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931.
Rizzi A Cosmina P Flego C Montanari L Seraglia R Traldi P 《Journal of mass spectrometry : JMS》2006,41(9):1232-1241
The molecular weight distribution of the asphaltene fractions of two types of crude oils from two different Italian fields (samples 1 and 2) was investigated. The analytical tools used to perform these analyses were matrix assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI) mass spectrometry. After observing that the use of the matrix (as well as the addition of Ag+) did not improve the quality of the data compared to that obtained in LDI conditions, all further measurements were performed with the latter technique. Operating under usual conditions of laser power and delay time, a very low resolution was observed, showing only macroscopic differences between the two samples in the molecular weight distribution of the different components. An accurate study on the possible reasons of this undesirable behavior indicates that it can originate from space charge phenomena occurring either in the ion source region or during the flight. A valid parameterization of the delay time and the laser power allowed higher quality spectra to be obtained. Surface-enhanced laser desorption ionization (SELDI) measurements were also performed using normal phase (silica) as the sample holder surface. Under these conditions, better results are obtained, proving that the sample-surface interaction is important to achieve, by means of laser irradiation, a homogeneous set of product ions. Both asphaltene samples were fractionated in five subfractions by gel-permeation chromatography (GPC) to obtain a better separation of the molecular weight distributions; the related spectra confirmed these findings. By using different approaches, relevant and reproducible differences between the asphaltene fractions of the two oil samples were observed. 相似文献
932.
Atmospheric deposition represents a significant source of heavy metals entering soil and aquatic ecosystems. The evaluation of their vulnerability can be carried out by the Critical Load criterion. In this work we focus the attention on the terrestrial ecosystems in the Province of Bologna, estimating the maximum tolerable load of cadmium and lead they are able to bear without sustain the occurrence of harmful ecotoxicological effects. To this aim the Steady-State Mass Balance method is applied on a small scale (10 x 10 Km EMEP grids) and the more suitable approach to define critical limits for the Province condition, effect-base or stand-still, is discussed. The opportunity of simplifying the input data collection is also considered, trying to deduce soil properties from geological information. Finally, the environmental risk due to the present deposition of Pb and Cd on provincial soils is described as exceedances over the critical loads. 相似文献
933.
Luciano Callipo Patrizia Foglia Riccardo Gubbiotti Roberto Samperi Aldo Laganà 《Analytical and bioanalytical chemistry》2009,394(3):811-820
A method for carbonic anhydrase II (CA II) absolute quantification in human serum is presented. This method is based on high-performance
liquid chromatography (HPLC)-Chip microfluidic device incorporating a nanoelectrospray source interfaced to a triple quadrupole
mass spectrometer. The fraction containing CA II was isolated by preparative reversed-phase HPLC, and peptides obtained from
the tryptic digest of the protein mixture were separated by the HPLC-Chip system. The multiple-reaction monitoring acquisition
mode of a selected suitable CA II peptide and peptide internal standard allowed the selective and sensitive determination
of a CA II. Absolute recovery of the method was 52 ± 12%, while analytical recovery was 81 ± 10%. For the eight samples analyzed,
the matrix effect was found to be only −14 ± 6%. A comparison among three regression lines type which were obtained by external
calibration, matrix-matched calibration, and standard addition method, respectively, demonstrated that the first one is adequate
in obtaining good accuracy and precision. Method quantification limit for CA II in serum was estimated to be 2 fmol/mL. CA
II mean concentration in sera from eight healthy subjects was found to be 56 pmol/mL (relative standard deviation 24%). 相似文献
934.
Rodrigo V. Salvatierra Luciano G. Moura Marcela M. Oliveira Marcos A. Pimenta Aldo J. G. Zarbin 《Journal of Raman spectroscopy : JRS》2012,43(8):1094-1100
Thin, transparent, and self‐assembled films of neat polyaniline and polyaniline/carbon nanotube nanocomposites were deposited over glass substrates by interfacial polymerization. The effect of the carbon nanotubes on the structure and conformation of the polyaniline, and the type of interaction between the polymer and the nanotubes, have been studied by resonant Raman spectroscopy and UV–Vis and Raman spectroelectrochemistry. The results indicate clearly that the carbon nanotubes induce important changes in the electronic structure of the polymer, resulting in a more polaronic organization. Additionally, an effective interaction between the polymer and the nanotube, based on a polyaniline‐to‐nanotube charge transfer, is proposed in this work. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
935.
