Finite-Time Blow-up of Solutions of an Aggregation Equation in <Emphasis Type="Italic">R</Emphasis><Superscript><Emphasis Type="Italic">n</Emphasis></Superscript>

We consider the aggregation equation in R ⁿ , n ≥ 2, where K is a rotationally symmetric, nonnegative decaying kernel with a Lipschitz point at the origin, e.g. K(x) = e ^−|x|. We prove finite-time blow-up of solutions from specific smooth initial data, for which the problem is known to have short time existence of smooth solutions.     

Parallelism error characterization with mechanical and interferometric methods

Two methods for measuring the parallelism error of gauge blocks are discussed. The first method makes use of contact probes, sampling the gauge thickness at fixed locations; the parallelism error is given by the difference between maximum and minimum thickness over the sampled area. The second method is based on interferometry, producing the height maps of the opposing surfaces with respect to one another; the parallelism error is obtained after processing of the interferometric data. The two methods have been implemented in different laboratories, and compared by measuring five different gauge blocks. The results are reported, showing that the first method is more straightforward and simple, but requires prior calibration and provides information only on a limited number of sample points. The second method is more demanding in terms of equipment and measuring procedure, but in principle it is an absolute method, and provides information over a large number of data points.     

Diastereoselectivity in the rhodium-catalyzed hydroformylation of (+)(R)-1-phenylethyl vinyl ether

The degree of diastereoselectivity in the rhodium-catalyzed hydroformylation of (+)(R)-1-phenylethyl vinyl ether is much higher than that in the hydroformylation of the related olefin, 4-phenyl-1-pentene.     

A bioorthogonal quadricyclane ligation

New additions to the bioorthogonal chemistry compendium can advance biological research by enabling multiplexed analysis of biomolecules in complex systems. Here we introduce the quadricyclane ligation, a new bioorthogonal reaction between the highly strained hydrocarbon quadricyclane and Ni bis(dithiolene) reagents. This reaction has a second-order rate constant of 0.25 M(-1) s(-1), on par with fast bioorthogonal reactions of azides, and proceeds readily in aqueous environments. Ni bis(dithiolene) probes selectively labeled quadricyclane-modified bovine serum albumin, even in the presence of cell lysate. We have demonstrated that the quadricyclane ligation is compatible with, and orthogonal to, strain-promoted azide-alkyne cycloaddition and oxime ligation chemistries by performing all three reactions in one pot on differentially functionalized protein substrates. The quadricyclane ligation joins a small but growing list of tools for the selective covalent modification of biomolecules.     

Protein glycoengineering enabled by the versatile synthesis of aminooxy glycans and the genetically encoded aldehyde tag

Homogeneously glycosylated proteins are important targets for fundamental research and for biopharmaceutical development. The use of unnatural protein-glycan linkages bearing structural similarity to their native counterparts can accelerate the synthesis of glycoengineered proteins. Here we report an approach toward generating homogeneously glycosylated proteins that involves chemical attachment of aminooxy glycans to recombinantly produced proteins via oxime linkages. We employed the recently introduced aldehyde tag method to obtain a recombinant protein with the aldehyde-bearing formylglycine residue at a specific site. Complex aminooxy glycans were synthesized using a new route that features N-pentenoyl hydroxamates as key intermediates that can be readily elaborated chemically and enzymatically. We demonstrated the method by constructing site-specifically glycosylated variants of the human growth hormone.     

Reverse undercompressive shock structures in driven thin film flow

We show experimental and computational evidence of a new structure: an undercompressive and reverse undercompressive shock for draining films driven by a surface tension gradient against gravity. The reverse undercompressive shock is unstable to transverse perturbations while the leading undercompressive shock is stable. Depending on the pinch-off film thickness, as controlled by the meniscus, either a trailing rarefaction wave or a compressive shock separates from the reverse undercompressive shock.     

Small molecule inhibitors of mucin-type O-linked glycosylation from a uridine-based library

The polypeptide N-acetyl-alpha-galactosaminyltransferases (ppGalNAcTs, also abbreviated ppGaNTases) initiate mucin-type O-linked glycosylation and therefore play pivotal roles in cell-cell communication and protection of tissues. In order to develop new tools for studying mucin-type O-linked glycosylation, we screened a 1338 member uridine-based library to identify small molecule inhibitors of ppGalNAcTs. Using a high-throughput enzyme-linked lectin assay (ELLA), two inhibitors of murine ppGalNAcT-1 (K(I) approximately 8 microM) were identified that also inhibit several other members of the family. The compounds did not inhibit other mammalian glycosyltransferases or nucleotide sugar utilizing enzymes, suggesting selectivity for the ppGalNAcTs. Treatment of cells with the compounds abrogated mucin-type O-linked glycosylation but not N-linked glycosylation and also induced apoptosis. These uridine analogs represent the first generation of chemical tools to study the functions of mucin-type O-linked glycosylation.     

Q2 evolution of the neutron spin structure moments using a 3He target

We have measured the spin structure functions g(1) and g(2) of 3He in a double-spin experiment by inclusively scattering polarized electrons at energies ranging from 0.862 to 5.058 GeV off a polarized 3He target at a 15.5 degrees scattering angle. Excitation energies covered the resonance and the onset of the deep inelastic regions. We have determined for the first time the Q2 evolution of Gamma(1)(Q2)= integral (1)(0)g(1)(x,Q2)dx, Gamma(2)(Q2)= integral (1)(0)g(2)(x,Q2)dx, and d(2)(Q2)= integral (1)(0)x(2)[2g(1)(x,Q2)+3g(2)(x,Q2)]dx for the neutron in the range 0.1< or =Q2< or =0.9 GeV2 with good precision. Gamma(1)(Q2) displays a smooth variation from high to low Q2. The Burkhardt-Cottingham sum rule holds within uncertainties and d(2) is nonzero over the measured range.