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101.
Mazzucchelli I Rapetti M Fattore C Franco V Gatti G Perucca E 《Analytical and bioanalytical chemistry》2011,401(3):1013-1021
The development of a simple and rapid high-performance liquid chromatography (HPLC) method for the determination of the new
antiepileptic drug rufinamide (RFN) in human plasma and saliva is reported. Samples (250 μl) are alkalinized with ammonium
hydroxide (pH 9.25) and extracted with dichloromethane using metoclopramide as internal standard. Separation is achieved with
a Spherisorb silica column (250 × 4.6 mm i.d., 5 μm) at 30 °C using as mobile phase a solution of methanol/dichloromethane/n-hexane
10/25/65 (vol/vol/vol) mixed with 6 ml ammonium hydroxide. The instrument used was a Shimadzu LC-10Av chromatograph and flow
rate was 1.5 ml min-1, with a LaChrom L-7400 UV detector set at 230 nm. Calibration curves are linear [r
2 = 0.998 ± 0.002 for plasma (n = 10) and r
2 = 0.999 ± 0.001 for saliva (n = 9)] over the range of 0.25–20.0 μg ml-1, with a limit of quantification at 0.25 μg ml-1. Precision and accuracy are within current acceptability standards. The assay is suitable for pharmacokinetic studies in
humans and for therapeutic drug monitoring. 相似文献
102.
Aldo Arrais Eliano Diana Domenica Marabello Giuliana Gervasio Pier Luigi Stanghellini 《Journal of organometallic chemistry》2011,696(11-12):2299-2305
The synthesis of organometal complexes from chromium hexacarbonyl with 1-methyl-naphthalene ligand is reported. Two arene-chromium-tricarbonyl isomers are formed at competitive yields, featured with the metal fragment coordinated to both the methylated and the benzenic aromatic ring. A single-crystal X-ray diffraction measurement has been performed on the [(η6-5,6,7,8,9,10-C11H10)Cr(CO)3] isomer, which presents the metal carbonyl moiety attached to the benzenic arene ligand. The products of reaction have been studied by UV–VIS–NIR, fluorescence and 1H NMR spectroscopies. A detailed vibrational characterisation by mean of experimental FT-IR and Raman spectroscopy and DFT calculations is reported. The electron ligand donation to the metal carbonyl system, determined by FT-IR spectroscopy, has been related to the actual decrease of resonance energy of the aromatic hydrocarbon in the complex and compared with other chromium tricarbonyl complexes of different polycyclic aromatic hydrocarbons provided with the naphthalenic moiety. 相似文献
103.
Giorgetti M Guadagnini L Tonelli D Minicucci M Aquilanti G 《Physical chemistry chemical physics : PCCP》2012,14(16):5527-5537
A deep structural investigation predominantly by X-ray spectroscopic techniques is conducted on films of copper hexacyanoferrate (CuHCF) deposited under different conditions, aimed at establishing structure-properties relationships. We show that the potentiodynamic electrosynthesis of CuHCF on carbon-based surfaces produces a highly disordered material, with a variable amount of Prussian Blue (PB). The subsequent Cu(2+) intercalation induces the partial conversion of PB into CuHCF, which explains the improved electrocatalytic properties after the intercalation process. Both Cu and Fe K-edge data have been recorded. For the sample with the lower amount of PB, we could perform a multiple edge data analysis to determine the local atomic environment around both metal centres using the same set of structural parameters. The presence of high multiplicity Cu-N-C-Fe linear chains has allowed us to determine accurately the local environment of Fe while fitting the Cu K-edge data only. Using this approach we have retrieved structural information around Fe for those samples in which the concomitant presence of PB would have made impossible the analysis of the Fe K-edge. The Fe-C, C-N and Cu-N bond distances have been found in agreement with those of the bulk structures, but higher values of [Fe(CN)(6)] vacancies for the building blocks have been evidenced, reaching a value of ~45% in one sample. XANES, Raman and SEM data agree with the model proposed for each studied electrode. 相似文献
104.
