High-energy collision-induced dissociation mass spectrometry of synthetic mannose-6-phosphate oligosaccharides

The high-energy collision-induced dissociation spectra of a series of linear and branched synthetic mannosyl oligosaccharides that contain 6-phosphate substituents on either or both non-reducing terminal or penultimate residues have been studied. These phosphorylated structures were designed to mimic those of naturally derived N-glycans (Man-6-PO₄) on lysosomal enzymes and to probe the minimally required binding motif for the Man-6-PO₄ receptors. When a phosphate group was present, the spectra were dominated by ions that arise from cleavages at the glycosidic bonds (single and double) with charge retention on the phosphate-containing fragments. The spectra of linear structures that bear the nonreducing terminal Man-6-phosphate residues were devoid of Y-type ions, unlike those with similar phosphorylation at the penultimate residue. The location of the phosphorylated residue was deduced from the presence or absence of unique B and Y ions. In neutral branched structures, the ions were formed by cleavage at the glycosidic bond at either one or both of the branch points and the aglycon, which was attached to the disubstituted mannosyl residue. Branched oligosaccharides that contained one or two terminal Man-6-PO₄ residues also showed double cleavages with charge retention on the phosphate-containing fragment. Our investigation shows that positive mode high energy collision-induced dissociation mass spectrometry can determine the location—terminal or penultimate—of Man-6-PO₄ residues in N-linked type oligosaccharides.     

The Patch Construction is Dual to Algebraic DCPO Representation

Using the parallel between the preframe and the suplattice approach to locale theory it is shown that the patch construction, as an action on topologies, is the same thing as the process of recovering a discrete poset from its algebraic dcpo (ideal completion).     

Numerical solutions of some unsteady flows of elastico-viscous liquids

Summary Consideration is given to the rectilinear flow of anOldroyd model fluid in a straight pipe of circular cross-section. A numerical solution of the full non-linear equations is obtained without the necessity for a perturbation analysis in terms of some small parameter. Results are presented for a number of different flow conditions.With 12 figures     

Proof of a tournament partition conjecture and an application to 1-factors with prescribed cycle lengths

In 1982 Thomassen asked whether there exists an integer f(k,t) such that every strongly f(k,t)-connected tournament T admits a partition of its vertex set into t vertex classes V ₁,…V _t such that for all i the subtournament T[V _i] induced on T by V _i is strongly k-connected. Our main result implies an affirmative answer to this question. In particular we show that f(k, t)=O(k ⁷ t ⁴) suffices. As another application of our main result we give an affirmative answer to a question of Song as to whether, for any integer t, there exists aninteger h(t) such that every strongly h(t)-connected tournament has a 1-factor consisting of t vertex-disjoint cycles of prescribed lengths. We show that h(t)=O(t ⁵) suffices.     

Identification of protein phosphorylation sites within Ser/Thr-rich cluster domains using site-directed mutagenesis and hybrid linear quadrupole ion trap Fourier transform ion cyclotron resonance mass spectrometry

We describe a method for the analysis of multi-site phosphorylation in serine/threonine (Ser/Thr)-rich protein sequences. Site-specific mutagenesis was used to introduce tryptic cleavage sites in the serine glutamine/threonine glutamine cluster domain (SCD) of the human checkpoint protein kinase (Chk2). The mutant proteins were shown to autophosphorylate on residues that are inducibly phosphorylated when mammalian cells are exposed to ionizing radiation (serine 33/35, serine 516, threonine 68 and threonine 432). Five Ser/Thr clusters within the SCD were flanked by arginine or lysine residues to produce tryptic peptides for nanospray liquid chromatography (nanoLC)/linear quadrupole ion trap Fourier transform ion cyclotron resonance mass spectrometry. Phosphorylation sites were assigned using accurate-mass-driven analysis and interpretation of low-energy collision-induced dissociation spectra acquired in the ion trap. In addition to verifying known phosphorylation sites, seventeen novel sites were identified within the SCD of Chk2. The approach should be applicable to other O-linked post-translational modifications that occur in proteins with Ser/Thr-rich sequences.     

