Surface chemistries of lithium: Detailed characterization of the reactions with O2 and H2O using XPS, EELS, AND microgravimetry

The surface chemical reactions of O₂ and H₂O on clean lithium have been studied by a combination of XPS, EELS and microgravimetry. Reactions with O₂ produce a monolayer of oxide which does not passivate the surface and which allows for the growth of several monolayers of additional oxide, probably as a result of the mixing of zero-valent metal into the oxide layer. The reaction of H₂O with the clean lithium surface results in the complete dissociation of the molecule and loss of hydrogen to form one monolayer of the oxide. This is followed by the formation of multilayers of hydroxide/oxide mixtures which are shown to be unstable over periods of minutes, converting back to the oxide form predominantly.     

A Constraint Programming Approach to Extract the Maximum Number of Non-Overlapping Test Forms

This paper introduces a novel approach for extracting the maximum number of non-overlapping test forms from a large collection of overlapping test sections assembled from a given item bank. The approach involves solving maximum set packing problems (MSPs). A branch-and-bound MSP algorithm is developed along with techniques adapted from constraint programming to estimate lower and upper bounds on the optimal MSP solution. The algorithm is general and can be applied in other applications including combinatorial auctions. The results of computer simulations and experiments with an operational item bank are presented. An erratum to this article is available at .     

Thermodynamics of Dipolar Chain Systems

The thermodynamics of a quantum system of layers containing perpendicularly oriented dipolar molecules is studied within an oscillator approximation for both bosonic and fermionic species. The system is assumed to be built from chains with one molecule in each layer. We consider the effects of the intralayer repulsion and quantum statistical requirements in systems with more than one chain. Specifically, we consider the case of two chains and solve the problem analytically within the harmonic Hamiltonian approach which is accurate for large dipole moments. The case of three chains is calculated numerically. Our findings indicate that thermodynamic observables, such as the heat capacity, can be used to probe the signatures of the intralayer interaction between chains. This should be relevant for near future experiments on polar molecules with strong dipole moments.     

New measurements of G using the measurement standards laboratory torsion balance

This Letter presents the results of a series of measurements of the Newtonian gravitational constant G using the compensated torsion balance developed at the Measurement Standards Laboratory. Since our last published result using the torsion balance in the compensated mode of operation [Meas. Sci. Technol. 10, 439 (1999)]], several improvements have been made to reduce the uncertainty in the final result. The new measurements have used both stainless steel and copper large masses. The values of G for the two sets of masses are in good agreement. After combining all of the measurements we get a value of G=6.673 87(0.000 27) x 10(-11) m3 kg(-1) s(-2). This new value is 5 parts in 10(5) smaller than our previous published values.     

Rapid high-resolution four-dimensional NMR spectroscopy using the filter diagonalization method and its advantages for detailed structural elucidation of oligosaccharides

Four-dimensional nuclear magnetic resonance spectroscopy with high resolution of signals in the indirect dimensions is reported as an implementation of the filter diagonalization method (FDM). Using an oligosaccharide derivatized with 13C-labeled acetyl isotags, a four-dimensional constant-time pulse sequence was tailored for conjoint use with the FDM. Results demonstrate that high resolution in all dimensions can be achieved using a relatively short experimental time period (19 h), even though the spectrum is highly congested in the direct and all three indirect dimensions. The combined use of isotags, constant-time pulse sequences, and FDM permits rapid isolation of sugar ring proton spin systems in multiple dimensions and enables all endocyclic J-couplings to be simply measured, the key goal to assigning sugar stereochemistry and anomeric configuration. A general method for rapid, unambiguous elucidation of spin systems in oligosaccharides has been a long-sought goal of carbohydrate NMR, and isotags combined with the FDM now enable this to be easily performed. Additional general advantages of the FDM program for generating high-resolution 2D slices in any dimension from a 4D spectrum are emphasized.     

Asymmetric Synthesis of Calyculin C. 2. Synthesis of the C(26)-C(37) Fragment and Model Wittig Couplings

We report our synthesis of the C(26)-C(37) fragment of serine/threonine protein phosphatase PP1 and PP2A inhibitor calyculin C (1). Outlined in this paper are synthetic approaches to the two components based on disconnection at the C(33)-N(3) amide bond. We report the successful synthesis of the C(33)-C(37) aza-sugar derived from D-lyxose which was coupled onto a C(26)-C(32) aminooxazole originating from L-pyroglutamic acid. Elaboration of the resulting amide to a fully deprotected C(26)-C(37) fragment of calyculin C completed our synthesis. This provided an appropriate phosphonium salt for use in a Wittig olefination for joining both halves of the natural product.     

Total synthesis of (+)-zaragozic acid C

A total synthesis of (+)-zaragozic acid C is described. Key features of the synthesis are the use of a double Sharpless asymmetric dihydroxylation reaction of diene 6 to control stereochemistry at four contiguous stereocenters from C3 to C6; the introduction of the C1-side chain by reaction between the anion derived from the dithiane monosulfoxide 27 and the core aldehyde 12; a high yielding, acid-mediated simultaneous acetonide deprotection-dithiane removal-ketalization procedure leading exclusively to the 2, 8-dioxabicyclo[3.2.1]octane core 34; and a novel triple oxidation procedure allowing installation of the tricarboxylic acid.     

Optimization of the Synthesis of 2,6–Dinitro-4-trifluoromethylphenyl Ether Substituted Cyclodextrin Bonded Chiral Stationary Phases

The comparisons of five different chiral stationary phases (CSPs) based on 2,6-dinitro-4-trifluoromethylphenyl (DNP-TFM) ether substituted β-cyclodextrin are presented. The five CSPs differ from each other in the linkage/spacer chemistry, or on the position of the substituents on β-cyclodextrin, or in the sequence of the synthetic procedure. The results show that there are two optimum combinations: (1) DNP-TFM randomly substituted on the β-cyclodextrin as the chiral selector along with a carbamate linkage chain bonding it to the silica support; and (2) β-cyclodextrin derivatized by DNP-TFM substituents only on the C-2 and C-3 positions of the cyclodextrin with an ether linkage chain anchoring it to the silica gel. These two combinations show complementary separations for some enantiomers. The spacer chain effect is much more pronounced for the CSP based on the β-cyclodextrin derivatives with DNP-TFM substituents only on C-2 and C-3 positions than its randomly substituted counterpart. The sequence of derivatizing the cyclodextrin and attaching it to silica gel also affects its selectivity and efficiency. The β-cyclodextrin should be derivatized before it is linked to the silica gel.