6-Hydroxyalkylamino-6-deoxy-cyclodextrins: Towards dendrimeric host-molecules

6-Perhydroxyalkylamino-6-perdeoxy--cyclodextrins have been synthesised by treating 6-perbromo-6-perdeoxy-cyclodextrins with hydroxyalkylamines. The products (1, 2) are precursors of dendrimeric cyclodextrins in which the cavity provides access for the guest to interact with the branches. A fluorescence study has demonstrated the effects of the branches on binding of anilinonaphthalene sulfonate probes. The hosts show selectivity towards guests, and pH-dependence of binding, consistent with polar interaction between guest sulfonate anions and the protonated amino groups of the dendrimeric structure.     

Oxidation of guanosine derivatives by a platinum(IV) complex: internal electron transfer through cyclization

Many transition-metal complexes mediate DNA oxidation in the presence of oxidizing radiation, photosensitizers, or oxidants. The DNA oxidation products depend on the nature of the metal complex and the structure of the DNA. Earlier we reported trans-d,l-1,2-diaminocyclohexanetetrachloroplatinum (trans-Pt(d,l)(1,2-(NH(2))(2)C(6)H(10))Cl(4), [Pt(IV)Cl(4)(dach)]; dach = diaminocyclohexane) oxidizes 2'-deoxyguanosine 5'-monophosphate (5'-dGMP) to 7,8-dihydro-8-oxo-2'-deoxyguanosine 5'-monophosphate (8-oxo-5'-dGMP) stoichiometrically. In this paper we report that [Pt(IV)Cl(4)(dach)] also oxidizes 2'-deoxyguanosine 3'-monophosphate (3'-dGMP) stoichiometrically. The final oxidation product is not 8-oxo-3'-dGMP, but cyclic (5'-O-C8)-3'-dGMP. The reaction was studied by high-performance liquid chromatography, (1)H and (31)P nuclear magnetic resonance, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. The proposed mechanism involves Pt(IV) binding to N7 of 3'-dGMP followed by nucleophilic attack of a 5'-hydroxyl oxygen to C8 of G and an inner-sphere, 2e(-) transfer to produce cyclic (5'-O-C8)-3'-dGMP and [Pt(II)Cl(2)(dach)]. The same mechanism applies to 5'-d[GTTTT]-3', where the 5'-dG is oxidized to cyclic (5'-O-C8)-dG. The Pt(IV) complex binds to N7 of guanine in cGMP, 9-Mxan, 5'-d[TTGTT]-3', and 5'-d[TTTTG]-3', but no subsequent transfer of electrons occurs in these. The results indicate that a good nucleophilic group at the 5' position is required for the redox reaction between guanosine and the Pt(IV) complex.     

Cationic beta-cyclodextrin bilayer vesicles

Cationic amphiphilic beta-cyclodextrins, substituted with hydrophobic n-alkylthio chains at the primary hydroxyl side and hydrophilic omega-amino-oligo(ethylene glycol) units at the secondary side, form bilayer vesicles with a diameter of 30-35 nm (when alkyl = hexadecyl) or nanoparticles with a diameter of ca. 120 nm (when alkyl = hexyl) in water.     

Acoustic backscatter measurements from littoral seabeds at shallow grazing angles at 4 and 8 kHz

Direct measurement of acoustic scattering from the seabed at shallow grazing angles and low kilohertz frequencies presents a considerable challenge in littoral waters. Specifically, returns from the air-water interface typically contaminate the signals of interest. To address this issue, DRDC Atlantic has developed a sea-going research system for measuring acoustic scatter from the seabed in shallow-water environs. The system, known as the wideband sonar (WBS), consists of a parametric array transmitter and a superdirective receiver. In this paper, backscatter measurements obtained with the WBS at two sandy, shallow-water sites off North America's Atlantic coast are presented. Data were collected at 4 and 8 kHz at grazing angles from 3 degrees-15 degrees. The backscattering strength is similar at both sites and, below about 8 degrees, it appears to be independent of frequency within the statistical accuracy of the data. The measurements show reasonable agreement with model estimates of backscatter from sandy sediments. A small data set was collected at one of the sites to examine the feasibility of using the WBS to measure the azimuthal variability of acoustic scatter. The data set--although limited--indicates that the parametric array's narrow beamwidth makes the system well-suited to this task.     

Alkali-stable high-pI isoelectric membranes for isoelectric trapping separations

Alkali-stable, high-pI isoelectric membranes have been synthesized from quaternary ammonium derivatives of cyclodextrins and poly(vinyl alcohol), and bifunctional cross-linkers, such as glycerol-1,3-diglycidyl ether. The new, high-pI isoelectric membranes were successfully applied as cathodic membranes in isoelectric trapping separations in place of the hydrolytically more labile, polyacrylamide-based cathodic isoelectric membranes, and permitted the use of catholytes as alkaline as 1 M NaOH. The new high-pI isoelectric membranes have shown excellent mechanical stability, low electric resistance and long life times, even when subjected to electrophoresis with current densities as high as 80 mA/cm2.     

Photoelectron imaging of helium droplets

The photoionization and photoelectron spectroscopy of He nanodroplets (10(4) atoms) has been studied by photoelectron imaging with photon energies from 22.5-24.5 eV. Total electron yield measurements reveal broad features, whose onset is approximately 1.5 eV below the ionization potential of atomic He. The photoelectron spectra are dominated by very low energy electrons, with less than 0.6 meV. These results are attributed to the formation and autoionization of highly vibrationally excited He(*)(n) Rydberg states within the cluster, followed by strong final state interactions between the photoelectron and the droplet.     

Entangled Porphyrins in Cyclodextrin Vesicles

The entanglement process between porphyrins and some amphiphiliccyclodextrins and the occurrence of different species have been proved by the combination of UV-Visabsorption, fluorescence anisotropy, resonance light scattering and ¹H NMR spectroscopy.