FTIR spectroscopic evidence for new isomers of 3-aminopyrazine-2-carboxylic acid formed in argon matrices upon UV irradiations.

The UV-induced photochemistry and molecular structure of 3-aminopyrazine-2-carboxylic acid were studied in argon matrices by Fourier-transform infrared spectroscopy and B3LYP/6-311++G(2d,2p) calculations. Out of seventeen possible isomers of this molecule located on the singlet potential energy surface the most stable one, APA1 comprising intramolecular O-H···N and N-H···O hydrogen bonds, was detected experimentally in the matrix after deposition. Two new conformers APA2 and APA3 were generated upon irradiation with λ = 280 nm by trans/cis-COOH isomerization and at λ = 360 nm by COOH group rotamerization, respectively, whereas an amino-imino tautomerization leading to IPA1 and IPA2 structures occurred at λ = 305 nm. The reverse reactions were also observed upon irradiation of the matrices at 265, 230 and 400 nm. Simultaneously with the photoisomerizations, a cleavage of the pyrazine ring along with CO2 elimination was observed leading to the formation of carbodiimide and cyanamide derivatives.

Phototransformations of 2-(1,2,4-Triazol-3-yl)benzoic Acid in Low Temperature Matrices.

Phototransformations of 2-(1,2,4-triazol-3-yl)benzoic acid induced by tunable UV laser were studied in low temperature matrices by FTIR spectroscopy. Out of 36 possible isomers of this molecule the most stable one, comprising the intramolecular N-H···O hydrogen bond, was detected experimentally in argon and xenon matrices after deposition. Upon irradiation with λ = 325 nm, two new conformers of the precursor were formed. The corresponding reverse photorotamerizations were also detected at 250 nm partly reproducing the initial molecules. In addition to the conformational changes, an interesting photoisomerization took place in the studied matrices leading to a proton transfer from N atom of the triazole ring to the carbonyl oxygen of the carboxylic group. As a result of this reaction, a new product with two OH groups was identified for the first time. The experimental studies were supported by DFT calculations in both ground and excited electronic states.

Towards breed formation by island model divergence in Korean cattle.

BACKGROUND: The main cattle breed in Korea is the brown Hanwoo, which has been under artificial selection within a national breeding program for several decades. Varieties of the Hanwoo known as Jeju Black and Chikso were not included in the breeding program and remained isolated from the effects of recent artificial selection advancements. We analysed the Jeju Black and Chikso populations in regards to their genetic variability, state of inbreeding, as well as level of differentiation from the mainland Hanwoo population. RESULTS: Jeju Black and Chikso were found to have small estimated effective population sizes (N e ) of only 11 and 7, respectively. Despite a small N e , higher than expected heterozygosity levels were observed (0.303 and 0.306), however, lower allelic richness was found for the two island populations (1.76 and 1.77) compared to the mainland population (1.81). The increase in heterozygosity could be due to environmental disease challenges that promoted maintenance of higher genetic variability; however, no direct proof exists. Increased heterozygosity due to a first generation crossing of genetically different populations is not recorded. The differentiation between the Korean populations had F ST values between 0.014 and 0.036 which is not as high as the differentiation within European beef or dairy cattle breeds (0.047-0.111). This suggests that the three populations have not separated into independent breeds. CONCLUSION: Results agree with an island model of speciation where the brown Hanwoo represents the ancestral breed, whilst the Jeju Black and Chikso diverge from this common ancestor, following different evolutionary trajectories. Nevertheless, differences are minor and whether Jeju Black and Chikso cattle will develop into discrete breeds or reintegrate with the main population has to be seen in the future and will largely depend on human management decisions. This offers a rare opportunity to accompany the development of new breeds but also poses challenges on how to preserve these incipient breeds and ensure their long term viability.

Preparation and characterization of copper-graphite composites by electrical explosion of wire in liquid.

Copper-graphite nanocomposites containing 5 vol.% graphite were prepared by a powder metallurgy route using an electrical wire explosion (EEW) in liquid method and spark plasma sintering (SPS) process. Graphite rods with a 0.3 mm diameter and copper wire with a 0.2 mm diameter were used as raw materials for EEWin liquid. To compare, a pure copper and copper-graphite mixture was also prepared. The fabricated graphite was in the form of a nanosheet, onto which copper particles were coated. Sintering was performed at 900 degrees C at a heating rate of 30 degrees C/min for 10 min and under a pressure of 70 MPa. The density of the sintered composite samples was measured by the Archimedes method. A wear test was performed by a ball-on-disc tribometer under dry conditions at room temperature in air. The presence of graphite effectively reduced the wear of composites. The copper-graphite nanocomposites prepared by EEW had lower wear rates than pure copper material and simple mixed copper-graphite.

Two new ergostane-type steroidal lactones from Withania coagulans.

Two new withanolides (steroidal lactones) named coagulin F [27-hydroxy-14,20-epoxy-1-oxo-(22R)-witha-3,5,24-trienolide] (1) and coagulin G [17beta,27-dihydroxy-14,20-epoxy-1-oxo-(22R)-witha-2,5, 24-trienolide] (2) were isolated from the whole plant of Withania coagulans, and their structures were deduced by spectral analysis.