Determination of airborne trialkyl and triaryl organophosphates originating from hydraulic fluids by gas chromatography-mass spectrometry. Development of methodology for combined aerosol and vapor sampling

Methodology for personal occupational exposure assessment of airborne trialkyl and triaryl organophosphates originating from hydraulic fluids by active combined aerosol and vapor sampling at 1.5L/min is presented. Determination of the organophosphates was performed by gas chromatography-mass spectrometry. Combinations of adsorbents (Anasorb 747, Anasorb CSC, Chromosorb 106, XAD-2 and silica gel) with an upstream cassette with glass fiber or PTFE filters and different desorption/extraction solvents (CS(2), CS(2)-dimethylformamide (50:1, v/v), toluene, dichloromethane, methyl-t-butyl ether and methanol) have been evaluated for optimized combined vapor and aerosol air sampling of the organophosphates tri-isobutyl, tri-n-butyl, triphenyl, tri-o-cresyl, tri-m-cresyl and tri-p-cresyl phosphates. The combination of Chromosorb 106 and 37 mm filter cassette with glass fiber filter and dichloromethane as desorption/extraction solvent was the best combination for mixed phase air sampling of the organophosphates originating from hydraulic fluids. The triaryl phosphates were recovered solely from the filter, while the trialkyl phosphates were recovered from both the filter and the adsorbent. The total sampling efficiency on the combined sampler was in the range 92-101% for the studied organophosphates based on spiking experiments followed by pulling air through the sampler. Recoveries after 28 days storage were 98-102% and 99-101% when stored at 5 and -20 degrees C, respectively. The methodology was further evaluated in an exposure chamber with generated oil aerosol atmospheres with both synthetic and mineral base oils with added organophosphates in various concentrations, yielding total sampling efficiencies in close comparison to the spiking experiments. The applicability of the method was demonstrated by exposure measurements in a mechanical workshop where system suitability tests are performed on different aircraft components in a test bench, displaying tricresyl phosphate air concentrations of 0.024 and 0.28 mg/m(3), as well as during aircraft maintenance displaying tri-n-butyl phosphate air concentrations of 0.061 and 0.072 mg/m(3).     

Electromagnetic momentum conservation in media

That static electric and magnetic fields can store momentum may be perplexing, but is necessary to ensure total conservation of momentum. Simple situations in which such field momentum is transferred to nearby bodies and point charges have often been considered for pedagogical purposes, normally assuming vacuum surroundings. If dielectric media are involved, however, the analysis becomes more delicate, not least since one encounters the electromagnetic energy–momentum problem in matter, the ‘Abraham–Minkowski enigma’, of what the momentum is of a photon in matter. We analyze the momentum balance in three nontrivial examples obeying azimuthal symmetry, showing how the momentum conservation is satisfied as the magnetic field decays and momentum is transferred to bodies present. In the last of the examples, that of point charge outside a dielectric sphere in an infinite magnetic field, we find that not all of the field momentum is transferred to the nearby bodies; a part of the momentum appears to vanish as momentum flux towards infinity. We discuss this and other surprising observations which can be attributed to the assumption of magnetic fields of infinite extent. We emphasize how formal arguments of conserved quantities cannot determine which energy–momentum tensor is more “correct”, and each of our conservation checks may be performed equally well in the Minkowski or Abraham framework.     

High-resolution diode-laser spectroscopy of calcium

Saturated-absorption signals on the calcium 657 nm transition are observed by direct absorption using diode lasers and a high flux atomic-beam cell. Line-widths as narrow as 65 kHz are observed with a high signal-to-noise ratio. Prospects for using this system as a compact wavelength/frequency reference are considered.     

