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 effects of word prediction and text-to-speech technologies on the narrative writing skills of students with specific learning disabilities

This study investigated the effects of word prediction and text-to-speech on the narrative composition writing skills of 6, fifth-grade Hispanic boys with specific learning disabilities (SLD). A multiple baseline design across subjects was used to explore the efficacy of word prediction and text-to-speech alone and in combination on four dependent variables: writing fluency (words per minute), syntax (T-units), spelling accuracy, and overall organization (holistic scoring rubric). Data were collected and analyzed during baseline, assistive technology interventions, and at 2-, 4-, and 6-week maintenance probes. ^ Participants were equally divided into Cohorts A and B, and two separate but related studies were conducted. Throughout all phases of the study, participants wrote narrative compositions for 15-minute sessions. During baseline, participants used word processing only. During the assistive technology intervention condition, Cohort A participants used word prediction followed by word prediction with text-to-speech. Concurrently, Cohort B participants used text-to-speech followed by text-to-speech with word prediction. ^ The results of this study indicate that word prediction alone or in combination with text-to-speech has a positive effect on the narrative writing compositions of students with SLD. Overall, participants in Cohorts A and B wrote more words, more T-units, and spelled more words correctly. A sign test indicated that these perceived effects were not likely due to chance. Additionally, the quality of writing improved as measured by holistic rubric scores. When participants in Cohort B used text-to-speech alone, with the exception of spelling accuracy, inconsequential results were observed on all dependent variables. ^ This study demonstrated that word prediction alone or in combination assists students with SLD to write longer, improved-quality, narrative compositions. These results suggest that word prediction or word prediction with text-to-speech be considered as a writing support to facilitate the production of a first draft of a narrative composition. However, caution should be given to the use of text-to-speech alone as its effectiveness has not been established. Recommendations for future research include investigating the use of these technologies in other phases of the writing process, with other student populations, and with other writing styles. Further, these technologies should be investigated while integrated into classroom composition instruction. ^