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The kinetics of the gas-phase reactions of selected monoterpenes and cyclo-alkenes with ozone and the NO3 radical
The relative rate method has been used to measure the room-temperature rate constants for the gasphase reactions of ozone and NO3 with selected monoterpenes and cyclo-alkenes with structural similarities to monoterpenes. Measurements were carried out at 298 ! 2 K and 760 ! 10 Torr. The following rate constants (in units of 10"18 cm3 molecule"1 s"1) were obtained for the reaction with ozone: methyl cyclohexene (132 ! 17), terpinolene (1290 ! 360), ethylidene cyclohexane (223 ! 57), norbornene (860 ! 240), t-butyl isopropylidene cyclohexane (1500 ! 460), cyclopentene (543 ! 94), cyclohexene (81 ! 18), cyclooctene (451 ! 66), dicyclopentadiene (1460 ! 170) and a-pinene (107 ! 13). For the reaction with NO3 the rate constants obtained (in units of 10"12 cm3 molecule"1 s"1) were: methyl cyclohexene (7.92 ! 0.95), terpinolene (47.9 ! 4.0), ethylidene cyclohexane (4.30 ! 0.24), norbornene (0.266 ! 0.029), cyclohexene (0.540 ! 0.017), cyclooctene (0.513 ! 0.029), dicyclopentadiene (1.20 ! 0.10) and a-pinene (5.17 ! 0.62). Errors are quoted as the root mean square of the statistical error (95% con!dence) and the quoted error in the rate constant for the reference compound. Combining these results with previous studies, new recommendations for the rate constants are presented. Molecular orbital energies were calculated for each alkene and the kinetic data are discussed in terms of the deviation from the structureeactivity relationship obtained from the rate constants for a series of simple alkenes. Lifetimes with respect to key initiators of atmospheric oxidation have been calculated suggesting that the studied reactions play dominant roles in the night-time removal of these compounds from the atmosphere
Comparing internal fixation constructs for scapular spine insufficiency fractures following reverse shoulder arthroplasty
© 2020 Journal of Shoulder and Elbow Surgery Board of Trustees Introduction: There is limited research on the surgical management techniques for scapular spine fractures after reverse shoulder arthroplasty (RTSA). As such, the purpose of this in vitro biomechanical study was to compare 4 fixation constructs to stabilize scapular spine insufficiency fractures. Methods: Twelve paired fresh-frozen cadaveric scapulae (N = 24) were randomized into 4 fixation groups: subcutaneous border plating (± hook) and supraspinatus fossa plating (± hook). A Levy type II fracture was simulated. Each specimen was cyclically loaded incrementally up to 700 N in 50 N steps or until failure. Between 50 and 200 N construct stiffness was measured, and stability failure was defined as displacement greater than 2.5 mm. Results: Seventy-nine percent (19 of 24) of the specimens failed before the maximum load of 700 N. The average survival force with subcutaneous border plating was 480 ± 80 N compared with 380 ± 30 N for supraspinatus fossa plating (P =.3). Fixation construct failure was significantly more likely with fossa plating over subcutaneous plating (P =.012). The presence of the lateral plate hook was beneficial in preventing failure of the lateral acromion (P =.016). Conclusion: When appropriately surgically indicated, a dorsally applied plate to the subcutaneous border of the scapular spine with a lateral inferior supporting hook may be advantageous for internal fixation of type II scapular spine insufficiency fractures after RTSA