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191.
An automated high-capacity sorption device for GC analysis of ultra trace components has been developed. The scope of the presented technique was to combine the simplicity of solid-phase microextraction (SPME) with the high extraction efficiency of the stir bar sorptive extraction technology. Sorptive extractions of water samples were performed using polydimethylsiloxane (PDMS) rubber tubing (120 microl) mounted onto a glass rod. The sampling procedure was carried out by a robotic autoinjector. Since the setup is fully automated, unattended and precise time-controlled extraction of samples is possible and makes quantitation with non-equilibrium extractions feasible. The sorption probes are easy to exchange, which facilitates off-line/in-field sampling. The system was evaluated with a test mixture of 44 environmentally hazardous compounds. Detection limits were found to be in the sub-ppt region. The performance of the system was demonstrated with the analysis of polycyclic aromatic hydrocarbons in urban snow. 相似文献
192.
Amendola V Mangano C Pallavicini P 《Dalton transactions (Cambridge, England : 2003)》2004,(18):2850-2854
Three-component systems made of a tetradentate bis-amino bis-quinoline ligand, a transition metal cation (Ni2+ or Cu2+) and a fluorescent indicator (Coumarin 343) have been studied in a water-dioxane (1 : 4 v/v) mixture, through potentiometric, pH-spectrophotometric and pH-fluorimetric titrations. For the Cu2+ containing systems, an "on-off-on" variation of fluorescence intensity vs. pH has been observed, whereas in the presence of Ni2+ a simple "on-off" profile of the fluorescence intensity vs. pH was obtained. These ternary systems thus behave as window-shaped or conventional pH-indicators, depending whether Cu2+ or Ni2+ is used as the cation. 相似文献
193.
We study the electronic and transport properties of artificial Au atomic chains on a NiAl(110) surface template using state-of-the-art first principles calculations. Au chains display remarkable one-dimensional electronic properties that can be tuned by the selective adsorption of small molecules: a single CO group is shown to modulate the electronic wave functions, acting as a "chemical scissor" along the chain, to strongly modify the coherent transport properties of the system, and to help design one-dimensional nanodevices through artificial profiling of energy barriers. 相似文献
194.
Di Cesare E Cerone G Enrici RM Tombolini V Anselmo P Masciocchi C 《Magnetic resonance imaging》2004,22(1):31-38
Our purpose was to evaluate the role of MRI in distinguishing fibrous from active residual masses in treated Hodgkin's disease. Forty patients with residual mediastinal mass larger than 1.5 cm underwent MRI 1, 3, 6, and 12 months after the end of cycles of prescribed chemotherapy or combined chemoradiotherapy. The MRI examinations were performed on a 0.5 and a 1.5 T systems, using T(1) before and after gadolinium injection and T(2)-weighted sequences. Each time the residual mass was evaluated in size and signal intensity on spin echo (SE) T(2)-weighted images and on SE T(1)-weighted images after contrast medium. Low signal intensity and low contrast enhancement were considered signs of inactive residues; homogeneous high signal intensity and high contrast enhancement were indicative of active residual disease; heterogeneous signal intensity and heterogeneous contrast enhancement were indicative of partial remission or necrotic/inflammatory phenomena. MR showed high diagnostic accuracy in the evaluation of Hodgkin's mediastinal residues after treatment, if performed at least 6 months after the end of therapy, reaching the highest sensitivity and specificity values at 12 month follow-up (considering the three parameters-T(2) signal intensity, contrast-enhancement, and size-all together). If we consider the single parameters individually, we can observe that size variation remains the more valuable parameter to predict or to exclude a relapse. MR diagnostic accuracy at the 6-month follow-up was lower due to the higher incidence of inhomogeneous pattern. The accuracy of MR performed at 1 and at 3 months after the end of therapy was not satisfying. This represents a clinical problem because the most important clinical decisions have to be taken just in this early post-treatment phase. 相似文献
195.
Sterpone F Pierleoni C Briganti G Marchit M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(11):4311-4314
Hydration of a spherical micelles of C12E6 in solution is studied by molecular dynamics simulation. The interface is found to be separated in an inner part composed of water and hydrophobic and hydrophilic moieties and an outer part with hydrophilic moiety and water only. Hydration numbers in the inner and in the outer parts are in excellent agreement with experimental data from various different methods. Temperature dehydration occurs in the inner region only and is related to the presence of water molecules directly in contact with the hydrophobic core at low temperature. 相似文献
196.
An integrated quantum mechanical approach for the structural and magnetic characterization of flexible free radicals in solution has been applied to a model of the glycyl radical engaged in peptidic chains. The hyperfine couplings computed using hybrid density functionals and purposely tailored basis sets are in good agreement with experiment when vibrational averaging effects from low frequency motions and solvent effects (both direct H bonding and bulk) are taken into the proper account. The g tensor shows a smaller dependence on the specific form of the density functional, the extension of the basis set over a standard double-zeta+polarization level, vibrational averaging, and bulk solvent effects. However, hydrogen bridges with solvent molecules belonging to the first solvation shell play a significant role. Together with their intrinsic interest, our results show that a comprehensive and reliable computational approach is becoming available for the complete characterization of open-shell systems of biological interest in their natural environment. 相似文献
197.
Fernandez YD Gramatges AP Amendola V Foti F Mangano C Pallavicini P Patroni S 《Chemical communications (Cambridge, England)》2004,(14):1650-1651
A new approach based on self-assembly inside micelles has been individuated to prepare a system behaving as a water-operating selective fluorescent sensor for Cu2+ and Ni2+. 相似文献
198.
Almost all studies of vortex states in helium II have been concerned with either ordered vortex arrays or disordered vortex tangles. This work numerically studies what happens in the presence of both rotation (which induces order) and thermal counterflow (which induces disorder). We find a new statistically steady state in which the vortex tangle is polarized along the rotational axis. Our results are used to interpret an instability that was discovered experimentally by Swanson et al. [Phys. Rev. Lett. 50, 190 (1983)]] and the vortex state beyond the instability that has been unexplained until now. 相似文献
199.
Grirrane A Pastor A Galindo A Ienco A Mealli C Rosa P 《Chemical communications (Cambridge, England)》2003,(4):512-513
The compound [Mn(tda)(bipy)] (tda = S(CH2COO)2(2-)) features the first structurally characterized tetra-carboxylate dimanganese antiferromagnetic system with 'copper acetate' core; the binuclear units, completed by bipyridine chelates, are doubly chained by the tda anions that adopt an unprecedented mu,mu'-eta1,eta1,eta1,eta1 coordination mode. 相似文献
200.