Crossed molecular beams experiments on dicarbon molecules, C2(X1sigmag+/a3piu), with unsaturated hydrocarbons acetylene (C2H2(X1sigmag+), ethylene (C2H4(X1Ag)), methylacetylene (CH3CCH(X1A1)), and allene (H2CCCH2 (X1A1)) were carried out at 18 collision energies between 10.6 and 50.3 kJ mol(-1) utilizing a universal crossed beams machine to untangle the reaction dynamics forming hydrogen deficient hydrocarbon radicals in circumstellar envelopes of carbons stars and in cold molecular clouds. We find that all reactions proceed without the entrance barrier through indirect (complex forming) scattering dynamics. Each bimolecular collision is initiated by an addition of the dicarbon molecule to the pi bond of the unsaturated hydrocarbon molecule yielding initially acyclic (triplet) and three- or four-membered cyclic collision complexes (triplet and singlet surface). On the singlet surface, the cyclic structures isomerize to form eventually diacetylene (HCCCCH; C2/C2H2), butatriene (H2CCCCH2; C2/C2H4), methyldiacetylene (CH3CCCCH; C2/CH3CCH), and pentatetraene (H2CCCCCH2; C2/H2CCCH2) intermediates. The latter were found to decompose via atomic hydrogen loss yielding the buta-1,3-diynyl [C4H(X2sigma+) HCCCC], 1-butene-3-yne-2-yl [i-C4H3(X2A') H2CCCCH], penta-2,4-diynyl-1 [C5H3(X2B1) HCCCCCH2], and penta-1,4-diynyl-3 radical [C5H3(X2B1) HCCCHCCH] under single collision conditions. The underlying characteristics of these dicarbon versus atomic hydrogen replacement pathways (indirect scattering dynamics; no entrance barrier; isomerization barriers below the energy of the separated reactants; exoergic reactions) suggest the enormous potential of the dicarbon plus unsaturated hydrocarbon reaction class to form highly hydrogen-deficient carbonaceous molecules in cold molecular clouds and in circumstellar envelopes of carbon stars. The studies therefore present an important advancement in establishing a comprehensive database of reaction intermediates and products involved in bimolecular collisions of dicarbon molecules with unsaturated hydrocarbons which can be utilized in refined astrochemical models and also in future searches of hitherto unidentified interstellar molecules. Implications of these experiments to understand related combustion processes are also addressed.
The landscape of genetic alterations in lung adenocarcinoma derived from Asian patients is largely uncharacterized. Here we present an integrated genomic and transcriptomic analysis of 335 primary lung adenocarcinomas and 35 corresponding lymph node metastases from Chinese patients. Altogether 13 significantly mutated genes are identified, including the most commonly mutated gene TP53 and novel mutation targets such as RHPN2, GLI3 and MRC2. TP53 mutations are furthermore significantly enriched in tumours from patients harbouring metastases. Genes regulating cytoskeleton remodelling processes are also frequently altered, especially in metastatic samples, of which the high expression level of IQGAP3 is identified as a marker for poor prognosis. Our study represents the first large-scale sequencing effort on lung adenocarcinoma in Asian patients and provides a comprehensive mutational landscape for both primary and metastatic tumours. This may thus form a basis for personalized medical care and shed light on the molecular pathogenesis of metastatic lung adenocarcinoma.
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