High-performance liquid chromatographic separation of detritylated oligonucleotides on highly cross-linked poly-(styrene-divinylbenzene) particles.

Detritylated oligonucleotides were separated by reversed-phase high-performance liquid chromatography on highly cross-linked polystyrene-based particles having a mean particle diameter of 2.3 microns. The addition of poly(vinyl alcohol) during polymerization, which resulted in the presence of hydroxyl groups on the surface of the poly(styrene-divinylbenzene) beads, was necessary to obtain baseline resolution of phosphorylated oligodeoxyadenylic acids with a chain length of up to 30 bases. The impact of temperature was investigated and optimum resolution was achieved at 40 degrees C. At pH 7.0, the retention times of oligonucleotides were found to depend on the ratio of bases and to increase in the order of C less than G less than A less than T. Under the same conditions, it was possible to separate phosphorylated from dephosphorylated oligonucleotides, the former being eluted earlier. Recoveries ranged from 92 to 100%.     

Near-infrared reflection spectroscopy and partial least squares regression for determining the total carbon coverage of silica packings for liquid chromatography

Near-infrared reflection spectroscopy (NIRS) was used in combination with principal component analysis (PCA) and partial least squares (PLS) regression to determine the silica packing properties, whether endcapped (EC) or non-endcapped, and the amount of surface total carbon coverage (%). A preparation technique for the reproducible analysis of bulk materials is covered as well as spectral data pretreatments to enhance prediction accuracy of the PLS models. Especially derivatives and scatter correction methods turned out to be well suited. A standard error of prediction (SEP) of 0.57% C for the determination of the total carbon load of octadecylated (C₁₈) silica was found. In case of the C₁₈-EC silica a SEP of 0.51% carbon gives rise to a robust and accurate model. The presented method allows the simultaneous determination of several parameters, e.g. particle and pore size or surface modifications, from a single spectrum and is amenable to implementation for in-line or on-line analysis in the silica producing industry.     

Intrinsic route to melt fracture in polymer extrusion: a weakly nonlinear subcritical instability of viscoelastic poiseuille flow

As is well known, the extrusion rate of polymers from a cylindrical tube or slit (a "die") is in practice limited by the appearance of "melt fracture" instabilities which give rise to unwanted distortions or even fracture of the extrudate. We present the results of a weakly nonlinear analysis which gives evidence for an intrinsic generic route to melt fracture via a weakly nonlinear subcritical instability of viscoelastic Poiseuille flow. This instability and the onset of associated melt fracture phenomena appear at a well-defined ratio of the elastic stresses to viscous stresses of the polymer solution.     

Newest results from the Mainz neutrino-mass experiment

The Mainz neutrino-mass experiment investigates the endpoint region of the tritium β-decay spectrum with a MAC-E spectrometer to determine the mass of the electron antineutrino. By the recent upgrade, the former problem of dewetting T₂ films has been solved, and the signal-to-background ratio was improved by a factor of 10. The latest measurement leads to $m_\nu ^2 = - 3.7 \pm 5.3(stat.) \pm 2.1(syst.){{eV^2 } \mathord{\left/ {\vphantom {{eV^2 } {c^4 }}} \right. \kern-0em} {c^4 }}$ , from which an upper limit of $m_\nu < 2.8{{eV^2 } \mathord{\left/ {\vphantom {{eV^2 } {c^2 }}} \right. \kern-0em} {c^2 }}(95\% C.L.)$ is derived. Some indication for the anomaly, reported by the Troitsk group, was found, but its postulated half-year period is contradicted by our data. To push the sensitivity on the neutrino mass below 1 eV/c ², a new larger MAC-E spectrometer is proposed. Besides its integrating mode, it could run in a new nonintegration operation MAC-E-TOF mode.     

Homoconjugation in the adamantane cage: DFT/IGLO studies of the 1, 3-dehydro-5-adamantyl cation, its isoelectronic boron analogue 1, 3-dehydro-5-boraadamantane, and related systems(1)(,)

The structure of 1,3-dehydro-5-adamantyl cation and its isoelectronic boron analogue 1,3-dehydro-5-boraadamantane as well as some related adamantane systems, hitherto unknown as persistent long-lived species, were investigated by using the density functional theory (DFT) method. (13)C and (11)B NMR chemical shifts of the compounds were also calculated using the IGLO method. Stabilization of the systems due to homoconjugation is discussed.     

Femtosecond surface vibrational spectroscopy of CO adsorbed on Ru(001) during desorption

Using time-resolved sum-frequency generation spectroscopy, the C- O stretch vibration of carbon monoxide adsorbed on a single-crystal Ru(001) surface is investigated during femtosecond near-IR laser excitation leading to desorption. A large transient redshift, a broadening of the resonance, and a strong decrease in intensity are observed. These originate from coupling of the C- O stretch to low-frequency modes, especially the frustrated rotation, that are highly excited in the desorption process.     

Hyperfine structure and isotope shifts of neutron-rich138–146Cs

The 6s²S_1/2-7_p ²P_3/2 transition in^138–142Cs (λ=455.5 nm) has been investigated by high-resolution collinear laser spectroscopy in a fast atomic beam. The isotopes are obtained by on-line mass separation of fission products. Nuclear moments and changes of mean-square charge radii are derived from hyperfine structure and isotope shift.     

Inhibition of the finite-time singularity during droplet fission of a polymeric fluid

When a drop of fluid detaches from a capillary, singular behavior ensues. We show that the addition of very small amounts of polymer inhibits this singularity in an abrupt way and gives rise, after a period of self-similar dynamics as for simple liquids, to long-lived cylindrical necks or filaments which thin exponentially in time. This abrupt change occurs when the elongation rate epsilon* becomes comparable to the inverse of the polymer relaxation time leading to a large elongational viscosity eta(E) of the dilute polymer solution.     

Survival of the d-wave superconducting state near the edge of antiferromagnetism in the cuprate phase diagram

In the cuprate superconductor YBa2Cu3O6+x, hole doping in the CuO2 layers is controlled by both oxygen content and the degree of oxygen ordering. At the composition YBa2Cu3O6.35, the ordering can occur at room temperature, thereby tuning the hole doping so that the superconducting critical temperature gradually rises from 0 to 20 K. Here we exploit this to study the c-axis penetration depth as a function of temperature and doping. The temperature dependence shows the d-wave superconductor surviving to very low doping, with no sign of another ordered phase interfering with the nodal quasiparticles. The only apparent doping dependence is a smooth decline of superfluid density as T(c) decreases.