Paolo Ciambelli Maria Sarno Giuliana Gorrasi Diana Sannino Mariarosaria Tortora 《Journal of Macromolecular Science: Physics》2013,52(5):779-795
Nanocomposite materials were prepared by incorporating multiwall carbon nanotubes (MWNTs), obtained by acetylene catalytic chemical vapor deposition (CCVD) on Co/Fe‐modified MgO, within poly(vinyl alcohol) (PVA). Before incorporation, nanotubes were oxidized to obtain better compatibilization with the polymer. It has been found that the addition of COOH‐functionalized and purified MWNTs improves the mechanical response, increases the glass transition temperature, and delays the thermal oxidation of PVA. Furthermore, the PVA crystallinity seems to be enhanced by the presence of nanotubes. 相似文献
105.
The stress-strength reliability $R=P(Y<X)$ , where $X$ and $Y$ are independent continuous random variables, has obtained wide attention in many areas of application, such as in engineering statistics and biostatistics. Classical likelihood-based inference about $R$ has been widely examined under various assumptions on $X$ and $Y$ . However, it is well-known that first order inference can be inaccurate, in particular when the sample size is small or in presence of unknown parameters. The aim of this paper is to illustrate higher-order likelihood-based procedures for parametric inference in small samples, which provide accurate point estimators and confidence intervals for $R$ . The proposed procedures are illustrated under the assumptions of Gaussian and exponential models for $(X,Y)$ . Moreover, simulation studies are performed in order to study the accuracy of the proposed methodology, and an application to real data is discussed. An implementation of the proposed method in the R software is provided. 相似文献
106.
Robert A. Mayanovic Alan J. Anderson Hingure A. N. Dharmagunawardhane Sakura Pascarelli Giuliana Aquilanti 《Journal of synchrotron radiation》2012,19(5):797-805
Radiolysis‐induced effects on aqueous tungsten ions are observed to form a precipitate within seconds upon exposure to a synchrotron X‐ray micro‐beam in a WO3 + H2O system at 873 K and 200 MPa. In situ Fe K‐edge energy‐dispersive X‐ray absorption spectroscopy (ED‐XAS) measurements were made on Fe(II)Cl2 aqueous solutions to 773 K in order to study the kinetics of high‐temperature reactions of Fe2+ and Fe3+ ions with transient radiolysis species. The radiolytic reactions in a fluid sample within a hydrothermal diamond anvil cell result in oxidation of the Fe2+ ion at 573 K and reduction of Fe3+ at temperatures between 673 and 773 K and of the Fe2+ ion at 773 K. The edge‐energy drift evident in the ED‐XAS data directly reflects the kinetics of reactions resulting in oxidation and/or reduction of the Fe2+ and Fe3+ ions in the aqueous solutions at high temperatures. The oxidation and reduction trends are found to be highly consistent, making reliable determinations of reaction kinetics possible. 相似文献
107.
Tommaso R. I. Cataldi Giampaolo Ricciardi Giuliana Bianco Daniela Pietrangeli Salvatore Abate 《Rapid communications in mass spectrometry : RCM》2009,23(13):1927-1933
Some newly synthesized 10B nido‐carborane derivatives, i.e., 7,8‐dicarba‐nido‐undecaborane monoanions ([7‐Me‐8‐R‐C2B9H10]‐K+, R = H, butyl, hexyl, octyl and decyl), have been fully characterised and examined by electrospray ionization and Fourier transform ion cyclotron resonance mass spectrometry with liquid chromatographic separation (LC/ESI‐FTICR‐MS). These boron‐containing compounds exhibit abundant molecular ions ([M]?) at m/z 140.22631 [CB9H14]?, m/z 196.28883 [CB9H22]?, m/z 224.32032 [CB9H26]?, m/z 252.35133 [CB9H30]? and m/z 280.38354 [CB9H34]? at the normal tube lens voltage setting of ?90 V, which was an instrumental parameter value selected in the tuning operation. Additional [M–nH2]? (n = 1?4) ions were observed in the mass spectra when higher tube lens voltages were applied, i.e., ?140 V. High‐resolution FTICR‐MS data revealed the accurate masses of fragment ions, bearing either an even or an odd number of electrons. Collision‐induced dissociation of the [M–nH2]? ions (n = 0–4) in the quadrupole linear ion trap (LTQ) analyzer confirmed the loss of hydrogen molecules from the molecular ions. It is suggested that the loss of H2 molecules from the alkyl chain is a consequence of the stabilization effect of the nido‐carborane charged polyhedral skeleton. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
108.
