The gas-phase radical-radical reaction dynamics of O(3P) + C3H5 --> H(2S) + C3H4O was studied at an average collision energy of 6.4 kcal/mol in a crossed beam configuration. The ground-state atomic oxygen [O(3P)] and allyl radicals (C3H5) were generated by the photolysis of NO2 and the supersonic flash pyrolysis of allyl iodide, respectively. Nascent hydrogen atom products were probed by the vacuum-ultraviolet-laser induced fluorescence spectroscopy in the Lyman-alpha region centered at 121.6 nm. With the aid of the CBS-QB3 level of ab initio theory, it has been found that the barrierless addition of O(3P) to C3H5 forms the energy-rich addition complexes on the lowest doublet potential energy surface, which are predicted to undergo a subsequent direct decomposition step leading to the reaction products H + C3H4O. The major counterpart C3H4O of the probed hydrogen atom is calculated to be acrolein after taking into account the factors of barrier height, reaction enthalpy, and the number of intermediates involved along the reaction pathway. The nascent H-atom Doppler profile analysis shows that the average center-of-mass translational energy of the H + C3H4O products and the fraction of the total available energy released as the translational energy were determined to be 3.83 kcal/mol and 0.054, respectively. On the basis of comparison with statistical calculations, the reaction proceeds through the formation of short-lived addition complexes rather than statistical, long-lived intermediates, and the polyatomic acrolein product is significantly internally excited at the moment of the decomposition.

Carnosic acid (CA) is a diterpene compound exhibiting antioxidative, anticancer, anti-angiogenic, anti-inflammatory, anti-metabolic disorder, and hepatoprotective and neuroprotective activities. In this study, the effect of CA on various skin inflammatory responses and its inhibitory mechanism were examined. CA strongly suppressed the production of IL-6, IL-8, and MCP-1 from keratinocyte HaCaT cells stimulated with sodium lauryl sulfate (SLS) and retinoic acid (RA). In addition, CA blocked the release of nitric oxide (NO), tumor necrosis factor (TNF)-α, and prostaglandin E2 (PGE2) from RAW264.7 cells activated by the toll-like receptor (TLR)-2 ligands, Gram-positive bacterium-derived peptidoglycan (PGN) and pam3CSK, and the TLR4 ligand, Gram-negative bacterium-derived lipopolysaccharide (LPS). CA arrested the growth of dermatitis-inducing Gram-positive and Gram-negative microorganisms such Propionibacterium acnes, Pseudomonas aeruginosa, and Staphylococcus aureus. CA also blocked the nuclear translocation of nuclear factor (NF)-κB and its upstream signaling including Syk/Src, phosphoinositide 3-kinase (PI3K), Akt, inhibitor of κBα (IκBα) kinase (IKK), and IκBα for NF-κB activation. Kinase assays revealed that Syk could be direct enzymatic target of CA in its anti-inflammatory action. Therefore, our data strongly suggest the potential of CA as an anti-inflammatory drug against skin inflammatory responses with Src/NF-κB inhibitory properties.

The radical-radical oxidation reaction, O(3P)+C3H3 (propargyl)-->H(2S)+C3H2O (propynal), was investigated using vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed-beam configuration, together with ab initio and statistical calculations. The barrierless addition of O(3P) to C3H3 is calculated to form energy-rich addition complexes on the lowest doublet potential energy surface, which subsequently undergo direct decomposition steps leading to the major reaction products, H+C3H(2)O (propynal). According to the nascent H-atom Doppler-profile analysis, the average translational energy of the products and the fraction of the average transitional energy to the total available energy were determined to be 5.09+/-0.36 kcal/mol and 0.077, respectively. On the basis of a comparison with statistical prior calculations, the reaction mechanism and the significant internal excitation of the polyatomic propynal product can be rationalized in terms of the formation of highly activated, short-lived addition-complex intermediates and the adiabaticity of the excess available energy along the reaction coordinate.

The radical–radical reaction dynamics of ground-state atomic oxygen [O(3P)] with propargyl radicals (C3H3) has first been investigated by applying laser induced fluorescence spectroscopy in a crossed beam configuration, together with ab initio calculations. A new exothermic channel of O(3P)+C3H3→C3H2+OH was identified and the nascent distributions of OH reaction product in the ground vibrational state (X 2Π:υ″=0) showed substantial rotational excitations with an unusual bimodal feature composed of the low- and high-N″ components. No spin–orbit propensities were observed, whereas the averaged ratios of Π(A′)/Π(A″) were determined to be 0.60±0.28. With the aid of the CBS-QB3 level of ab initio theory it is predicted that on the lowest doublet potential energy surface the reaction proceeds through the addition complexes formed through the barrierless addition of O(3P) to C3H3, and that the counterpart of C3H2 of the probed OH product is cyclopropenylidene (1c-C3H2). On the basis of the comparison with statistical prior and rotational surprisal analyses, the ratio of population partitioning for the low- and high-N″ regimes is estimated to be about 1:2 and the reaction is described in terms of two competing addition-complex mechanisms: a major short-lived dynamic complex in the high-N″ regime and a minor long-lived statistical complex in the low-N″ regime.

The radical-radical reaction dynamics of ground-state atomic oxygen [O(3P)] with propargyl radicals (C3H3) has first been investigated in a crossed beam configuration. The radical reactants O(3P) and C3H3 were produced by the photodissociation of NO2 and the supersonic flash pyrolysis of precursor propargyl bromide, respectively. A new exothermic channel of O(3P) + C3H3 --> C3H2 + OH was identified and the nascent distributions of the product OH in the ground vibrational state (X 2Pi:nu" = 0) showed bimodal rotational excitations composed of the low- and high-N" components without spin-orbit propensities. The averaged ratios of Pi(A')/Pi(A") were determined to be 0.60 +/- 0.28. With the aid of ab initio theory it is predicted that on the lowest doublet potential energy surface, the reaction proceeds via the addition complexes formed through the barrierless addition of O(3P) to C3H3. The common direct abstraction pathway through a collinear geometry does not occur due to the high entrance barrier in our low collision energy regime. In addition, the major reaction channel is calculated to be the formation of propynal (CHCCHO) + H, and the counterpart C3H2 of the probed OH product in the title reaction is cyclopropenylidene (1c-C3H2) after considering the factors of barrier height, reaction enthalpy and structural features of the intermediates formed along the reaction coordinate. On the basis of the statistical prior and rotational surprisal analyses, the ratio of population partitioning for the low- and high-N" is found to be about 1:2, and the reaction is described in terms of two competing addition-complex mechanisms: a major short-lived dynamic complex and a minor long-lived statistical complex. The observed unusual reaction mechanism stands in sharp contrast with the reaction of O(3P) with allyl radical (C3H5), a second significant conjugated hydrocarbon radical, which shows totally dynamic processes [J. Chem. Phys. 117, 2017 (2002)], and should be understood based upon the characteristic electronic structures and reactivity of the intermediates on the potential energy surface.