Spirometallodendrimers: terpyridine-based intramacromolecular cyclization upon complexation

The first examples of metallodendritic spiranes have been obtained via incorporation of single terpyridine units within each dendritic quadrant.     

The free surface on a liquid between cylinders rotating at different speeds. Part III

Summary This paper is a further contribution to our work on the Weissenberg effect. One goal of our work is to show how the free-surface deformations on a viscoelastic fluid which is sheared between two concentric rotating cylinders can be used to determine rheological data about the fluid. In this paper we report the results of an experimental program in which free surface shapes have been measured on three viscoelastic fluids undergoing shearing in an apparatus consisting of a stationary outer cylinder and four interchangeable rotating inner cylinders. Experimentally-measured profiles are compared with profiles predicted from second-order theory, and found to be in excellent agreement for STP and TLA-227 in the range of applicability of the second-order theory, but there is some disagreement in the results for a 2% solution of polyacrylamide in 49% water –49% glycerin.

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Zusammenfassung Diese Arbeit stellt einen weiteren Beitrag zu unseren Untersuchungen über den Weissenberg-Effekt dar. Ein Ziel dieser Untersuchungen ist es zu zeigen, wie die Deformation der freien Oberfläche einer zwischen zwei konzentrischen Zylindern gescherten viskoelastischen Flüssigkeit dazu verwendet werden kann, rheologische Kenngrößen der Flüssigkeit zu gewinnen. In dieser Arbeit wird über die Ergebnisse einer experimentellen Untersuchung berichtet, in der die Gestalt der freien Oberfläche bei drei viskoelastischen Flüssigkeiten gemessen wurde, die in einem Apparat geschert wurden, der aus einem stationären Außenzylinder und vier auswechselbaren rotierenden Innenzylindern bestand. Die experimentell bestimmten Profile werden mit solchen verglichen, die aufgrund einer Theorie zweiter Ordnung vorausgesagt worden sind. Man findet im Bereich der Anwendbarkeit dieser Theorie für STP und TLA-227 eine ausgezeichnete Übereinstimmung, wohingegen die Ergebnisse bei einer 2%igen Polyacrylamid-Lösung in einer 1:1-Wasser-Glycerin-Mischung gewisse Diskrepanzen aufweisen.

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With 12 figures and 1 table     

Nanomanipulator-assisted fabrication and characterization of carbon nanotubes inside scanning electron microscope

We have installed two nanomanipulators, which can travel about 20mm with a minimum increment of 1 nm, for manipulation of nanostructured materials inside field-emission scanning electron microscope (FE-SEM). Both manipulators render motions in x, y, and z directions, providing various manipulation freedoms such as moving, bending, cutting, and biasing. In addition, we have conducted in situ characterization of the electrical breakdown of multi-walled carbon nanotubes (MWCNTs). Our results demonstrate the possibility that MWCNTs can be used as a gas sensor.     

Preparative and stereoselective synthesis of the versatile intermediate for carbocyclic nucleosides: effects of the bulky protecting groups to enforce facial selectivity

The preparative and stereoselective synthesis (45-50% overall yields) of the target compound 17 has been accomplished from D-ribose. The bulky protecting groups such as TBDPS and Trityl enforced the facial selectivity during Grignard reaction to give the tertiary beta-allylic alcohol 16 as the sole product, which was oxidatively rearranged to the key molecule 17 in excellent yield.     

Evolution of a stress-driven pattern in thin bilayer films: spinodal wrinkling

We report the full spectrum of the evolution of the wrinkle pattern formation in a thin bilayer film of an elastic metal on a viscoelastic polymer. Although the origin is different, the transition of an initial islandlike pattern to a labyrinthine structure without any change in the wavelength (q approximately t(0)) and the overall evolutionary process is strikingly similar to that in the spinodal system but the process is robust and takes place on a long time scale (about 10 days). The change into a mountainous topography in the late stages is accompanied by an increase in the length scale from an initial wavelength to another. This change, due to the relaxation of the confined polymer that results in a transition from elastic- to viscouslike behavior, induces wave coarsening (q approximately t(-1.04+/-0.08)) and macroscopic roughening.     

Polymeric enzyme mimics: catalytic activity of ribose-containing polymers for a phosphate substrate

The polymers containing ribose rings: poly(5'-acrylamido-5'-deoxy-1',2'-O-isopropylidene-alpha-D-ribose) (11), poly(5'-acrylamido-5'-deoxy-alpha-D-ribose) (12) and poly(5'-acrylamido-5'-deoxy-1'-O-methyl-D-ribose) (13) were prepared as enzyme mimics. Polymers 12 and 13 with free vic-cis-diol groups catalyzed the hydrolysis of phosphodiester (ethyl p-nitrophenyl phosphate and N-methylpyridinium 4-tert-butylcatechol cyclic phosphate) and phosphomonoester substrates with a rate acceleration of 10 approximately equal to 10(3) compared with the uncatalyzed reaction. They also catalyzed the reverse reactions, i.e., the esterification of phosphomonoester to phosphodiester and the phosphorylation of alcohols with phosphate ions. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles. The catalytic activity was negligible for polymer 11 where vic-cis-diol groups were blocked with isopropylidene groups. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles.     

Analysis of vasopressin using capillary electrophoresis with laser-induced fluorescence detector based on competitive immunoassay

A competitive immunoassay based on CE-LIF has been developed for the determination of vasopressin in biological mixtures. Vasopressin participates in the hormonal control of water metabolism and the constriction of arterioles in humans. Thus, detection of vasopressin is important in diagnosing pathological conditions and physiological water metabolism. The peptides were fluorescently tagged with FITC and purified by HPLC. The purified product was then mixed with the cerebrospinal fluid sample followed with the addition of anti-vasopressin antibody. It was possible to separate antibody-bound and free FITC-tagged vasopressin within 10 min by CE-LIF analysis using uncoated fused-silica capillary with high reproducibility.     

Martensitic fcc-to-hcp transformation observed in xenon at high pressure

Angle-resolved x-ray diffraction patterns of Xe to 127 GPa indicate that the fcc-to-hcp transition occurs martensitically between 3 and 70 GPa in diamond-anvil cells without an intermediate phase. These data also reveal that the transition occurs by the introduction of stacking disorder in the fcc lattice at low pressure, which grows into hcp domains with increasing pressure. The small energy difference between the hcp and the fcc structures may allow the two phases to coexist over a wide pressure range. Evidence of similar stacking disorder and incipient growth of an hcp phase are also observed in solid Kr.     

Complex Forming Ability of a Family of Isolated Cyclosophoraoses with Ergosterol and Its Monte Carlo Docking Computational Analysis

Neutral cyclosophoraoses (unbranched cyclic -1,2-d-glucans) produced by the Rhizo-bium meliloti 2011 were prepared by size exclusion and anion-exchange chromatographic techniques. The degree of polymerization (DP) of isolated cyclosophoraoses was determined by matrix associated laser desorption/ionization mass spectrometry (MALDI/MS) techniques. A family of purified neutral cyclosophoraoses (DP 17–27) was used as a host for the inclusion complexation with hardly soluble ergosterol. High performance liquid chromatographic (HPLC) analysis showed that it induced much enhanced solubility of ergosterol compared to -cyclodextrin. In order to understand the molecular basis of the complex forming ability of cyclosophoraoses, a Monte Carlo (MC) docking-minimization method was used for host-guest complex formation of cyclosophoraoses or -cyclodextrin with ergosterol. From the MC simulation we propose the `hand-shake' mechanism for complexation of cyclosophoraoses with ergosterol.