Synthesis and structure determination of kahalalide F (1,2).

Kahalalide F, the only member of the family of peptides called kahalalides, isolated from the sacoglossan mollusc Elysia rufescens and the green alga Bryopsis sp., with important bioactivity, is in clinical trials for treatment of prostate cancer. An efficient solid-phase synthetic approach is reported. Kahalalide F presents several synthetic difficulties: (i) an ester bond between two beta-branched and sterically hindered amino acids; (ii) a didehydroamino acid; and (iii) a rather hydrophobic sequence with two fragments containing several beta-branched amino acids in a row, one of them terminated with a saturated aliphatic acid. The cornerstones of our strategy were (i) a quasiorthogonal protecting system with allyl, tert-butyl, fluorenyl, and trityl-based groups, (ii) azabenzotriazole coupling reagents, (iii) formation of the didehydroamino acid residue on the solid phase, and (iv) cyclization and final purification in solution. HPLC, high-field NMR, and biological activity studies showed that the correct stereochemistry of the natural product is that proposed by Rinehart et al. whereas the stereochemistry proposed by Scheuer et al. is that of a biologically less active diastereoisomer.     

Eventualités de la division arithmétique

Annali di Matematica Pura ed Applicata (1867-1897) -     

Two Unusual Trimers of Diketene

Formation of two unknown, tricyclic trimers of diketene, 3 and 4 , was observed in diketene solutions containing (CH₃)₃SiCl/NaI or TsOH.     

Über Triphenylmethane,deren Benzolkerne miteinander verbunden sind

Ohne Zusammenfassung     

Spin-state splittings, highest-occupied-molecular-orbital and lowest-unoccupied-molecular-orbital energies, and chemical hardness

It is known that the exact density functional must give ground-state energies that are piecewise linear as a function of electron number. In this work we prove that this is also true for the lowest-energy excited states of different spin or spatial symmetry. This has three important consequences for chemical applications: the ground state of a molecule must correspond to the state with the maximum highest-occupied-molecular-orbital energy, minimum lowest-unoccupied-molecular-orbital energy, and maximum chemical hardness. The beryllium, carbon, and vanadium atoms, as well as the CH(2) and C(3)H(3) molecules are considered as illustrative examples. Our result also directly and rigorously connects the ionization potential and electron affinity to the stability of spin states.     

Observable T7 lepton flavor symmetry at the Large Hadron Collider

More often than not, models of flavor symmetry rely on the use of nonrenormalizable operators (in the guise of flavons) to accomplish the phenomenologically successful tribimaximal mixing of neutrinos. We show instead how a simple renormalizable two-parameter neutrino mass model of tribimaximal mixing can be constructed with the non-Abelian discrete symmetry T(7) and the gauging of B-L. This is also achieved without the addition of auxiliary symmetries and particles present in almost all other proposals. Most importantly, it is verifiable at the Large Hadron Collider.