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71.
Cristina Giovannoli Gianfranco Giraudi Cinzia Tozzi Marcello Dolci 《Analytica chimica acta》2003,478(2):271-280
An enzyme-linked immunosorbent assay (ELISA) was used for the determination of fenoxycarb in apple leaf samples. Single step extraction procedures with phosphate-citrate buffered solution containing different amounts of methanol were tested showing that a solvent percentage of 20% (v/v) was the best condition, with recoveries between 85 and 100% in the working range of 25-500 μg kg−1 and a negligible matrix effect. The low detection limit reached, 1 μg kg−1 against 50 μg kg−1 for the recommended liquid chromatographic method, makes the ELISA more suitable for determinations of the fenoxycarb residues in apple leaf samples. The reliability of the ELISA was evaluated by assaying the insecticide in spiked and contaminated samples by three different approaches: direct determination, standard addition method with a calibration graph, and the dilution test. The corresponding coefficients of variation were, respectively, 11, 22 and 27%. The direct determination on the (1+1) diluted apple leaf extract was used to measure the insecticide residues in samples collected in the north-eastern Italian regions of Veneto and Trentino-Alto Adige. 相似文献
72.
Cristina Tealdi Lorenzo Malavasi Giorgio Flor 《Journal of solid state chemistry》2004,177(11):4359-4367
Atomistic computer simulation techniques have been used, for the first time, to reproduce the crystal structure of MgTa2O6 and to investigate the defect chemistry and dopant properties of this material. The calculated defect energetics suggest that the concentration of intrinsic atomic defects in this phase is insignificant and that the system is probably stable to both oxidation and reduction. Dopant solution energy versus ion size trends are found for both isovalent and aliovalent dopant incorporation at Mg and Ta sites. Divalent dopants (e.g. Ca, Cu) preferentially occupy the Mg site whereas dopants with higher charge (e.g. Sc, Zr, Nb) are more favorable on the Ta site. High migration activation energies (>2 eV) predict limited ionic conductivity in this material. 相似文献
73.
Complete 1H and 13C NMR assignments of aurasperone A and fonsecinone A, two bis-naphthopyrones produced by Aspergillus aculeatus 总被引:1,自引:0,他引:1
Campos FR Barison A Daolio C Ferreira AG Rodrigues-Fo E 《Magnetic resonance in chemistry : MRC》2005,43(11):962-965
Complete assignments of 1H and 13C NMR chemical shifts of the polyketides aurasperone A and fonsecinone A were made by means of nuclear Overhauser enhancement and heteronuclear NMR correlation experiments. These compounds were isolated for the first time from Aspergillus aculeatus, an endophytic fungus obtained from leaves of Melia azedarach(Meliaceae). 相似文献
74.
Ribeiro da Silva MA Gomes JR Ferreira AI 《The journal of physical chemistry. B》2005,109(27):13356-13362
The standard (p degrees = 0.1 MPa) molar enthalpies of formation of 2-, 3-, and 4-chloroaniline were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high-temperature vacuum sublimation technique was used to measure the enthalpies of vaporization or sublimation of the three isomers. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the three isomers of chloroaniline, in the gaseous phase, at T = 298.15 K, as 53.4 +/- 3.1 kJ.mol(-1) for 2-chloroaniline, 53.0 +/- 2.8 kJ.mol(-1) for 3-chloroaniline, and 59.7 +/- 2.3 kJ.mol(-1) for 4-chloroaniline. These values, which correct previously published data, were used to test the computational methodologies used. Therewith, gas-phase acidities, proton affinities, electron donor capacities, and N-H bond dissociation enthalpies were calculated and found to compare well with available experimental data for these parameters. 相似文献
75.
Nieto-Oberhuber C López S Echavarren AM 《Journal of the American Chemical Society》2005,127(17):6178-6179
New Au(I) complexes with bulky, biphenyl phosphines are the most reactive catalysts for the cyclizations of enynes. 1,6-Enynes with an aryl ring at the alkyne give 2,3,9,9a-tetrahydro-1H-cyclopenta[b]naphthalenes by a 5-exo-dig cyclization followed by a Nazarov-type ring expansion. 1,8-Dien-3-ynes also cyclize by a 5-exo-dig pathway to form hydrindanes. 相似文献
76.