Romo Arago Dougu Kentsop Valeria Iobbi Giuliana Donadio Barbara Ruffoni Nunziatina De Tommasi Angela Bisio 《Molecules (Basel, Switzerland)》2021,26(17)
Salvia corrugata Vahl. is an interesting source of abietane and abeo-abietane compounds that showed antibacterial, antitumor, and cytotoxic activities. The aim of the study was to obtain transformed roots of S. corrugata and to evaluate the production of terpenoids in comparison with in vivo root production. Hairy roots were initiated from leaf explants by infection with ATCC 15834 Agrobacterium rhizogenes onto hormone-free Murashige and Skoog (MS) solid medium. Transformation was confirmed by polymerase chain reaction analysis of rolC and virC1 genes. The biomass production was obtained in hormone-free liquid MS medium using Temporary Immersion System bioreactor RITA®. The chromatographic separation of the methanolic extract of the untransformed roots afforded horminone, ferruginol, 7-O-acetylhorminone and 7-O-methylhorminone. Agastol and ferruginol were isolated and quantified from the hairy roots. The amount of these metabolites indicated that the hairy roots of S. corrugata can be considered a source of these compounds. 相似文献
109.
Giuliana Gorrasi Liberata Guadagno Concetta D'Aniello Carlo Naddeo Gennaro Romano Vittoria Vittoria 《Macromolecular Symposia》2003,203(1):285-294
Three syndiotactic polypropylene samples were crystallized under different conditions in order to obtain different polymorphs. A first sample was crystallized at high temperature, obtaining the helical form I; a second was crystallized from the melt at 0°C for many days obtaining the trans-planar mesophase; a third sample was obtained by solvent induced crystallization followed by annaeling of the trans-planar mesophase, leading to a mixture of both the helical forms I and II. In the dynamic-mechanical analysis the helical form I showed only one peak of tan δ corresponding to the amorphous glass transition. The other polymorphs also showed this transition centered at about the same temperature. Beside the peak corresponding to the Tg, the trans-planar mesophase was characterized by a peak appearing at 70°C, and the helical form II by a peak at 100°C. These peaks, unambiguously associated to transitions of the different forms, can be considered a distinctive evidence for the polymorphs obtained in different processing conditions. 相似文献
110.
Fulvia Felluga Maurizio Fermeglia Marco Ferrone Giuliana Pitacco Sabrina Pricl Ennio Valentin 《Helvetica chimica acta》2002,85(11):4046-4054
Enantiomerically pure methyl esters of (+)‐(2R,3S)‐ and (−)‐(2S,3R)‐5‐oxo‐2‐pentylpyrrolidine‐3‐carboxylic acid with 99% and 98% ee were obtained by enzymatic resolution of the corresponding racemic mixture using α‐chymotrypsin and pig‐liver acetone powder, respectively. Their absolute configurations were established by chemical methods, i.e., conversion of the trans‐γ‐lactam moiety to the corresponding γ‐lactone of known configuration. The favorable interactions between the trans‐γ‐lactam and α‐chymotrypsin were rationalized by molecular‐mechanics calculations, which suggest a different situation for the cis‐diastereoisomer. 相似文献