The kinetics of pyrolysis of barrelene[1]: A concerted process on the C8H8 energy surface

The static vessel pyrolysis of bicyclo[2.2.2]octa-2,5,7-triene (barrelene) has been studied between 483 and 523 K. The products were acetylene and benzene (in equal quantities) with no other detectable C₈H₈ isomer (down to less than 1% of total). The time dependence fitted first-order kinetics, and the data are consistent with a homogeneous unimolecular reaction close to, if not at, its high-pressure limit at 0.25 torr. The rate constant was fitted to the Arrhenius equation These Arrhenius parameters are shown to imply a concerted single-step process. Alternative mechanisms are discussed and a comparison is made with the retro-Diels—Alder reactions of other bicyclo[2.2.2]octa-olefin systems.     

Flavor changing neutral currents and multileptons in e+e- and vμN,vμN

New quarks and new flavor-changing neutral currents give multiple lepton plus hadron final states in e⁺e^-, $\text{v}{}_{\mathrm{\mu }}\text{N,}\text{v}{}_{\mathrm{\mu }}\text{N}$. We observe that (i) e⁺e^- is a favored place to search for their effects through inclusive ratios σ(e⁺e^-+x:σ (μ⁺μ^- +x): σ(e±μ±+x) and same sign leptons e±e±+x, μ±μ±+x,e±μ±+x. Above a new flavor threshold four charged lrpton final states may become important. (ii) Trilepton final states in $\text{v}{}_{\mathrm{\mu }}\text{N,}\text{v}{}_{\mathrm{\mu }}\text{N}$ are not sensitive to the presence of flavor-changing neutral currents. Much more sensitive are the processes $\text{v}{}_{\mathrm{\mu }}\text{N}$ are ⁺e^-+βand (for charm changing neutral currents) $\text{v}{}_{\mathrm{\mu }}\text{N→e}{}^{\mathrm{+}}\text{β}$.     

Multijet structure in quantum chromodynamics

Field theories naturally give rise to multiple jets of hadrons in short-distance processes, such as e⁺ e^? annihilation. In particular, a low-energy jet of hadrons distributed in some cone of opening angle δ would be naively expected to evolve at high energies into multiple jets within the angle δ. We explore to what extent this will happen in quantum chromodynamics.     

Comparison of Tm : ZBLAN and Tm : silica fiber lasers; Spectroscopy and tunable pulsed laser operation around 1.9 μm

Tm-doped ZBLAN and Tm-doped silica glass are compared spectroscopically and the fiber lasing of the Tm ³F₄³H₆ transition around 1.9 m in ZBLAN and silica fibers is compared. The spectroscopy of these materials indicates that Tm:ZBLAN possesses advantages over Tm:silica glass due to the lower phonon energies. The phonon energy in these glass hosts influences both the pump manifold lifetime, the Tm ³H₄, and the upper laser manifold lifetime, the Tm ³F₄. The maximum phonon energy in Tm:ZBLAN, 500 cm^-1 , compared to Tm:silica, 1100 cm^-1, leads to better Tm–Tm self quenching towards populating the Tm ³F₄, as well as better Tm ³F₄³H₆ quantum efficiency. A spectroscopic analysis using the Judd–Ofelt theory and measured lifetimes are used to assess the merits of Tm:ZBLAN over Tm:silica as a fiber laser material. Diode-pumped fiber lasing experiments show that Tm:ZBLAN possesses advantages over Tm:silica that are believed to be due to a lower phonon energy. Data is presented for launched pump energy versus laser energy, fiber length versus slope efficiency, and output mirror reflectivity versus slope efficiency. Tm:ZBLAN is demonstrated to possess higher slope efficiencies and lower thresholds, than Tm:silicate. A grating tuned Tm:ZBLAN laser is also demonstrated for tunable operation between 1.893 m and 1.955 m. PACS 42.55.Wd; 42.55.Xi; 42.62.Fi; 78.55.Qr     

Vancomycin assembly: nature's way

Antibiotics are precious resources in the fight to combat bacterial infections caused by pathogenic organisms. Vancomycin is one of the antibiotics of last resort in the treatment of life-threatening infections by gram-positive bacteria. The rules by which nature assembles the glycopeptide (vancomycin) and lipoglycopeptide (teicoplanin) antibiotics are becoming elucidated and verified: first amino acids are synthesized, then joined together and cross-linked. This knowledge opens up approaches for reprogramming strategies at the level of altered monomers, swapped assembly lines, and different post-assembly tailoring enzymes.     

Epoxide-opening and group-transfer reactions mediated by monomeric zirconium imido complexes

N-tert-Butylimidozirconocene (Cp2Zr=Nt-Bu) and its analogue (ebthi)Zr=NAr (ebthi = ethylenebis(tetrahydroindenyl), Ar = 2,6-dimethylphenyl) undergo overall cycloaddition reactions at ambient temperature with epoxides that lack accessible beta-hydrogens. The process results in addition of the Zr=N bond to an epoxide C-O bond, leading to azazirconacyclopentanes. The regio- and stereochemistry of the products implicate a stepwise mechanism, with the intermediacy of zwitterions having substantial carbocation character at the substituted carbon of the ring-opened epoxide-derived fragment. The azametallacycles undergo facile cleavage to beta-amino alcohols upon addition of mild acid.     

Synthesis of proposed oxidation-cyclization-methylation intermediates of the coumarin antibiotic biosynthetic pathway

[structure: see text] A chemoenzymatic synthesis was described to prepare proposed oxidation-cyclization-methylation intermediates of the coumarin antibiotic biosynthetic pathway. The successful synthesis of these fragile molecules relies heavily on mild enzymatic deprotection and efficient enzymatic kinetic resolution to minimize epimerization, decomposition, multiple orthogonal protections, and retro aldol reactions often encountered in their chemical synthesis.     

Highly enantioselective catalytic phenylation of ketones with a constrained geometry titanium catalyst

[reaction: see text] The catalytic asymmetric addition of phenyl groups from diphenylzinc to ketones is reported. The catalyst, generated from a dihydroxy bis(sulfonamide) ligand and titanium tetraisopropoxide, gives good to excellent enantioselectivities with a range of substrates.