ClaudiaG. Martínez Annette Neuner Cristina Martí Santi Nonell AndrM. Braun Esther Oliveros 《Helvetica chimica acta》2003,86(2):384-397
We have investigated the effect of a series of 18 solvents and mixtures of solvents on the production of singlet molecular oxygen (O2(1Δg), denoted as 1O2) by 9H‐fluoren‐9‐one (FLU). The normalized empirical parameter E derived from ET(30) has been chosen as a measure of solvent polarity using Reichardt's betaine dyes. Quantum yields of 1O2 production (ΦΔ) decrease with increasing solvent polarity and protic character as a consequence of the decrease of the quantum yield of intersystem crossing (ΦISC). Values of ΦΔ of unity have been found in alkanes. In nonprotic solvents of increasing polarity, ΦISC and, therefore, ΦΔ decrease due to solvent‐induced changes in the energy levels of singlet and triplet excited states of FLU. This compound is a poor 1O2 sensitizer in protic solvents, because hydrogen bonding considerably increases the rate of internal conversion from the singlet excited state, thus diminishing ΦΔ to values much lower than those in nonprotic solvents of similar polarity. In mixtures of cyclohexane and alcohols, preferential solvation of FLU by the protic solvent leads to a fast decrease of ΦΔ upon addition of increasing amounts of the latter. 相似文献
77.
Moret I Gambaro A Piazza R Corami F Ravazzi C Andreoli C Truzzi C Lambertucci L Scarponi G 《Annali di chimica》2004,94(5-6):373-387
During the period March 1997-March 1998 dimethyl sulphide (DMS), dimethylsulphoniopropionate (DMSP) and carbon disulphide (CS2) were determined weekly in the water of the Lagoon of Venice, Italy (at three stations located in the Giudecca Canal, the San Secondo Canal and the Rio di San Nicolò). At the same time, the following hydrological and biological variables were also measured: tide height, temperature, transmittance, fluorescence, pH, salinity, chlorinity, sulphate, ammonia, nitrite, nitrate, phosphate, silicate, chlorophyll a, phaeopigments, phytoplankton (abundance and biomass). Principal component analysis (PCA), applied as a dimension reduction tool, made it possible to summarize multivariate information in a small number of components, which highlighted the relationships between the temporal evolutions of the sulphur compounds with hydrological and biological variables in the seasonal biogeochemical cycle of the lagoon. In particular the overall temporal cycle, which begins with the development of biological activity in late winter and spring, followed by the predominance of degradation processes during the late summer and the remineralization of nutrients in autumn, is clearly described in the plane of the first two principal components, together with the interrelationships between all the relevant variables. 相似文献
78.
Abrunhosa F Faria S Gomes P Tomaz I Pessoa JC Andreu D Bastos M 《The journal of physical chemistry. B》2005,109(36):17311-17319
The interaction of two hybrid peptides of cecropin A and melittin [CA(1-8)M(1-18) and CA(1-7)M(2-9)] with liposomes was studied by differential scanning calorimetry (DSC), circular dichroism (CD), and quasi-elastic light scattering (QELS). The study was carried out with large unilamellar vesicles (LUVs) of three different lipid compositions: 1,2-dimyristoil-sn-glycero-3-phosphocholine (DMPC), 1,2-dimyristoyl-sn-glycero-3-phospho-rac-(1-glycerol) (DMPG) and a binary mixture of DMPC/DMPG, in a wide range of peptide-to-lipid (P:L) molar ratios (0 to 1:7). DSC results indicate that, for both peptides, the interaction depends on membrane composition, with very different behavior for zwitterionic and anionic membranes. CD data show that, although the two peptides have different secondary structures in buffer (random coil for CA(1-7)M(2-9) and predominantly beta-sheet for CA(1-8)M(1-18)), they both adopt an alpha-helical structure in the presence of the membranes. Overall, results are compatible with a model involving a strong electrostatic surface interaction between the peptides and the negatively charged liposomes, which gives place to aggregation in the gel phase and precipitation after a threshold peptide concentration. In the case of zwitterionic membranes, a progressive surface coverage with peptide molecules destabilizes the membrane, eventually leading to membrane disruption. Moreover, delicate modulations in behavior were observed depending on the peptide. 相似文献
79.
