Bonding situations in tricoordinated beryllium phenyl complexes

The bonding situation in the tricoordinated beryllium phenyl complexes [BePh₃]⁻, [(pyridine)BePh₂] and [(trimethylsilyl-N-heterocyclic imine)BePh₂] is investigated experimentally and computationally. Comparison of the NMR spectroscopic properties of these complexes and of their structural parameters, which were determined by single crystal X-ray diffraction experiments, indicates the presence of π-interactions. Topology analysis of the electron density reveals elliptical electron density distributions at the bond critical points and the double bond character of the beryllium-element bonds is verified by energy decomposition analysis with the combination of natural orbital for chemical valence. The present beryllium-element bonds are highly polarized and the ligands around the central atom have a strong influence on the degree of π-delocalization. These results are compared to related triarylboranes.     

Predissociation of chlorobenzene, beyond the pseudo-diatomic model

Dissociation of chlorobenzene via the lowest singlet excited state has been investigated by means of pump–probe femtosecond spectroscopy and spin–orbit corrected ab initio quantum chemistry. We have found that the so far accepted model with a ¹ππ^* → ³π/nσ^* reaction mechanism has to be amended. We suggest that the mechanism goes via a transition from ¹ππ^* to a πσ^* state that is to 90% a singlet. Further, three nuclear degrees of freedom required to describe the dissociation have been defined.     

Biological Pretreatment of Chicken Feather and Biogas Production from Total Broth

Chicken feathers are available in large quantities around the world causing environmental challenges. The feathers are composed of keratin that is a recalcitrant protein and is hard to degrade. In this work, chicken feathers were aerobically pretreated for 2–8 days at total solid concentrations of 5, 10, and 20 % by Bacillus sp. C₄, a bacterium that produces both α- and β-keratinases. Then, the liquid fraction (feather hydrolysate) as well as the total broth (liquid and solid fraction of pretreated feathers) was used as substrates for biogas production using anaerobic sludge or bacteria granules as inoculum. The biological pretreatment of feather waste was productive; about 75 % of feather was converted to soluble crude protein after 8 days of degradation at initial feather concentration of 5 %. Bacteria granules performed better during anaerobic digestion of untreated feathers, resulting in approximately two times more methane yield (i.e., 199 mlCH₄/gVS compared to 105 mlCH₄/gVS when sludge was used). Pretreatment improved methane yield by 292 and 105 % when sludge and granules were used on the hydrolysate. Bacteria granules worked effectively on the total broth, yielded 445 mlCH₄/gVS methane, which is 124 % more than that obtained with the same type of inoculum from untreated feather.     

Mixing of the Glauber dynamics for the ferromagnetic Potts model

We present several results on the mixing time of the Glauber dynamics for sampling from the Gibbs distribution in the ferromagnetic Potts model. At a fixed temperature and interaction strength, we study the interplay between the maximum degree (Δ) of the underlying graph and the number of colours or spins (q) in determining whether the dynamics mixes rapidly or not. We find a lower bound L on the number of colours such that Glauber dynamics is rapidly mixing if at least L colours are used. We give a closely‐matching upper bound U on the number of colours such that with probability that tends to 1, the Glauber dynamics mixes slowly on random Δ‐regular graphs when at most U colours are used. We show that our bounds can be improved if we restrict attention to certain types of graphs of maximum degree Δ, e.g. toroidal grids for Δ = 4. © 2014 Wiley Periodicals, Inc. Random Struct. Alg., 48, 21–52, 2016     

Merging Iron Catalysis and Biocatalysis—Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker‐type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities.     

Realizing the analytic surgery group of Higson and Roe geometrically part III: higher invariants

We construct an isomorphism between the geometric model and Higson-Roe’s analytic surgery group, reconciling the constructions in the previous papers in the series on “Realizing the analytic surgery group of Higson and Roe geometrically” with their analytic counterparts. Following work of Lott and Wahl, we construct a Chern character on the geometric model for the surgery group; it is a “delocalized Chern character”, from which Lott’s higher delocalized \(\rho \)-invariants can be retrieved. Following work of Piazza and Schick, we construct a geometric map from Stolz’ positive scalar curvature sequence to the geometric model of Higson-Roe’s analytic surgery exact sequence.     

Realizing the analytic surgery group of Higson and Roe geometrically part II: relative $$\eta $$ η -invariants

Mathematische Annalen - We apply the geometric analog of the analytic surgery group of Higson and Roe to the relative $$\eta $$ -invariant. In particular, by solving a Baum–Douglas type index...     

Efficient metal-catalyzed direct benzylation and allylic alkylation of 2,4-pentanediones

[reaction: see text] A highly effective metal-catalyzed benzylation and allylic alkylation of 2,4-pentanediones has been developed. This new bismuth-catalyzed direct carbon-carbon bond forming reaction provides the corresponding monoalkylated dicarbonyl compounds in high yields after short reaction times using the lowest amounts of catalyst (1 mol %) and the free alcohol. In addition, a new route to substituted indenes is presented.