An investigation of calibration materials for the measurement of metals in ambient particulate matter on filters by LA-ICP-MS

Three different types of simple and low-cost calibration material for the measurement of the metals content of ambient particulate matter (PM) on filters using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) have been compared: cellulose ester filters spiked with multi-element calibration solutions, pellets of compressed ambient particulate matter certified reference material (CRM), and powdered ambient particulate matter CRM adhered to a surface. Elements determined were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn, each at approximate levels of 1000?ng per filter. Blank filters spiked with multi-elemental standards were found to be significantly more reproducible and repeatable than materials based on powdered reference materials. However, a comparison of these spiked filters with real samples of ambient PM showed that the analytical sensitivities obtained per mass of analyte were significantly different. It is concluded that the spiked filters could act as very effective quality control standards correcting, to within 1%, drifts in LA-ICP-MS measurements of up to 10%, or as indirect calibration materials supported by additional measurements using traditional wet chemical techniques.     

Use of labelled nitrogen to measure gross and net rates of mineralization and microbial activity in permanent pastures following fertilizer applications at different time intervals

Measurements of some of the main internal N-cycling processes in soil were obtained by labelling the inorganic N pool with the stable isotope of nitrogen ((15)N). The (15)N mean pool dilution technique, combined with other field measurements, enabled gross and net N-mineralization rates to be resolved in grassland soils, which had previously either received fertilizer N (F), or had remained unfertilized (U) for many years. The two soils were subdivided into plots that received N at different time intervals (over 3 weeks), prior to (15)N measurements being made. By this novel approach, possible 'priming' effects over time were investigated to try to overcome some of the temporal problems of isotopic labelling of soil N (native plus fertilizer) and to identify possible changes in a range of primary N-transformation processes. The results suggested that an overall stimulation of microbially mediated processes occurred with all N treatments, but there were inconsistencies associated with the release of N, both in the timing and the degree to which different processes responded to the application of fertilizer N. The rates of these processes were, however, within the range of previously reported data and the (15)N measurements were not adversely affected by the differences in N pools created by the treatments. Thus, the mean pool dilution technique was shown to be applicable to agricultural soils, under conditions relevant to grass swards receiving fertilizer. For example, between the U and F treatments, the size of inorganic N pools increased by five-fold and gross rates of mineralization reached 3.5 and 4.8 microg N g(-1) (dry soil) d(-1), respectively, but did not vary greatly with the timing of N applications. A correlation (r(2) = 0.57) was found between soil respiration (which is relatively simple to measure) and net mineralization (which is more time consuming), suggesting that the former might be used as an indicator of the latter. Although this relationship was stronger in previously unfertilized soils, the similarities found with fertilized soils suggest that this approach could be used to obtain information of wider agronomic value and would, therefore, warrant further work under a range of soil conditions.     

Counterexamples in measuring the distance between binary trees

Examples are given to show that the closest partition distance measure need not agree with the nearest neighbor interchange distance for unordered labeled binary trees. Proposed algorithms for computing the closest partition distance are shown to be of exponential complexity and hence may not be useful in approximating the nearest neighbor interchange distance.     

Moduli of twisted spin curves

In this note we give a new, natural construction of a compactification of the stack of smooth -spin curves, which we call the stack of stable twisted -spin curves. This stack is identified with a special case of a stack of twisted stable maps of Abramovich and Vistoli. Realizations in terms of admissible -spaces and -line bundles are given as well. The infinitesimal structure of this stack is described in a relatively straightforward manner, similar to that of usual stable curves.

We construct representable morphisms from the stacks of stable twisted -spin curves to the stacks of stable -spin curves and show that they are isomorphisms. Many delicate features of -spin curves, including torsion free sheaves with power maps, arise as simple by-products of twisted spin curves. Various constructions, such as the -operator of Seeley and Singer and Witten's cohomology class go through without complications in the setting of twisted spin curves.

     

High throughput liquid chromatography/mass spectrometric analyses using a novel multiplexed electrospray interface

A novel four- channel multiplexed electrospray liquid chromatography interface is described. This device has been used to analyse both single components and mixtures by liquid chromatography/mass spectrometry (LC/MS) as well as synthetic samples prepared by automated procedures. These data provided unambiguous molecular weight assignments to both major components and synthetic by-products in these samples. In this work particular attention has also been paid to the elimination of interchannel crosstalk. Copyright 1999 John Wiley & Sons, Ltd.     

Molecular orientation in biaxially oriented sheets of poly(ethylene terephthalate) II. Correlation of orientation averages with measured mechanical compliances

The aggregate model is extended to examine the relationship between mechanical anisotropy and molecular orientation in one-way drawn sheets of poly(ethylene terephthalate). It is assumed that both the aggregate and the unit of structure have orthorhombic symmetry. On the basis of a number of detailed assumptions regarding the appropriate application of the model, calculated bounds are obtained for the elastic constants that are in reasonable agreement with the experimental values. The implications of these results with regard to molecular orientation are considered, and it is concluded that both the chain orientation and orientation around the chain axis are important in determining the mechanical anisotropy.     