This paper discusses the partitioning of metals (K, Na, Ca, Mg, Al, Cu, Fe, Pb and Zn) between the aqueous phase and the suspended insoluble material in fog samples collected in the Po Valley during two extensive fields campaigns. Metals represent on average 11% of the mass of suspended insoluble matter, while the main component is carbon (both organic carbon, OC = 35%, and black carbon, BC = 8%). The unaccounted suspended matter mass is very high, on average 46%, and is attributable to non metallic species, such as O and N and of Si. The principal metals in the insoluble suspended fraction are Fe and Al (2-5%), while the contributions of other metals (Na, Mg, Cu, Pb and Zn) are lower than 1%. Ca and K exhibited high blank values and could not be detected above blank detection limit threshold. The main components in the aqueous phase are NO3- (34%), WSOC (23%), SO4(2-) (18%) and NH4+ (19%), while trace metals and remaining cations and anions accounted for less than 1% of solute mass. The main dissolved trace metals in fog droplets are Zn, Al and Fe, while the main metallic cations are Na and Ca. Fe and Al are the only metals preferentially distributed in the suspended insoluble matter of fog droplets (partitioning ratio respectively 37% and 33%). All other metals are mostly dissolved in the aqueous phase (mean partitioning ratios of Mg, Pb, Zn, Cu and Na are 69%, 70%, 77%, 81% and 87%). These findings are in agreement with literature data on metal speciation in cloud and rain samples. The dependence of partitioning ratios on pH is investigated for the different metals, with only Al showing a clear partitioning ratio decrease with increasing pH. Conversely, the other metals show no dependence or a complex and highly variable behaviour. The partitioning ratio of iron (mean 37%) observed in the Po Valley fog samples is much higher than the water extractable iron in aerosol particles (typically 1-2 %): this fact can be explained by differences in the aerosol sources and composition among sites and by chemical processes in the aqueous phase, such as complexation and redox reactions involving organic ligands (oxalate, or other organic acids as humic-like organic matter) which may promote Fe solubility. 相似文献
80.
Matthew N. Idso Ajay Suresh Akhade Mario L. Arrieta-Ortiz Bert T. Lai Vivek Srinivas James P. Hopkins Jr. Ana Oliveira Gomes Naeha Subramanian Nitin Baliga James R. Heath 《Chemical science》2020,11(11):3054
Antibiotic resistant infections are projected to cause over 10 million deaths by 2050, yet the development of new antibiotics has slowed. This points to an urgent need for methodologies for the rapid development of antibiotics against emerging drug resistant pathogens. We report on a generalizable combined computational and synthetic approach, called antibody-recruiting protein-catalyzed capture agents (AR-PCCs), to address this challenge. We applied the combinatorial protein catalyzed capture agent (PCC) technology to identify macrocyclic peptide ligands against highly conserved surface protein epitopes of carbapenem-resistant Klebsiella pneumoniae, an opportunistic Gram-negative pathogen with drug resistant strains. Multi-omic data combined with bioinformatic analyses identified epitopes of the highly expressed MrkA surface protein of K. pneumoniae for targeting in PCC screens. The top-performing ligand exhibited high-affinity (EC50 ∼50 nM) to full-length MrkA, and selectively bound to MrkA-expressing K. pneumoniae, but not to other pathogenic bacterial species. AR-PCCs that bear a hapten moiety promoted antibody recruitment to K. pneumoniae, leading to enhanced phagocytosis and phagocytic killing by macrophages. The rapid development of this highly targeted antibiotic implies that the integrated computational and synthetic toolkit described here can be used for the accelerated production of antibiotics against drug resistant bacteria.Antibody-recruiting protein-catalyzed capture agent (AR-PCCs) are a new class of all-synthetic and highly targeted antibiotics that recruit endogenous immune responses to eliminate drug-resistant microbes. 相似文献