Functionalized nanoparticles for liquid atmospheric pressure matrix-assisted laser desorption/ionization peptide analysis

Nanoparticles for the extraction of peptides and subsequent analysis using atmospheric pressure matrix-assisted laser desorption/ionization (APMALDI) have been evaluated. The atmospheric pressure source allows for particles to be directly introduced in the liquid matrix, minimizing sample loss and analysis time. Described in this work are two sample preparation procedures for liquid APMALDI analysis: a C18 functionalized silica nanoparticle for hydrophobic extractions, and an aptamer functionalized magnetite core nanoparticle for rapid, affinity extractions. The C18 particles provide a non-selective support for rapid profiling applications, while the aptamer particles are directed towards reducing the complexity in biological samples. The aptamer functionalized particles provide a more selective analyte-nanoparticle interaction whereby the tertiary structure of the analyte becomes more critical to the extraction. In both cases, the liquid APMALDI matrix provides a support for ionization, and acts as the releasing agent for the analyte-particle interaction. Additionally, analyte enrichment was possible due to the large surface-to-volume ratio of the particles. The experiments conducted with functionalized nanoparticles, in an atmospheric pressure liquid matrix, present a basis for further methodologies and utilities of silica nanoparticles to be developed.     

Natural anti-HIV agents. Part 3: Litseaverticillols A-H, novel sesquiterpenes from Litsea verticillata

Bioassay directed-fractionation led to the identification of litseaverticillols A-H (1-8) from the leaves and twigs of Litsea verticillata Hance. These new sesquiterpenes possess a unique skeleton that was recently designated as ‘litseane’. The structures of these compounds were determined by spectroscopic means including 1D and 2D NMR data. Structural configurations were determined by ROESY experiments. Mosher ester reactions and optical rotation measurements established the sesquiterpenes 1-8 as racemates. Isolates 1-8 inhibited HIV-1 replication in HOG.R5 cells with IC₅₀ values ranging from 2 to 15 μg/ml (8-58 μM) while affecting the growth of HOG.R5 at concentrations 2-3-fold higher. Based on this data, structure-activity relationships can be discerned, suggesting compounds of this class are good candidates for analog production.     

Lattice-BGK approach to simulating granular flows

Many continuum theories for granular flow produce an equation of motion for the fluctuating kinetic energy density (granular temperature) that accounts for the energy lost in inelastic collisions. Apart from the presence of an extra dissipative term, this equation is very similar in form to the usual temperature equation in hydrodynamics. It is shown how a lattice-kinetic model based on the Bhatnagar-Gross-Krook (BGK) equation that was previously derived for a miscible two-component fluid may be modified to model the continuum equations for granular flow. This is done by noting that the variable corresponding to the concentration of one species follows an equation that is essentially analogous to the granular temperature equation. A simulation of an unforced granular fluid using the modified model reproduces the phenomenon of clustering instability, namely the spontaneous agglomeration of particles into dense clusters, which occurs generically in all granular flows. The success of the continuum theory in capturing the gross features of this basic phenomenon is discussed. Some shear flow simulations are also presented.     

Variable-Energy Photoelectron Spectroscopy of (eta(5)-C(5)H(5))NiNO: Molecular Orbital Assignment and Xalpha-SW Calculations

Variable-energy valence and inner-valence photoelectron spectra have been recorded for the CpNiNO complex (Cp = eta(5)-C(5)H(5)) between 21.2 and 100 eV, using He I radiation and synchrotron radiation. The ground state electronic structure has been calculated by using the Xalpha-SW method. Photoionization cross sections (sigma) have also been calculated for the valence ionizations using the Xalpha-SW method. The theoretical branching ratios (sigma(i)/ summation operatorsigma) have been compared with the observed branching ratios (A(i)()/ summation operatorA) between 21.2 and 100 eV. The assignment of the photoelectron spectrum based on the analysis of intensity variations and width of vibrational peaks is consistent with the ion state orbital ordering 5e(1)(1) < 7a(1)(2) < 3e(2)(3) < 4e(1)(4) (band numbers are in parentheses) and is inconsistent with another recently proposed ordering 5e(1)(1), 5e(1)(2) < 7a(1), 3e(2)(3) < 4e(1)(4), which takes the 5e(1) vibronic effects into consideration. The experimental branching ratio results indicate a Ni 3p resonance effect around 75 eV in the photoionization process. The inner-valence spectrum has also been assigned with the aid of the Xalpha-SW calculations.     

Self-intersections of curves on surfaces

Let M be a compact orientable surface with nonempty boundary (x(M)<0) and fundamental group . Let be a geodesic on M (with a fixed hyperbolic structure), and let W be a (cyclically reduced) word in a fixed set of generators of which represents . In this paper, we give an algorithm to count the number of self-intersections of in terms of W, generalizing a result of Birman and Series, where an algorithm was given to decide if was simple. Some applications of the algorithm to surfaces with one boundary and the Markoff spectrum are also given.