Biosynthesis of the polyene antifungal antibiotic nystatin in Streptomyces noursei ATCC 11455: analysis of the gene cluster and deduction of the biosynthetic pathway

BACKGROUND: The polyene macrolide antibiotic nystatin produced by Streptomyces noursei ATCC 11455 is an important antifungal agent. The nystatin molecule contains a polyketide moiety represented by a 38-membered macrolactone ring to which the deoxysugar mycosamine is attached. Molecular cloning and characterization of the genes governing the nystatin biosynthesis is of considerable interest because this information can be used for the generation of new antifungal antibiotics. RESULTS: A DNA region of 123,580 base pairs from the S. noursei ATCC 11455 genome was isolated, sequenced and shown by gene disruption to be involved in nystatin biosynthesis. Analysis of the DNA sequence resulted in identification of six genes encoding a modular polyketide synthase (PKS), genes for thioesterase, deoxysugar biosynthesis, modification, transport and regulatory proteins. One of the PKS-encoding genes, nysC, was found to encode the largest (11,096 amino acids long) modular PKS described to date. Analysis of the deduced gene products allowed us to propose a model for the nystatin biosynthetic pathway in S. noursei. CONCLUSIONS: A complete set of genes responsible for the biosynthesis of the antifungal polyene antibiotic nystatin in S. noursei ATCC 11455 has been cloned and analyzed. This represents the first example of the complete DNA sequence analysis of a polyene antibiotic biosynthetic gene cluster. Manipulation of the genes identified within the cluster may potentially lead to the generation of novel polyketides and yield improvements in the production strains.     

Rapid reagentless quantification of alginate biosynthesis in Pseudomonas fluorescens bacteria mutants using FT-IR spectroscopy coupled to multivariate partial least squares regression

Alginate is an important medical and commercial product and currently is isolated from seaweeds. Certain microorganisms also produce alginate and these polymers have the potential to replace seaweed alginates in some applications, mainly because such production will allow much better and more reproducible control of critical qualitative polymer properties. The research conducted here presents the development of a new approach to this problem by analysing a transposon insertion mutant library constructed in an alginate-producing derivative of the Pseudomonas fluorescens strain SBW25. The procedure is based on the non-destructive and reagent-free method of Fourier transform infrared (FT-IR) spectroscopy which is used to generate a complex biochemical infrared fingerprint of the medium after bacterial growth. First, we investigate the potential differences caused by the growth media fructose and glycerol on the bacterial phenotype and alginate synthesis in 193 selected P. fluorescens mutants and show that clear phenotypic differences are observed in the infrared fingerprints. In order to quantify the level of the alginate we also report the construction and interpretation of multivariate partial least squares regression models which were able to quantify alginate levels successfully with typical normalized root-mean-square error in predictions of only approximately 14%. We have demonstrated that this high-throughput approach can be implemented in alginate screens and we believe that this FT-IR spectroscopic methodology, when combined with the most appropriate chemometrics, could easily be modified for the quantification of other valuable microbial products and play a valuable screening role for synthetic biology.     

Electrostrictive counterforce on fluid microdroplet in short laser pulse

When a micrometer-sized fluid droplet is illuminated by a laser pulse, there is a fundamental distinction between two cases. If the pulse is short in comparison with the transit time for sound across the droplet, the disruptive optical Abraham-Minkowski radiation force is countered by electrostriction, and the net stress is compressive. In contrast, if the pulse is long on this scale, electrostriction is cancelled by elastic pressure and the surviving term of the electromagnetic force, the Abraham-Minkowski force, is disruptive and deforms the droplet. Ultrashort laser pulses are routinely used in modern experiments, and impressive progress has moreover been made on laser manipulation of liquid surfaces in recent times, making a theory for combining the two pertinent. We analyze the electrostrictive contribution analytically and numerically for a spherical droplet.     

Redox processes in the evaporation of N-phenylpyridinium salts in the mass spectrometer

N-Phenylpyridinium and 1,4-diphenylpyridinium halides undergo both one and two electron reductions to the N-phenyl- and 1,4-diphenylpyridine free radicals and the corresponding 1,2- and 1,4-dihydro derivatives respectively, prior to evaporation in the mass spectrometer. In addition, a third component is found in the gas phase, possibly due to dimerization of the free radical followed by dehydration.     

OPTICAL PROPERTIES OF HUMAN BRAIN

Abstract— Optical properties of the human brain in the wave-length region from blue to near infrared are presented. There are significant variations in the optical penetration depth from the neonatal and to the adult brain. Typical values for the penetration depth in the adult brain are: 0.5 mm for blue/green, 1.5 mm for red and 3.5 mm for near infrared. The values for the neonatal brain are typically 2–3 times larger.