Conditioning saliva for use in a microfluidic biosensor

This report details an approach to saliva conditioning for compatibility of raw patient samples with microfluidic immunoassay components, principally biosensor surfaces susceptible to fouling. Stimulated whole human saliva spiked with a small molecule analyte (phenytoin, 252 Da) was first depleted of cells, debris and high molecular weight glycoproteins (mucins) using membrane filtration. This process significantly reduced but did not eliminate fouling of biosensor surfaces exposed to the sample. An H-filter, which separates solutes from mixed samples based on their diffusion in laminar flow, was used to extract the analyte from the remaining large molecular weight species in the filtered saliva sample. Patient samples treated in this way retained 23% of the analyte with 97% and 92% reduction in glycoproteins and proteins, respectively, and resulted in 3.6 times less surface fouling than either untreated or filtered saliva alone. These sample conditioning steps will enable the use of fouling-sensitive detection techniques in future studies using clinical saliva samples.     

Incorporation of platinum nanoparticles in ordered mesoporous carbon

Platinum nanoparticles were incorporated within the pore system of ordered mesoporous carbon (OMC) by impregnating the carbon with a water-in-oil (w/o) microemulsion containing dissolved platinum salt followed by reduction of the platinum ions in situ inside the carbon pore system. The procedure provides preparation of metallic nanoparticles from hydrophilic precursors inside the hydrophobic carbon support structure with simultaneous control of the maximum metal particle size. Electron tomography was used to verify the presence of platinum nanoparticles inside the carbon material.     

Identifying promising compounds in drug discovery: genetic algorithms and some new statistical techniques

Throughout the drug discovery process, discovery teams are compelled to use statistics for making decisions using data from a variety of inputs. For instance, teams are asked to prioritize compounds for subsequent stages of the drug discovery process, given results from multiple screens. To assist in the prioritization process, we propose a desirability function to account for a priori scientific knowledge; compounds can then be prioritized based on their desirability scores. In addition to identifying existing desirable compounds, teams often use prior knowledge to suggest new, potentially promising compounds to be created in the laboratory. Because the chemistry space to search can be dauntingly large, we propose the sequential elimination of level combinations (SELC) method for identifying new optimal compounds. We illustrate this method on a combinatorial chemistry example.     

Numerical Simulation of Non-premixed Turbulent Combustion Using the Eddy Dissipation Concept and Comparing with the Steady Laminar Flamelet Model

Numerical simulations of the Sandia flame CHNa and the Sydney bluff-body stabilized flame HM1E are reported and the results are compared to available experimental data. The numerical method is based on compressible URANS formulations which were implemented recently in the OpenFOAM toolbox. In this study, the calculations are carried out using the conventional compressible URANS approach and a standard k- ?? turbulence model. The Eddy Dissipation Concept with a detailed chemistry approach is used for the turbulence-chemistry interaction. The syngas (CO/H₂) chemistry diluted by 30 % nitrogen in the Sandia flame CHNa and CH₄/H₂ combustion in the Sydney flame HM1E are described by the full GRI-3.0 mechanism. A robust implicit Runge-Kutta method (RADAU5) is used for integrating stiff ordinary differential equations to calculate the reaction rates. The radiation is treated by the P1-approximation model. Both target flames are predicted with the Steady Laminar Flamelet model using the commercial code ANSYS FLUENT as well. In general, there is good agreement between present simulations and measurements for both flames, which indicates that the proposed numerical method is suitable for this type of combustion, provides acceptable accuracy and is ready for further combustion application development.     

Solid-State P and H NMR Investigations of Amorphous and Crystalline Calcium Phosphates Grown Biomimetically From a Mesoporous Bioactive Glass

By exploiting (1)H and (31)P magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy, we explore the proton and orthophosphate environments in biomimetic amorphous calcium phosphate (ACP) and hydroxy-apatite (HA), as grown in vitro at the surface of a 10CaO-85SiO(2)-5P(2)O(5) mesoporous bioactive glass (MBG) in either a simulated body fluid or buffered water. Transmission electron microscopy confirmed the presence of a calcium phosphate layer comprising nanocrystalline HA. Two-dimensional (1)H-(31)P heteronuclear correlation NMR established predominantly (1)H(2)O?(31)PO(4) (3-) and O(1)H?(31)PO(4) (3-) contacts in the amorphous and crystalline component, respectively, of the MBG surface-layer; these two pairs exhibit distinctly different (1)H→(31)P cross-polarization dynamics, revealing a twice as large squared effective (1)H-(31)P dipolar coupling constant in ACP compared with HA. These respective observations are mirrored in synthetic (well-crystalline) HA, and the amorphous calcium orthophosphate (CaP) clusters that are present in the pristine MBG pore walls: besides highlighting very similar local (1)H and (31)P environments in synthetic and biomimetic HA, our findings evidence closely related NMR characteristics, and thereby similar local structures, of the CaP clusters in the pristine MBG relative to biomimetic ACP.     