Photocatalytic water oxidation with nonsensitized IrO2 nanocrystals under visible and UV light

Rutile IrO(2) is known as being among the best electrocatalysts for water oxidation. Here we report on the unexpected photocatalytic water oxidation activity of 1.98 nm ± 0.11 nm succinic acid-stabilized IrO(2) nanocrystals. From aqueous persulfate and silver nitrate solution the nonsensitized particles evolve oxygen with initial rates up to 0.96 μmol min(-1), and with a quantum efficiency of at least 0.19% (measured at 530 nm). The catalytic process is driven by visible excitations from the Ir-d(t(2g)) to the Ir-d(e(g)) band (1.5-2.75 eV) and by ultraviolet excitations from the O-p band to the Ir-d(e(g)) (>3.0 eV) band. The formation of the photogenerated charge carriers can be directly observed with surface photovoltage spectroscopy. The results shed new light on the role of IrO(2) in dye- and semiconductor-sensitized water splitting systems.     

Characterization of sulfurous acid, sulfite, and bisulfite aerosol systems

Acidic tropospheric aerosols contain inorganic species such as sulfurous acid (H(2)SO(3)). As the main alkaline species, ammonia (NH(3)) plays an important role in the heterogeneous neutralization of these acidic aerosols. An aerosol flow-tube apparatus was used to obtain simultaneous optical and size distribution measurements using FTIR and SMPS measurements, respectively, as a function of relative humidity and aerosol chemical composition. A novel chemiluminescence apparatus was also used to measure ammonium ion concentration [NH(4)(+)]. The interactions between ammonia and hydrated sulfur dioxide (SO(2)·H(2)O) were studied at different humidities and concentrations. SO(2)·H(2)O is an important species as it represents the first intermediate in the overall atmospheric oxidation process of sulfur dioxide to sulfuric acid (H(2)SO(4)). This complex was produced within gaseous, aqueous, and aerosol SO(2) systems. The addition of ammonia gave mainly hydrogen sulfite (SHO(3)(-)) tautomers and disulfite ions (S(2)O(5)(2-)). These species were prevalent at high humidities enhancing the aqueous nature of sulfur(IV) species. Their weak acidity is evident due to the low [NH(4)(+)] produced. Size distributions obtained correlated well with the various stages of particulate compositional development.     

A chemiluminescence study of madder lakes on paper

The photo degradation of watercolour drawings prepared with madder lake pigments on gelatine-sized paper was studied by chemiluminometry, viscometry, and colorimetry. A method of recto irradiation and verso measurement was developed to overcome absorption of the emitted photons by the paint layer. A complex relationship between paper substrate, applied chromophores and associated transition metals was observed with strong correlations between the presence of transition metals associated with the madder lakes and the degradation of the paper substrate and the applied paint layer as well as evidence of pro-oxidative activity by the chromophores in the applied paint layers. The pro-oxidant behaviour appears to be dependent on the type of transition metal present. This is the first in-depth research into the photodegradation of madder lake-based watercolours which attempts to understand the chemistry of the processes.     

Investigation of two-dimensional acoustic resonant modes in a particle separator

Within an acoustic standing wave particles experience acoustic radiation forces, a phenomenon which is exploited in particle or cell manipulation devices. When developing such devices, one-dimensional acoustic characteristics corresponding to the transducer(s) are typically of most importance and determine the primary radiation forces acting on the particles. However, radiation forces have also been observed to act in the lateral direction, perpendicular to the primary radiation force, forming striated patterns. These lateral forces are due to lateral variations in the acoustic field influenced by the geometry and materials used in the resonator. The ability to control them would present an advantage where their effect is either detrimental or beneficial to the particle manipulation process. The two-dimensional characteristics of an ultrasonic separator device have been modelled within a finite element analysis (FEA) package. The fluid chamber of the device, within which the standing wave is produced, has a width to height ratio of approximately 30:1 and it is across the height that a half-wavelength standing wave is produced to control particle movement. Two-dimensional modal analyses have calculated resonant frequencies which agree well with both the one-dimensional modelling of the device and experimentally measured frequencies. However, these two-dimensional analyses also reveal that these modes exhibit distinctive periodic variations in the acoustic pressure field across the width of the fluid chamber. Such variations lead to lateral radiation forces forming particle bands (striations) and are indicative of enclosure modes. The striation spacings predicted by the FEA simulations for several modes compare well with those measured experimentally for the ultrasonic particle separator device. It is also shown that device geometry and materials control enclosure modes and therefore the strength and characteristics of lateral radiation forces, suggesting the potential use of FEA in designing for the control of enclosure modes in similar particle manipulator devices.