Incompressible quantum liquids and new conservation laws

In this Letter, we investigate a class of Hamiltonians which, in addition to the usual center-of-mass momentum conservation, also have center-of-mass position conservation. We find that, regardless of the particle statistics, the energy spectrum is at least q-fold degenerate when the filling factor is p/q, where and are coprime integers. Interestingly, the simplest Hamiltonian respecting this type of symmetry encapsulates two prominent examples of novel states of matter, namely, the fractional quantum Hall liquid and the quantum dimer liquid. We discuss the relevance of this class of Hamiltonian to the search for featureless Mott insulators.     

The hypertree poset and the ℓ<Superscript>2</Superscript>-Betti numbers of the motion group of the trivial link

We give explicit formulae for the Euler characteristic and ²-cohomology of the group of motions of the trivial link, or isomorphically the group of free group automorphisms that send each standard generator to a conjugate of itself. The method is primarily combinatorial and ultimately relies on a computation of the Möbius function for the poset of labelled hypertrees.Partially supported by NSF grant no. DMS-0101506Partially supported by an AMS Centennial Research Fellowship     

Selective selenocatalytic allylic chlorination

Ene-chlorination of olefins by N-chlorosuccinimide is catalyzed by phenylselenenyl chloride. This reaction demonstrates the catalytic conversion of C-H bonds into more reactive C-Cl bonds. [reaction: see text]     

Berkeleydione and berkeleytrione, new bioactive metabolites from an acid mine organism

[structure: see text] Two novel hybrid polyketide-terpenoid metabolites were isolated from a Penicillium sp. growing in the Berkeley Pit Lake of Butte, Montana. Their structures were deduced by spectroscopic analysis and confirmed by single-crystal X-ray analysis on berkeleydione (1). Both compounds inhibited matrix metalloproteinase-3 and caspase-1, and berkeleydione showed activity toward non-small-cell lung cancer in NCI's human cell line antitumor screen.     

Electronic control of chiral quaternary center creation in the intramolecular asymmetric heck reaction

The Boehringer-Ingelheim phosphinoimidazoline (BIPI) ligands were applied to the formation of chiral quaternary centers in the asymmetric Heck reaction. Several different substrates were examined in detail, using more than 70 members of this new ligand class. Hammett relationships were determined through systematic variation of the ligand electronics. All substrates showed essentially the same Hammett behavior, where enantioselectivity increased as the ligands were made more electron-deficient. Ligand optimization has led to catalysts which give the highest enantioselectivities reported to date for these difficult systems.     

The mechanism of NO formation from the decomposition of dialkylamino diazeniumdiolates: density functional theory and CBS-QB3 predictions

The mechanism of decomposition of dialkylamino diazeniumdiolate salts, R(2)N[NONO](-)M(+), to form nitric oxide, NO, was explored using theoretical methods. B3LYP/6-311+G(d) density functional theory calculations gave the optimized geometries, and energetics were further evaluated with the high accuracy CBS-QB3 method, when feasible. Relative pK(a) values were estimated using the PCM model for aqueous solvation. The terminal oxygen is the most basic site, followed closely by the internal oxygen. Protonation of these sites does not lead to decomposition. However, protonation of the weakly basic amino nitrogen leads to very rapid decomposition and NO generation.     

Selenium-catalyzed halolactonization: nucleophilic activation of electrophilic halogenating reagents

Diphenyl diselenide catalyzes the halolactonization of unsaturated acids with N-halosuccinimides under mild conditions. The diselenide not only accelerates the reactions, but in some cases affords regiocontrol in favor of gamma-lactone products. Experiments show that the regioselectivity in favor of gamma-lactones is a result of kinetic rather than thermodynamic control.     

Structural and functional analogue of the active site of polysulfide reductase from Wolinella succinogenes

Synthesis of [PPh4]2[Mo(SPh)2(S2C2(CN)2)2] (2) from [PPh4]2[MoO(S2C2(CN)2)2] (1) has been achieved to mimic the postulated [Mo(S)6] core of polysulfide reductase with two thiolates and two bis(ene-dithiolate) ligands. Compound 2 reacts with polysulfide to yield H2S, modeling the function of polysulfide reductase. The facile conversion of 2 back to 1 in moist solvent suggests that the interconversion of the [MoIV = O] and [MoIV - X] (X = O-Ser, S-Cys, Se-Cys) moieties might occur in the DMSO reductase class of enzymes under appropriate hydrophobic/hydrophilic conditions.     

Three-dimensional tracking of fluorescent nanoparticles with subnanometer precision by use of off-focus imaging

We show that the position of a fluorescent nanoparticle can be measured in three dimensions with subnanometer precision and 100-ms temporal resolution by use of standard epifluorescence video imaging in off-focus mode. The particle can be tracked without feedback in a volume of at least 40 microm x 60 microm x 3 microm. With the technique presented, the structure-mobility relationship of 216-nm latex particle in a porous polymer network was studied in three dimensions.