Photoinduced Rearrangement of Dienones and Santonin Rerouted by Amines

The photoinduced rearrangement pathways of simple 2,5‐dienones and the natural product santonin were found to be effectively rerouted by amines, giving rise to unprecedented products. Either cis olefins or cyclobutenes were obtained from 4,4‐disubstituted 2,5‐dienone upon irradiation (365 nm) in the presence of various amines depending on the solvent. Previously undescribed [4.4.0] and [5.3.0] fused‐ring‐containing products were obtained when santonin was irradiated (365 nm) in the presence of methylamine. The amines present in these reactions were incorporated into the products by means of amide‐group formation.     

A Proof of Hozo's Conjecture on the Homology of a Class of Nilpotent Lie Algebras

LetPbe a rooted tree with rootrand vertex set {1, 2,…,n}. ConsiderPto be a poset by sayingu ≤ vifuis on the path fromrtov. LetZ[P] be the span of all matricesz_uvsuch thatu <_P v, wherez_uvis then × nmatrix with a 1 in theu, ventry and 0's elsewhere. Note thatZ[P] is a nilpotent Lie subalgebra of ?_n(). I. Hozo (Electron. J. Combin., to appear) studied the Laplacian of the Koszul complex for computing the Lie algebra homology ofZ[P]. He showed that the tree structure ofPforces significant simplifications in the Laplacian. He went on to conjecture that the eigenvalues of the Laplacian are indexed by certain labellings ofPby partitions. He gave a simple method for determining the eigenvalue indexed by a labelling. In this paper we prove Hozo's conjecture. As a consequence, we deduce that all eigenvalues of the Laplacian are integers.     

Cyclic homology and the Macdonald conjectures

Summary LetA+(k) denote the ring [t]/t ^k+1 and letG be a reductive complex Lie algebra with exponentsm ₁, ...,m n. This paper concerns the Lie algebra cohomology ofGA ₊(k) considered as a bigraded algebra (here one of the gradings is homological degree and the other, which we callweight, is inherited from the obvious grading ofGA ₊(k)). We conjecture that this Lie algebra cohomology is an exterior algebra withk+1 generators of homological degree 2m _s +1 fors=1,2, ...,n. Of thesek+1 generators of degree 2m _s +1, one has weight 0 and the others have weights (k+1)m _s +t fort=1,2, ...,k.It is shown that this conjecture about the Lie algebra cohomology of A ₊(k) implies the Macdonald root system conjectures. Next we consider the case thatG is a classical Lie algebra with root systemA _n ,B _n ,C _n , orD _n. It is shown that our conjecture holds in the limit onn asn approaches infinity which amounts to the computation of the cyclic and dihedral cohomologies ofA+(k). Lastly we discuss the relevance of this limiting case to the case of finiten in this situation.Partially supported by NSF grant number MCS-8401718 and a Bantrell Fellowship     

Replication in UV-lrradiated Caenorhabditis elegans Embryos

Abstract— Replication continues in wild-type (but not rad mutant) Caenorhabditis elegans embryos even after exposure to massive fluences of UV radiation. It is of interest to elucidate the mechanism(s) for this "damage-resistant" DNA synthesis. In this study, DNA from unirradiated and UV-irradiated wild-type embryos was examined using the electron microscope. Large fluences of UV radiation (180 J m⁻²) had little effect on either replication bubble size or distances between bubbles in wild-type embryos, indicating that the damage-resistant DNA synthesis was not grossly aberrant. Conversely, UV irradiation significantly decreased center-to-center distances between bubbles in excision-repair-deficient rad-3 embryos. This suggests that the decreased DNA synthesis observed after UV irradiation in rad-3 embryos is due largely to blockage of elongation of DNA synthesis.     

Preparation of β′-phenylsulfonyl α,β-unsaturated ketones and unsymmetric dialkenyl ketones from 2-alkenyl-2-methoxycyclopropyl phenyl sulfones

β′-Phenylsulfonyl α,β-unsaturated ketones, which can be easily converted to unsymmetric dialkenyl ketones, were prepared via ring opening reactions of 2-alkenyl-2-methoxycyclopropyl phenyl sulfones.     

Highly selective electrocatalytic conversion of CO2 to CO at -0.57 V (NHE) by carbon monoxide dehydrogenase from Moorella thermoacetica

We found that CODH is a fascinating enzyme for the electrochemical conversion of CO2 to CO. It could reduce CO2 to CO at -0.57 V vs NHE with approximately 100% current efficiency in 0.1 M phosphate buffer (pH 6.3). Nature's unique structure of C-cluster in CODH would be responsible for the low overpotential and the selective and fast conversion of CO2. The turnover number per C-cluster is 700 h-1, and the pH optimum is 6.3.