The classification of texts has become a major endeavor with so much electronic material available, for it is an essential task in several applications, including search engines and information retrieval. There are different ways to define similarity for grouping similar texts into clusters, as the concept of similarity may depend on the purpose of the task. For instance, in topic extraction similar texts mean those within the same semantic field, whereas in author recognition stylistic features should be considered. In this study, we introduce ways to classify texts employing concepts of complex networks, which may be able to capture syntactic, semantic and even pragmatic features. The interplay between various metrics of the complex networks is analyzed with three applications, namely identification of machine translation (MT) systems, evaluation of quality of machine translated texts and authorship recognition. We shall show that topological features of the networks representing texts can enhance the ability to identify MT systems in particular cases. For evaluating the quality of MT texts, on the other hand, high correlation was obtained with methods capable of capturing the semantics. This was expected because the golden standards used are themselves based on word co-occurrence. Notwithstanding, the Katz similarity, which involves semantic and structure in the comparison of texts, achieved the highest correlation with the NIST measurement, indicating that in some cases the combination of both approaches can improve the ability to quantify quality in MT. In authorship recognition, again the topological features were relevant in some contexts, though for the books and authors analyzed good results were obtained with semantic features as well. Because hybrid approaches encompassing semantic and topological features have not been extensively used, we believe that the methodology proposed here may be useful to enhance text classification considerably, as it combines well-established strategies. 相似文献
936.
Emiliano L. Muñoz Marcio E. Mercurio Moacir R. Cordeiro Luciano F.D. Pereira Artur W. Carbonari Mario Rentería 《Physica B: Condensed Matter》2012,407(16):3121-3124
In this work, we present results of Time-Differential γ–γ Perturbed-Angular-Correlations (PAC) experiments performed in 111Cd-doped ZnO semiconductor. The PAC technique has been applied in order to characterize the electric-field-gradient (EFG) tensor at (111In (EC)→) 111Cd nuclei located, as was later demonstrated, at defect-free cation sites of the ZnO host structure. The PAC experiments were performed in the temperature range of 77–1075 K. At first glance, the unexpected presence of low-intensity dynamic hyperfine interactions was observed, which were analyzed with a perturbation factor based on the Bäverstam and Othaz model. The experimental EFG results were compared with ab initio calculations performed with the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) method, in the framework of the Density Functional Theory (DFT), using the Wien2K code. The presence of the dynamic hyperfine interactions has been analyzed enlightened by the FP-APW+lo calculations of the EFG performed as a function of the charge state of the cell. We could correlate the large strength of the dynamic hyperfine interaction with the strong variation of the EFG due to changes in the electronic charge distribution in the Cd vicinity during the time-window of the PAC measurement. It was also revealed that the Cd impurity decays to a final stable neutral charge state (Cd2+) fast enough (in few ns) to produce the nearly undamped observed PAC spectra. 相似文献
937.
There are an extensive variety of experiments in quantum optics that emphasize the non-local character of the coincidence measurements recorded by spatially separated photocounters. These are the cases of ghost image and other interference experiments based on correlated photons produced in, for instance, the process of parametric down-conversion or photon cascades. We propose to analyse some of these correlations in the light of stochastic optics, a local formalism based on classical electrodynamics with added background fluctuations that simulate the vacuum field of quantum electrodynamics, and raise the following question: can these experiments be used to distinguish between quantum entanglement and classical correlations? 相似文献
938.
Rodrigo A. Lemos Silva Daniel F. Scalabrini Machado Núbia Maria Nunes Rodrigues Heibbe C. B. de Oliveira Luciano Ribeiro Demtrio A. da Silva Filho 《Molecules (Basel, Switzerland)》2022,27(9)
In this work, a theoretical investigation of the effects caused by the doping of C20 with silicon (Si) atom as well as the adsorption of CO, CO2 and N2 gases to C20 and C19Si fullerenes was carried out. In concordance with previous studies, it was found that the choice of the doping site can control the structural, electronic, and energetic characteristics of the C19Si system. The ability of C20 and C19Si to adsorb CO, CO2 and N2 gas molecules was evaluated. In order to modulate the process of adsorption of these chemical species to C19Si, an externally oriented electric field was included in the theoretical calculations. It was observed that C19Si is highly selective with respect to CO adsorption. Upon the increase of the electric field intensity the adsorption energy was magnified correspondingly and that the interaction between CO and C19Si changes in nature from a physical adsorption to a partial covalent character interaction. 相似文献
939.
940.
Maurizio Chiminelli Dr. Andrea Serafino Davide Ruggeri Prof. Luciano Marchiò Prof. Franca Bigi Prof. Raimondo Maggi Prof. Max Malacria Prof. Giovanni Maestri 《Angewandte Chemie (International ed. in English)》2023,62(12):e202216817
Dearomative cycloadditions are a powerful tool to access a large chemical space exploiting simple and ubiquitous building blocks. The energetic burden due to the loss of aromaticity has however greatly limited their synthetic potential. We devised a general intramolecular method that overcomes these limitations thanks to the photosensitization of allenamides. The visible-light-promoted process gives complex [2.2.2]-(hetero)-bicyclooctadienes at room temperature, likely through the stabilization of transient (bi)radicals by naphthalene. The reaction tolerates several valuable functionalities, offering a convenient handle for a myriad of applications, including original isoindoles and metal complexes. 相似文献