A unifying coordinate family for the Kerr–Newman metric

A new unified metric form is presented for the Kerr–Newman geometry. The new form is a generalization of the Boyer–Lindquist metric involving an arbitrary gauge function of the spheroidal radial variable. Each choice of the gauge function corresponds to a coordinate system including four of the most important coordinate systems for Kerr–Newman (Boyer–Lindquist, Kerr, Kerr–Schild and Doran coordinates). The representation is given in terms of a single Minkowski frame together with the gauge function. This Minkowski frame arises by boosting a static orthonormal frame which is adapted to spheroidal coordinates. Properties of the boost reflect the rotating nature of the Kerr–Newman solution including an identification of the angular velocities of the disk and the horizon matching previously known values obtained in other ways.     

Positive shrinkage, improved pretest and absolute penalty estimators in partially linear models

Shrinkage estimators of a partially linear regression parameter vector are constructed by shrinking estimators in the direction of the estimate which is appropriate when the regression parameters are restricted to a linear subspace. We investigate the asymptotic properties of positive Stein-type and improved pretest semiparametric estimators under quadratic loss. Under an asymptotic distributional quadratic risk criterion, their relative dominance picture is explored analytically. It is shown that positive Stein-type semiparametric estimators perform better than the usual Stein-type and least square semiparametric estimators and that an improved pretest semiparametric estimator is superior to the usual pretest semiparametric estimator. We also consider an absolute penalty type estimator for partially linear models and give a Monte Carlo simulation comparisons of positive shrinkage, improved pretest and the absolute penalty type estimators. The comparison shows that the shrinkage method performs better than the absolute penalty type estimation method when the dimension of the parameter space is much larger than that of the linear subspace.     

Coordination Polymers Constructed from Paddle-Wheel Building Units

The two structurally related coordination polymers [Cu(ndc)(pyridine)], CPO-2-Cu, and [Zn(ndc)(3,4-lutidine)], CPO-2-Zn, were obtained by hydrothermal reactions between 2,6-naphthalenedicarboxylic acid (ndc), pyridine and copper(II) nitrate (CPO-2-Cu) and ndc, 3,4-lutidine and zinc(II) nitrate (CPO-2-Zn), respectively. The compounds are based on the binuclear paddle-wheel building unit. In both compounds these building units are connected into 2D sheets by naphthalene rings. In the third dimension there are weaker interactions involving the axial ligands pyridine and 3,4-lutidine. The sheets are stacked so that large 1D channels are formed into which the axial ligands protrude. The crystal structure of CPO-2-Cu was solved from synchrotron powder X-ray data, while the crystal structure of CPO-2-Zn was solved from conventional single-crystal X-ray data. Crystal data for CPO-2-Cu: Monoclinic space group C2/m (No. 12), a=10.2252(2), b=19.0915(4), c=8.0521(2) Å, β=98.824(1)°, V=1553.30(7) ų and Z=4. Crystal data for CPO-2-Zn: Triclinic space group P−1 (No. 2), a=7.540(1), b=10.711(1), c=11.196(2) Å, α=66.490(5)°, β=87.265(6)°, χ=88.470(6)°, V=828.2(2) ų and Z=2. The thermal properties of both compounds were investigated as well as the magnetic properties of CPO-2-Cu.     

Mass spectrometry of onium compounds-XVIII: Evaporation of N-arylpyridinium-3-oxides

Comparision of the fragmentation patterns and ionisation potentials for 3-hydroxy-2-phenylpyridine and N-arylpyridinium-3-oxides shows that the latter are evaporated as mesoins. The 2,4-dinitrophenyl derivative constitutes an exception in that transarylation to the corresponding ether takes place before evaporation.