Atmospheric Degradation of CH═C(CH)C(O)O[CH]CH by OH Radicals: Reactivity, POCP, and Carbonyl Formation.

Relative rate studies of the gas-phase reaction of amyl methacrylate, CH═C(CH)C(O)O[CH]CH, with OH radicals were performed at (298 ± 2) K and 1000 mbar. The experiments were conducted in an atmospheric Pyrex chamber coupled to Fourier transform infrared spectroscopy (FTIR). The rate coefficient obtained from the average of several experiments was = (8.

Kinetics of the reaction of OH radical with ethylfluoroacetate, ethyl 4,4,4-trifluorobutyrate, and butylfluoroacetate.

Kinetics of the gas-phase reactions of •OH radicals with a series of fluoroesters were studied for the first time at 298 ± 3 K and atmospheric pressure. Relative rate coefficients were determined by in situ FTIR spectroscopy in nitrogen and GC-FID in air to monitor the decay of reactants and references. The following coefficient values (in 10 cm/(molecule•sec)) were obtained for ethyl fluoroacetate (EFA), ethyl 4,4,4-trifluorobutyrate (ETB), and butyl fluoroacetate (BFA), respectively: k (EFA + OH) = 1.

Atmospheric chemistry of trifluorodicarbonyls initiated by Cl atoms: Reactivity trends, mechanism, and acid formation yields.

Rate coefficients of the gas-phase reactions of Cl atoms with a series of fluorinated diketones (FDKs): CFC(O)CHC(O)CH (TFP), CFC(O)CHC(O)CHCH (TFH) and CFC(O)CHC(O)CH(CH) (TFMH), have been measured at (298 ± 2) K and under atmospheric pressure. The experiments were performed using the relative-rate method with a GC-FID detection system. From different determinations and references used, the following rate coefficients were obtained (in cm/(molecule·sec)): k(TFP + Cl) = (1.

Transient proliferation by reversible YAP and mitogen-control of the cyclin D1/p27 ratio.

Hippo-YAP signaling orchestrates epithelial tissue repair and is therefore an attractive target in regenerative medicine. Yet it is unresolved how YAP integrates with mitogen signaling and contact inhibition to control the underlying transient proliferative response. Here we show that reduced contact inhibition, increased mitogen signaling, and YAP-TEAD activation converge on increasing the nuclear cyclin D1/p27 protein ratio during G1 phase, towards a threshold ratio that dictates whether individual cells enter or exit the cell cycle.

Unexpected high yield of acrolein underlies the importance of the hydrogen-abstraction mechanism in photooxidation of allyl methyl sulfide (AMS).

This work explores theoretically the gas phase oxidation of allyl methyl sulfide (AMS, HCCHCHSCH) initiated by OH radicals, focusing on the H-abstraction pathway at the M06-2X-D3/aug-cc-pVTZ and MN15/aug-cc-pVTZ levels of theory (m06Tz and mn15Tz). The formation of a prereactive complex (PRC) is involved in H-abstraction processes with two potential directions of approach for the OH radical, denoted as "α" and "β". The PRCs, demonstrate increased reactivity, primarily due to the interaction between the sulfur atoms and the hydroxyl hydrogen.