Non-covalent stabilization of a beta-hairpin peptide into liposomes

An oligopeptide modified on both the N- and C-termini with hydrophobic moieties was prepared on a solid phase and anchored into a liposome, stabilizing the fold of the peptide into a beta-hairpin, which would otherwise be a random coil.     

Alternative solvents for elevated-temperature solid-phase parallel synthesis. Application to thionation of amides

A new class of higher-boiling solvents was investigated for elevated-temperature solid-phase parallel synthesis. Extremely low vapor pressures at high temperature and a broader range of solvent effect tuning make this new class of solvents an ideal choice for high-temperature parallel solid-phase synthesis. Benzyl benzoate is identified as a superior high-boiling solvent for parallel solid-phase Lawesson's thionation reactions.     

Evaluation of the two-dimensional reversed-phase-reversed-phase separations of low-molecular mass polystyrenes

The resolving power of four reversed-phase-reversed-phase two-dimensional (2D) chromatographic systems was evaluated using information theory (IT) and a geometric approach to factor analysis. The first separation dimension employed a C18 column, while the second separation dimension employed a carbon clad zirconia column. Mobile phases in each dimension were either methanol or acetonitrile. The sample matrix that was employed in this study contained a mixture of 58 components, comprised of stereoisomers and structural isomers of a systematic variation in molecular weight. Each of the components were oligostyrenes, with between two and five configurational repeating units having either n-butyl, sec-butyl or tert-butyl end groups. In the two-dimensional systems employed in this study, between 46 and 49 of the 58 components could be separated, depending on the mobile phase combinations--with apparent resolution that could not possibly be achieved in a single one-dimensional separation. The results from this study indicate that in order to fully evaluate the resolving power of a 2D system multiple methods of analysis that evaluate the separation potential are most appropriate. This becomes increasingly important when the sample contains components that are very closely related and the retention of solutes displays a high degree of solute crowding.     

A multi-component reaction (MCR) approach to the synthesis of highly diverse polymers with polypeptide-like features

A new strategy for the combinatorial synthesis of new materials has been developed through the consecutive application of an Ugi 4CC reaction and a ring-opening metathesis polymerization (ROMP) reaction. Norbornenyl aldehydes and carboxylic acids could be used in the Ugi MCR to give highly diverse monomers that were converted to the corresponding polymers by exposure to the second-generation Grubbs' catalyst. These polymers have structural features reminiscent of polypeptides and the process could be extended to the preparation of chiral materials.     

Stability of low levels of perchlorate in drinking water and natural water samples

Perchlorate ion (ClO₄⁻) is an environmental contaminant of growing concern due to its potential human health effects, impact on aquatic and land animals, and widespread occurrence throughout the United States. The determination of perchlorate cannot normally be carried out in the field. As such, water samples for perchlorate analysis are often shipped to a central laboratory, where they may be stored for a significant period before analysis. The stability of perchlorate ion in various types of commonly encountered water samples has not been generally examined—the effect of such storage is thus not known. In the present study, the long-term stability of perchlorate ion in deionized water, tap water, ground water, and surface water was examined. Sample sets containing approximately 1000, 100, 1.0, and 0.5 μg l⁻¹ perchlorate ion in deionized water and also in local tap water were formulated. These samples were analyzed by ion chromatography for perchlorate ion concentration against freshly prepared standards every 24 h for the first 7 days, biweekly for the next 4 weeks, and periodically after that for a total of 400 or 610 days for the two lowest concentrations and a total of 428 or 638 days for the high concentrations. Ground and surface water samples containing perchlorate were collected, held and analyzed for perchlorate concentration periodically over at least 360 days. All samples except for the surface water samples were found to be stable for the duration of the study, allowing for holding times of at least 300 days for ground water samples and at least 90 days for surface water samples.     

The effect of polyacrylic acid and reaction conditions on nanocluster formation of precipitated calcium carbonate on microcellulose

The precipitation of micro- and nanoparticles of calcium carbonate onto lignocellulosic microfibers was investigated at different microfiber concentrations with and without polyacrylic acid (PAA), i.e. a polymer commonly used to form polymer-induced liquid precursors of CaCO₃. Concentrations of PAA, Ca(OH)₂, CO₂ and microfiber were varied in order to study the impact of reaction conditions on PCC formation in a batch reactor operated at ambient temperature. High resolution scanning electron micrographs of the samples show that both microfiber concentration and PAA dosage affected the nucleation and crystal growth of PCC filler on cellulosic fiber. Interestingly, at higher microfiber concentrations, larger amount of nano-sized spherical crystals were formed on the microfibers. A higher dosage of PAA, on the other hand, resulted in less nucleation on the microfiber, suggesting a preferential bulk nucleation mechanism. A higher concentration of PAA during the precipitation also led to the formation and stabilization of amorphous CaCO₃, which was supported by SEM images and XRD analysis (lack of characteristic crystal structure).     

C 1, α Interior Regularity for Nonlinear Nonlocal Elliptic Equations with Rough Kernels

We prove a C ^{1, α} interior regularity theorem for fully nonlinear uniformly elliptic integro-differential equations without assuming any regularity of the kernel. We then give some applications to linear theory and higher regularity of a special class of nonlinear operators.     

On 1-factors of point determining graphs

A graph G is said to be point determining if and only if distinct points of G have distinct neighborhoods. For such a graph G, the nucleus is defined to be the set G″ consisting of all points ν of G for which G-ν is a point determining graph.In [4], Summer exhibited several families of graphs H such that if G⁰ = H, for some point determining graph G, then G has a 1-factor. In this paper, we extend this class of graphs.     

Halo-enediynes: probing the electronic and stereoelectronic contributions to the Bergman cycloaromatization

A series of halogen-substituted cyclic enediynes were prepared with use of carbenoid coupling strategy. DFT analysis, initially used to identify synthesis candidates, was also employed to rationalize the propensity for cycloaromatization of the compounds. In all cases studied the halogen atom had a strongly retardative effect on the thermal Bergman cycloaromatization reaction. The isolation of the first C-9 monochloroenediyne is noteworthy, and may find application in prodrug design.