New limit on CPT violation

A search for antiproton decay has been made at the Fermilab Antiproton Accumulator. Limits are placed on fifteen antiproton decay modes. The results are used to place limits on the characteristic mass scale m(X) that could be associated with CPT violation accompanied by baryon number violation.     

Preparation of trifluoromethylpyridine libraries

S-Alkylation followed by heterocyclization of trifluoromethyl-3-cyano-2(1H)-pyridinethiones was used for preparation of libraries of S-alkyl trifluoromethylpyridines and thieno[2,3-b]pyridines. The S-alkylation (in water--DMF mixtures) was successful for all 18 alkylating agents employed (yields typically > 50%). S-Alkyl derivatives were further converted to corresponding thieno[2,3-b]pyridines via heterocyclization in base conditions (yields > 65%). Structures of new compounds were elucidated by a combination of IR and 1H NMR spectroscopy and elemental analysis and were confirmed by means of single-crystal X-ray diffraction analysis.     

Evidence for intra-ionic anharmonicity in the Raman spectra of cubic ionic crystals

The importance of intra-ionic anharmonicity for Raman spectra in cubic ionic crystals is discussed. A calculation of the second order Raman spectra of of MgO assuming such an anharmonicity is presented and a satisfactory agreement with experiment is obtained.     

Tradeoff directions in multiobjective optimization problems

Multiobjective optimization problems (MOP) typically have conflicting objectives wherein a gain in one objective is at the expense of another. Tradeoff directions, which measure the change in some objectives relative to changes in others, provide important information as to the best direction of improvement from the current solution. In this paper we present a general definition of tradeoffs as a cone of directions and provide a general method of calculating tradeoffs at every Pareto optimal point of a convex MOP. This extends current definitions of tradeoffs which assume certain conditions on the feasible set and the objective functions. Two comprehensive numerical examples are provided to illustrate the tradeoff directions and the methods used to calculate them.     

The unidentified object problem in a shallow ocean with a fluid-like sediment layer overlaying a rigid seabed 1

We use a modified Intersecting Canonical Domain Method to determine the shape of a submerged acoustically-soft object in a finite depth ocean with a fluid-like sediment overlying a rigid seabed     

Direct visualisation of peptide hormones in cultured pancreatic islet alpha- and beta-cells by intact-cell mass spectrometry

The application of intact-cell mass spectrometry (ICM) by matrix-assisted laser desorption/ionisation time-of-flight (MALDI-TOF) mass spectrometry to achieve direct protein-profiling of bacterial species is now well established. However, this methodology has not to our knowledge been applied to the analysis of mammalian cells in routine culture. Here, we describe a novel application of ICM by which we have identified proteins in intact cells from two lines representative of pancreatic islet alpha- and beta-cells. Adherent alphaTC1 clone 9 and betaTC6 F7 cells were harvested into phosphate-buffered saline (PBS) using enzyme-free dissociation buffer before 1 microL of cell suspension was spotted onto MALDI plates. Cells were overlaid with sinapinic acid then washed with pure water before application of a final coat of sinapinic acid. Data in the 2000-20,000 m/z range were acquired in linear mode on a Voyager DE-Pro mass spectrometer. The proteins which ionised were composed in large part of peptide hormones (e.g. insulin and glucagon) known to be packaged into the secretory granules of the beta- and alpha-cells respectively. However, in addition to visualising the peptides expected to be associated with these cells, a mass consistent with oxyntomodulin was identified in the cultured alpha-cells, a finding not previously reported to our knowledge. In summary, this paper describes, for the first time, a rapid and direct method useful for identifying secretory products in intact endocrine cells.     

Pattern formation in draining thin film suspensions

We demonstrate the emergence of complexity from remarkably simple and ubiquitous systems: draining thin-film suspensions exhibiting a striking transition between two classes of self-organizing patterns. Vertical channels form when attractive forces lead to transient gelation, while horizontal bands result from granular mixtures. We propose an explanation whereby the generic physical mechanisms require only the existence of viscous and excluded-volume couplings among the particles, solvent, and substrate. System-specific, small inhomogeneities trigger large-scale pattern formation, through collective dynamics, where jamming plays a crucial role. Our results shed light on emergent complexity in bio- and geophysical processes and have implications for coatings and food industries.     

Conformation-specific spectroscopy and populations of diastereomers of a model monolignol derivative: chiral effects in a triol chain

Single-conformation spectroscopy of two diastereomers of 1-(4-hydroxy-3-methoxyphenyl)propane-1,2,3-triol (HMPPT) has been carried out under isolated, jet-cooled conditions. HMPPT is a close analog of coniferyl alcohol, one of the three monomers that make up lignin, the aromatic biopolymer that gives structural integrity to plants. In HMPPT, the double bond of coniferyl alcohol has been oxidized to produce an alkyl triol chain with chiral centers at C(α) and C(β), thereby incorporating key aspects of the β-O-4 linkage between monomer subunits that occurs commonly in lignin. Both (R,S)- and (R,R)-HMPPT diastereomers have been synthesized in pure form for study. Resonant two-photon ionization (R2PI), UV hole-burning (UVHB)/IR-UV hole-burning (IR-UV HB), and resonant ion-dip infrared (RIDIR) spectroscopy have been carried out, providing single-conformation UV spectra in the S(0)-S(1) region (35200-35800 cm(-1)) and IR spectra in the hydride stretch region. Five conformers of (R,S)- and four conformers of (R,R)-HMPPT are observed and characterized, leading to assignments for all nine conformers. Spectroscopic signatures for α-β-γ, γ-β-α, and α-γ-β-π chains and two cyclic forms [(αβγ) and (αγβ)] of the glycerol side chain are determined. Infrared ion-gain (IRIG) spectroscopy is used to determine fractional abundances for the (R,S) diastereomer and constrain the populations present in (R,R). The two diastereomers have very different conformational preferences. More than 95% of the population of (R,R) configures the glycerol side chain in a γ-β-α triol chain, while in (R,S)-HMPPT, 51% of the population is in α-β-γ chains that point in the opposite direction, with an additional 21% of the population in H-bonded cycles. The experimental results are compared with calculations to provide a consistent explanation of the diastereomer-specific effects observed.     

New volatile strontium and barium imidazolate complexes for the deposition of group 2 metal oxides

We report the synthesis, characterization, and experimental density function theory-derived properties of new volatile strontium and barium imidazolate complexes, which under atomic layer deposition conditions using ozone as a reagent can deposit crystalline strontium oxide at 375 °C.     

M?F Interactions and Heterobimetallics: Furthering the Understanding of Heterobimetallic Stabilization

Heterobimetallic complexes containing alkali, alkaline‐earth, and divalent europium metals utilizing the perfluoro‐tert‐butoxide (PFTB) ligand following the general formula, [AM(PFTB)₃(co‐ligand)_x] (A=Na, K; M=Mg, Sr, Ba, Eu; co‐ligand=THF, toluene), have been isolated. These compounds sublime at low temperatures with low residual weight indicating their potential as metal–organic chemical‐vapor deposition (MOCVD) precursors. The complexes have unique molecular architectures that are strongly influenced by M? F interactions, as was verified in the solid state by using X‐ray crystallography. The significance of these interactions were further reinforced by bond‐valence sums analysis and ¹⁹F VT‐NMR spectroscopy, in which rotational energies of 18.75 and 19.08 kcal mol^?1 were measured.