Polymeric emulsion and crosslink-mediated synthesis of super-stable nanoparticles as sustained-release anti-tuberculosis drug carriers

This study focused on evaluating four emulsion-based processing strategies for polymeric nanoparticle synthesis to explicate the mechanisms of nanoparticle formation and the influence on achieving sustained-release of two anti-tuberculosis drugs, isoniazid and rifampicin. Poly(lactic-co-glycolic acid) (PLGA) nanoparticles were formulated with and without sorbitan mono-oleate as a stabilizer using emulsion-solvent-surfactant-evaporation (ESSE) and emulsion-solvent-evaporation (ESE) approaches. An alginate solution gelled by ionic crosslinking with calcium chloride was employed to prepare alginate hydrogel nanoparticles via reverse-emulsion-cationic-gelification (RECG) and reverse-emulsion-surfactant-cationic-gelification (RESCG) approaches. In vitro drug release analysis was performed. The size, zeta potential and morphology of the nanoparticles were analyzed. Molecular mechanics energy relationships (MMER) were employed to explore the spatial disposition of alginate and PLGA with respect to the emulsifying profile of sorbitan monooleate and to corroborate the experimental findings. Results revealed that particle size of the PLGA nanoparticles was influenced by the stabilizer concentration. Nanoparticles synthesized by the ESSE approach had smaller sizes of 240±8.7 nm and 195.5±5.4 nm for rifampicin- and isoniazid-loaded nanoparticles, respectively. This was a substantial size reduction from nanoparticles generated by the ESE approach (>1000 nm). The RESCG approach produced stable and higher nanoparticle yields with desirable size (277±1.0 nm; 289±1.2 nm), a low polydispersity index (27.1±0.3 mV; 28.5±0.5 mV) and drug entrapment efficiency of 73% and 75% for isoniazid and rifampicin, respectively. Drug release from the ESSE and RESCG synthesized nanoparticles displayed desirable release of the two anti-TB drugs with sustained zero-order kinetics over a period of 8h. MMER supported the mechanisms of nanoparticle formation with a sphericalized interlaced network configuration.     

Direct detection of products from the pyrolysis of 2-phenethyl phenyl ether

The pyrolysis of 2-phenethyl phenyl ether (PPE, C(6)H(5)C(2)H(4)OC(6)H(5)) in a hyperthermal nozzle (300-1350 °C) was studied to determine the importance of concerted and homolytic unimolecular decomposition pathways. Short residence times (<100 μs) and low concentrations in this reactor allowed the direct detection of the initial reaction products from thermolysis. Reactants, radicals, and most products were detected with photoionization (10.5 eV) time-of-flight mass spectrometry (PIMS). Detection of phenoxy radical, cyclopentadienyl radical, benzyl radical, and benzene suggest the formation of product by the homolytic scission of the C(6)H(5)C(2)H(4)-OC(6)H(5) and C(6)H(5)CH(2)-CH(2)OC(6)H(5) bonds. The detection of phenol and styrene suggests decomposition by a concerted reaction mechanism. Phenyl ethyl ether (PEE, C(6)H(5)OC(2)H(5)) pyrolysis was also studied using PIMS and using cryogenic matrix-isolated infrared spectroscopy (matrix-IR). The results for PEE also indicate the presence of both homolytic bond breaking and concerted decomposition reactions. Quantum mechanical calculations using CBS-QB3 were conducted, and the results were used with transition state theory (TST) to estimate the rate constants for the different reaction pathways. The results are consistent with the experimental measurements and suggest that the concerted retro-ene and Maccoll reactions are dominant at low temperatures (below 1000 °C), whereas the contribution of the C(6)H(5)C(2)H(4)-OC(6)H(5) homolytic bond scission reaction increases at higher temperatures (above 1000 °C).     

Surface chemical modification to control molecular interactions with porous silicon

Interactions between porous silicon (pSi) particles and probe molecules were evaluated to determine the effect of pSi and probe molecule chemistry on adsorption. Methylene blue, ethyl violet and orange G dyes were chosen for investigation as they possess distinct functionalities and charges. Several distinct pSi surface species were produced via thermal oxidation at 200-800 °C and their effect on adsorption investigated. The adsorption mechanisms were elucidated from equilibrium adsorption and desorption isotherms. Methylene blue adsorption was attributed to electrostatic attraction where a gradual increase in adsorption with oxidation temperature was observed. Significant methylene blue desorption was observed at pH 3, confirming adsorption occurs via electrostatic attraction. Ethyl violet demonstrated an increase in plateau adsorption capacity and affinity with increased oxidation temperatures and adsorption was initially attributed to electrostatic attraction, however desorption of ethyl violet was not observed, thus indicating potential chemisorption. Orange G exhibited high affinity adsorption for Si(y)SiH(x) terminated surfaces but no orange G desorption was detected, indicating a chemisorption adsorption mechanism. It has been successfully demonstrated that the surface modification of pSi enabled the manipulation of molecular interactions. By interacting probe molecules with similar functionalities to drug molecule with pSi, greater understanding of drug-pSi interactions can be ascertained which are of great importance. pSi surface chemistry can be tailored to enable control over molecular interactions and ultimately dictate loading, encapsulation and release behavior.     

Born Reciprocity and the Granularity of Spacetime

The Schrödinger-Robertson inequality for relativistic position and momentum operators X ^μ, P _ν, μ, ν = 0, 1, 2, 3, is interpreted in terms of Born reciprocity and ‘non-commutative’ relativistic position-momentum space geometry. For states which saturate the Schrödinger-Robertson inequality, a typology of semiclassical limits is pointed out, characterised by the orbit structure within its unitary irreducible representations, of the full invariance group of Born reciprocity, the so-called ‘quaplectic’ group U(3, 1) #x2297;_s H(3, 1) (the semi-direct product of the unitary relativistic dynamical symmetry U(3, 1) with the Weyl-Heisenberg group H(3, 1)). The example of the ‘scalar’ case, namely the relativistic oscillator, and associated multimode squeezed states, is treated in detail. In this case, it is suggested that the semiclassical limit corresponds to the separate emergence of spacetime and matter, in the form of the stress-energy tensor, and the quadrupole tensor, which are in general reciprocally equivalent.