10-100 eV Ar+ ion induced damage to D-ribose and 2-deoxy-D-ribose molecules in condensed phase

We report that 10-100 eV Ar+ ion irradiation induces severe damage to the biologically relevant sugar molecules D-ribose and 2-deoxy-D-ribose in the condensed phase on a polycrystalline Pt substrate. Ar+ ions with kinetic energies down to 15 eV induce effective decomposition of both sugar molecules, leading to the desorption of abundant cation and anion fragments, including CH3+, C2H3+, C3H3+, H3O+, CHO+, CH3O+, C2H3O+, H-, O-, and OH-, etc. Use of isotopically labelled molecules (5- 13C D-ribose and 1-D D-ribose) reveals the site specificity for some of the fragment origins, and thus the nature of the chemical bond breaking. It is found that all of the chemical bonds in both molecules are vulnerable to ion impact at energies down to 15 eV, particularly both the endo- and exocyclic C-O bonds. In addition to molecular fragmentation, several chemical reactions are also observed. A small amount of O-/O fragments abstract hydrogen to form OH-. It is found that the formation of the H3O+ ion is related to the hydroxyl groups of the sugar molecules, and is associated with additional hydrogen loss from the parent or adjacent molecules via hydrogen abstraction or proton transfer. The formation of several other cation fragments also requires hydrogen abstraction from its parent or an adjacent molecule. These fragmentations and reactions are likely to occur in a real biomedium during ionizing radiation treatment of tumors and thus bear significant radiobiological relevance.     

Copper-coated microsprayer interface for on-line sheathless capillary electrophoresis electrospray mass spectrometry of carbohydrates

A sturdy home-built sheathless CE/ESI-QTOF-MS system was developed and optimized for carbohydrate analysis. The interface and employed methodology provided a simple analytical solution to laborious CE/MS interfacing methods and to problems in characterization of complex carbohydrate mixtures that require high-resolution separation of the components. The CE/ESI interface, feasible in any MS laboratory, consists of a one-piece CE column having the CE terminus in-laboratory shaped as a microsprayer and coated with copper. The CE microsprayer was inserted into an in-house made stainless steel clenching device and the whole assembly was mounted onto a quadrupole TOF mass spectrometer. The analytical potential of the interface in terms of suitability, microsprayer performance, copper coat durability, ionization efficiency, spray stability, and sensitivity was tested first on a simple mixture of standard saccharides, which were separated, resolved, and detected with high separation efficiency. The approach was next assessed for the screening of a biological sample, a complex mixture of O-glycosylated sialylated amino acids from urine of a patient suffering from Schindler disease. Preliminary data allow this method to be considered as one of general applicability in structural glycobiology and glycomics and easy to be implemented for proteomic surveys as well.     

Preconditioners for Incompressible Navier-Stokes Solvers

<正>In this paper we give an overview of the present state of fast solvers for the solution of the incompressible Navier-Stokes equations discretized by the finite element method and linearized by Newton or Picard's method.It is shown that block preconditioners form an excellent approach for the solution,however if the grids are not to fine preconditioning with a Saddle point ILU matrix(SILU) may be an attractive alternative. The applicability of all methods to stabilized elements is investigated.In case of the stand-alone Stokes equations special preconditioners increase the efficiency considerably.     

Reactive scattering damage to DNA components by hyperthermal secondary ions

We have observed reactive scattering damage to fundamental DNA building blocks by the type of hyperthermal secondary ions that are produced along heavy ion tracks in biological media. Reactions include carbon abstraction by N+, and hydrogen abstraction by O- and N+, at collision energies down to 1 eV. Our results show that localized reactive scattering by hyperthermal secondary fragments can lead to important physicochemical damage to DNA in cells irradiated by heavy ions. This suggests a fundamentally different picture of nascent DNA damage induced by heavy ion tracks, compared to conventional (x or gamma) radiation tracks.     

Graph operations that are good for greedoids

S is a local maximum stable set of a graph G, and we write S∈Ψ(G), if the set S is a maximum stable set of the subgraph induced by S∪N(S), where N(S) is the neighborhood of S. In Levit and Mandrescu (2002) [5] we have proved that Ψ(G) is a greedoid for every forest G. The cases of bipartite graphs and triangle-free graphs were analyzed in Levit and Mandrescu (2003) [6] and Levit and Mandrescu (2007) [7] respectively.In this paper we give necessary and sufficient conditions for Ψ(G) to form a greedoid, where G is:

(a)

the disjoint union of a family of graphs;

(b)

the Zykov sum of a family of graphs;

(c)

the corona X°{H₁,H₂,…,H_n} obtained by joining each vertex x of a graph X to all the vertices of a graph H_x.

     

Rational Design of a Cocktail of Inhibitors against Aβ Aggregation

It has been reported that many molecules could inhibit the aggregation of Aβ (amyloid-β) through suppressing either primary nucleation, secondary nucleation, or elongation processes. In order to suppress multiple pathways of Aβ aggregation, we screened 23 small molecules and found two types of inhibitors with different inhibiting mechanisms based on chemical kinetics analysis. Trp-glucose conjugates ( AS2 ) could bind with fibril ends while natural products ( D3 and D4 ) could associate with monomers. A cocktail of these two kinds of molecules achieved co-inhibition of various fibrillar species and avoid unwanted interference.     

On the Upper Limits of Oxidation States in Chemistry

The concept of oxidation state ( OS ) is based on the concept of Lewis electron pairs, in which the bonding electrons are assigned to the more electronegative element. This approach is useful for keeping track of the electrons, predicting chemical trends, and guiding syntheses. Experimental and quantum‐chemical results reveal a limit near +8 for the highest OS in stable neutral chemical substances under ambient conditions. OS =+9 was observed for the isolated [IrO₄]⁺ cation in vacuum. The prediction of OS =+10 for isolated [PtO₄]²⁺ cations is confirmed computationally for low temperatures only, but hasn't yet been experimentally verified. For high OS species, oxidation of the ligands, for example, of O^?2 with formation of ^.O^?1 and O?O bonds, and partial reduction of the metal center may be favorable, possibly leading to non‐Lewis type structures.     

Kinetics of manganese ferrite generation from aqueous solution of MnO2 and FeSO4·7H2O through copreotitation and ageing

The authors present a kinetic investigation of the generation of manganese ferrite by the ageing of some coprecipitates in contact with the residual solution.