Asymmetric Reductive Carbocyclization Using Engineered Ene Reductases

Ene reductases from the Old Yellow Enzyme (OYE) family reduce the C=C double bond in α,β‐unsaturated compounds bearing an electron‐withdrawing group, for example, a carbonyl group. This asymmetric reduction has been exploited for biocatalysis. Going beyond its canonical function, we show that members of this enzyme family can also catalyze the formation of C?C bonds. α,β‐Unsaturated aldehydes and ketones containing an additional electrophilic group undergo reductive cyclization. Mechanistically, the two‐electron‐reduced enzyme cofactor FMN delivers a hydride to generate an enolate intermediate, which reacts with the internal electrophile. Single‐site replacement of a crucial Tyr residue with a non‐protic Phe or Trp favored the cyclization over the natural reduction reaction. The new transformation enabled the enantioselective synthesis of chiral cyclopropanes in up to >99 % ee.     

A new critical point in the non-linear conductivity due to variable range hopping in Si

A critical point in the non-linear conductivity has been observed in epitaxial silicon in the variable range hopping regime, due to a negative differential resistance with a dc bias currentI _dc. This gives thermal breakdown via the electron-phonon coupling and circuit-limited oscillations with a frequencyf∝I _dc, below a critical temperatureT _c. This critical behaviour is intrinsic, and forR(T)=R ₀ exp(T ₀ /T)^1/2 we show thatT _c=0.00512T ₀.     

Group actions on C*-algebras, 3-cocycles and quantum field theory

We study group extensions , where acts on a C^*-algebraA. Given a twisted covariant representation ,V of the pairA, we construct 3-cocycles on with values in the centre of the group generated byV(). These 3-cocycles are obstructions to the existence of an extension of byV() which acts onA compatibly with . The main theorems of the paper introduce a subsidiary invariant which classifies actions of onV() and in terms of which a necessary and sufficient condition for the the cohomology class of the 3-cocycle to be non-trivial may be formulated. Examples are provided which show how non-trivial 3-cocycles may be realised. The framework we choose to exhibit these essentially mathematical results is influenced by anomalous gauge field theories. We show how to interpret our results in that setting in two ways, one motivated by an algebraic approach to constrained dynamics and the other by the descent equation approach to constructing cocycles on gauge groups. In order to make comparisons with the usual approach to cohomology in gauge theory we conclude with a Lie algebra version of the invariant and the 3-cocycle.