Halocarbons in Antarctic Surface Waters

Abstract

Surface water samples taken during the 1988–89, 1989–90 and 1990–91 Italian expeditions were analyzed for the presence of carbon tetrachloride, trichloroethylene and tetrachloroethylene. The sample analysis was carried out by solvent extraction and capillary GC-ECD-MS determination. The above-mentioned halocarbons were at ng/l level in all water samples investigated.     

Secondary Metabolites,including a New 5,6-Dihydropyran-2-One,Produced by the Fungus Diplodia corticola. Aphicidal Activity of the Main Metabolite,Sphaeropsidin A

An undescribed 5,6-dihydropyran-2-one, namely diplopyrone C, was isolated and characterized from the cultures of an isolate of the fungus Diplodia corticola recovered from Quercus suber in Algeria. The structure and relative stereostructure of (5S,6S,7Z,9S,10S)-5-hydroxy-6-(2-(3-methyloxiran-2-yl)vinyl)-5,6-dihydro-2H-pyran-2-one were assigned essentially based on NMR and MS data. Furthermore, ten known compounds were isolated and identified in the same cultures. The most abundant product, the tetracyclic pimarane diterpene sphaeropsidin A, was tested for insecticidal effects against the model sucking aphid, Acyrthosiphon pisum. Results showed a toxic dose-dependent oral activity of sphaeropsidin A, with an LC₅₀ of 9.64 mM.     

On-line analysis of volatile chlorinated hydrocarbons in air by gas chromatography–mass spectrometry: Improvements in preconcentration and injection steps

An analytical system composed of a cryofocusing trap injector device coupled to a gas chromatograph with mass spectrometric detection (CTI-GC–MS) specific for the on-line analysis in air of volatile chlorinated hydrocarbons (VCHCs) (dichloromethane; chloroform; 1,1,1-trichloroethane; tetrachloromethane; 1,1,2-trichloroethylene; tetrachloroethylene) was developed. The cryofocusing trap injector was the result of appropriate low cost modifications to an original purge-and-trap device to make it suitable for direct air analysis even in the case of only slightly contaminated air samples, such as those from remote zones. The CTI device can rapidly and easily be rearranged into the purge-and-trap allowing water and air analysis with the same apparatus. Air samples, collected in stainless steel canisters, were introduced directly into the CTI-GC–MS system to realize cryo-concentration (at −120 °C), thermal desorption (at 200 °C) and for the subsequent analysis of volatiles. The operating phases and conditions were customised and optimized. Recovery efficiency was optimized in terms of moisture removal, cold trap temperature and sampling mass flow. The injection of entrapped volatiles was realized through a direct transfer with high chromatographic reliability (capillary column–capillary column). These improvements allowed obtaining limits of detection (LODs) at least one order of magnitude lower than current LODs for the investigated substances. The method was successfully employed on real samples: air from urban and rural areas and air from remote zones such as Antarctica.     

Analytical and Experimental Investigation of Squeeze-Film Dampers Executing Circular Orbits

We have referred here the first results obtained in the course of an experimental research intended to examine oil film pressure of a squeeze film damper (with inertialess lubricant) executing circular orbits. An analytical expression for pressure arising into the gap was obtained before, for the short bearing SFD, in the general case of offset circular orbits. The expression obtained has permitted, in a simple way, the examination of the influence of the offset on pressure. Two approximated expressions for pressure (the one for pressure as a function of time at a fixed measuring section, the other for pressure along the circumference of the bearing at a given time), corresponding to centered orbits, were compared with the exact ones. We observed that the limits within which the nondimensional offset can be considered negligible, change according to comparisons between circumferential pressure diagrams or between pressure diagrams as functions of time. In the second case they are much wider. The experimental results concerned offset orbits with nominal radius r=0.5C and offset <0.1. Good accordance between theoretical and experimental pressure trends has been found, as concerns the positive part of dynamic pressure. As concerns the negative part of dynamic pressure, tests have shown that cavitation takes place for a more or less wide length, depending on feeding groove pressure, other conditions being equal. Complete effective pressure diagram coinciding with the theoretical one has been found for particular feeding conditions. Oil film tensile stresses have been frequently detected with both complete and incomplete diagrams owing to cavitation. Maximum measured tensile stress was about 220kN/m². It was finally found that theoretical and experimental trends are coincident only if the SFD is not starved. Analytical expression for pressure in the long bearing SFD executing offset circular orbits is referred in the appendix.     

