pre-exponential values caused by steric hindrance. ^

The knowledge and promotion of exercise to older adults with type 2 diabetes by dietitian diabetes educators

The extent to which Registered Dietitians (RD) promote exercise as part of diabetes self-management education to older diabetic adults has not been established. This study explored the exercise-related knowledge, design, and content of educational programs among RDs who were Certified Diabetes Educators (CDEs) and non-CDEs. The Exercise Teaching Questionnaire was completed by 94 CDEs and 73 non-CDEs in Florida, California, and Texas. ^ CDEs had significantly (p < 0.001) higher mean Knowledge, Design, and Content scores (11.8 ± 1.1, 33.5 ± 9.4, 26.9 ± 4.8, respectively) than non-CDEs (11.1 ± 1.6, 29.2 ± 11.1, 22.4 ± 7.4, respectively). However, Knowledge means for both CDEs and non-CDEs were above the 85 percentile. Design and content scale responses showed that while dietitians provided basic information about safety and benefits related to exercise, they frequently reported “never” or only “sometimes” making exercise recommendations. ^ Although these results suggest that RDs are knowledgeable about exercise for older adults with Type 2 diabetes, greater importance should be made on training RDs to promote exercise, perhaps with an emphasis on a comprehensive team approach. ^