HPLC determination of the aromatic fraction of gasoline

Summary This work reports a rapid and easy procedure for the analysis of the aromatic fraction in gasoline. No sample pretreatment is required, since the gasoline is diluted in methanol and directly injected into a liquid chromatograph. A spectrophotometer detector and a spectrofluorimeter detector are used in series. The procedure has been applied to a large number of Italian and European refined gasoline samples.Dedicated to Prof. Dr. A. Liberti on the occasion of his 70th birthday.     

Approximate values for force constant and wave number associated with a low-frequency concerted motion in proteins can be evaluated by a comparison of X-ray structures

Low-frequency internal motions in protein molecules play a key role in biological functions. A direct relationship between low-frequency motions and enzymatic activity has been suggested for bovine pancreatic ribonuclease (RNase A). The flexibility-function relationship in this enzyme has been attributed to a subtle and concerted breathing motion of the beta-sheet regions occurring upon substrate binding and release. Here, we calculate an approximate value for the force constant and the wave number of the low-frequency beta-sheet breathing motion of RNase A, by using the Boltzmann hypothesis on a set of data derived from a simple conventional structural superimposition of an unusual large number of X-ray structures available for the protein. The results agree with previous observations and with theoretical predictions on the basis of normal-mode analysis. To the best of our knowledge, this is the first example in which the wave number and the force constant of a low-frequency concerted motion in a protein are directly derived from X-ray structures.     

Structural and stereochemical revision of isocyanide and isothiocyanate amphilectenes from the Caribbean marine sponge Cribochalina sp.

The absolute stereochemistry of amphilectene metabolites from Cribochalina sp. has been revised by a detailed NMR spectroscopic study of the Mosher ester derivatives of a related alcohol. The relative stereochemistry of the previously described amphilectenes has been reinvestigated and reassigned on the basis of the X-ray structural analysis carried out on one of them. The structure of a new amphilectene metabolite, which is an isothiocyanato analogue is also presented.     

Evaluation of volatile chlorinated hydrocarbons distribution along depth profiles in the Ross Sea, Antarctica

The presence and the distribution along depth profiles of volatile chlorinated hydrocarbons (VCHCs) were evaluated in seawater samples collected in the Ross Sea (Southern Ocean, Antarctica) during the 2002-2003 Italian expedition. Sampling areas were located where the Circumpolar Deep Water interacts with the shelf waters that supply the Ross Sea.The VCHCs investigated were: 1,1,1-trichloroethane (C₂H₃Cl₃), tetrachloromethane (CCl₄), trichloroethylene (C₂HCl₃), tetrachloroethylene (C₂Cl₄). The analytical procedure consisted of a liquid-liquid extraction carried out with n-hexane directly in Antarctica, followed by gas chromatographic analysis with electron capture detection carried out in Italy.Concentration levels for the VCHCs analysed ranged from digits to hundreds of ng/L according to the station, depth and substance considered. Important differences in concentration levels between the three stations near the Ross Ice Shelf and the two stations located in the Cape Adare area were observed. In particular the stations situated in the Cape Adare zone, at certain depths, showed a thermal inversion due to the mixing of the Circumpolar Deep Water with the waters generated inside the Ross Sea Basin. The lowest concentration levels were recorded at this temperature increase.     

Evolution of the nth Stokes-wave due to stimulated Raman scattering in single-mode fibers

The evolution of the nth analytical solutions of commonly used Raman equations, analyzed by numerical simulation and experimentally, is reported. In the experiment, a 1 km undoped single-mode fiber was pumped with an ytterbium doped fiber laser system (FL) in continuous wave regime at 1064 nm in a free running configuration. We showed that it is possible to obtain up to the nth power thresholds and the maximum power for each Stokes wave by using compact analytical solutions as a first approximation in a simple, quick process.