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51.
Maria Helena Garcia Pedro Florindo Maria de Fátima M. Piedade Stefano Maiorana Emanuela Licandro 《Polyhedron》2009
A series of organometallic complexes possessing new tetrathia-[7]-helicene nitrile derivative ligands [TH-7] as chromophores, of general formula [MCp(P–P)(NC{TH-[7]-Y}Z)][PF6] (M = Ru, Fe, P–P = DPPE, Y = H, NO2, Z = H, C≡N; M = Ru, L–L = 2PPh3, Y = H, Z = H) has been synthesized and fully characterized. 1H NMR, FT-IR and UV–Vis. spectroscopic data were analyzed with in order to evaluate the existence of electronic delocalization from the metal centre to the coordinated ligand to have some insight on the potentialities of these new compounds as non-linear optical molecular materials. Slow crystallization of compound [RuCp(PPh3)2(NC{TH-[7]-H}H)][PF6] 2Ru revealed an interesting isomerization of the helical ligand with formation of two carbon-carbon bonds between the two terminal thiophenes, leading to the total closure of the helix (2*Ru). 相似文献
52.
Daniela Chirio Marina Gallarate Michele Trotta Maria Eugenia Carlotti Emanuela Calcio Gaudino Giancarlo Cravotto 《Journal of inclusion phenomena and macrocyclic chemistry》2009,65(3-4):391-402
Solid lipid nanoparticles (SLN) made of different triglycerides (TG) in the presence and in the absence of various modified α- and γ-cyclodextrins (CD) were prepared by the solvent injection technique. A new synthesis of lipophilic derivatives of γ- CD was developed in this work. Curcumin (CU), a natural polyphenol with antitumor, antioxidant and anti-inflammatory properties, was used as model drug. SLNs mean sizes were in the 250–800 nm range and afforded CU entrapment efficiency in the 12–85% range. The presence of CD derivatives with almost the same chain length of TG induced an improvement of nanoparticle characteristics decreasing mean size values and increasing CU entrapment efficiency. A significant reduction in CU photodegradation was noted only when the drug was vehicled in tristearin-SLN, which became less pronounced in the presence of CD-derivatives, determining a loss in photoprotection. The hydrolytic stability of curcumin was highly improved by drug loading in tristearin-SLN, and only slightly by loading it in tricaprin-SLN, and this seemed not to be influenced by the presence of CD derivatives. Skin uptake studies revealed an increase in CU skin accumulation when CU was loaded in SLN obtained with all CD derivatives, particularly with most lipophilic one. 相似文献
53.
Giuseppe Fiume Annalisa Rossi Emanuela Di Salle Carmen Spatuzza Massimo Mallardo Giuseppe Scala Ileana Quinto 《Computational Biology and Chemistry》2009,33(6):434-439
MicroRNAs (miRNAs) are small single-stranded RNA molecules that play an essential role in the regulation of gene expression and cell physiology. Gene rearrangements occurring in the miRNA sequence are associated with cancer. The IBTK genetic locus is located in the genomic sequence 6q14.1 that undergoes chromosomal aberration in lymphoproliferative disorders. The IBTK gene encodes the proteins IBtk-α, β and γ that regulate the B cell receptor signalling through Bruton's tyrosine kinase, which promotes B cell survival and differentiation. Pro-MirII-based analysis predicted four precursors of microRNAs (pre-miR) encoded by introns 17, 21, 26 and the 3′ un-translated region of the IBTK gene. Pre-miR-IBTK3, which was encoded by intron 26, was the effective substrate of RNase III Dicer in vitro as well as the precursor of an IBtk miRNA generated in vivo. By CLUSTALW-based analysis, pre-miR-IBTK3 homologues were found in Pan troglodytes, Pongo pygmaeus and Macaca mulatta, suggesting an evolutionary conserved function in primates. 相似文献
54.
Fidani M Casagni E Montana M Pasello E Pecoraro C Gambaro V 《Rapid communications in mass spectrometry : RCM》2006,20(16):2441-2446
Bacteria frequently found in equine urine samples may cause degradation of 17beta-OH steroids. A simple liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed to evaluate the microbiological contamination of equine urine as a marker of poor storage conditions. Norethandrolone was used as the internal standard, and the linearity, sensitivity, precision and accuracy of the method were evaluated. 17beta-OH oxidation was demonstrated for testosterone, nandrolone, trenbolone and boldenone, but did not occur in alpha-epimers such as alpha-boldenone and epitestosterone, demonstrating the stereoselectivity of the reaction. A rapid test was performed by spiking one of the four 17beta-OH steroids in samples of diluted equine urine. The steroids were transformed into their respective ketones in the presence of bacterial activity. The test allows direct injection of diluted samples into the LC/MS system, without the need for prior extraction. Results show that the best method of storage is freezing at -18 degrees C. Urine specimens should be analyzed as soon as possible after thawing. This allows bacterial degradation of equine urine to be arrested temporarily, so that the urine can be used for qualitative or quantitative analysis of 17beta-OH steroids. 相似文献
55.
Soxhlet extraction, ultrasound-assisted extraction (USAE) and microwaves-assisted extraction (MAE) in closed system have been investigated to determine the content of coumarin, o-coumaric and melilotic acids in flowering tops of Melilotus officinalis. The extracts were analyzed with an appropriate HPLC procedure. The reproducibility of extraction and of chromatographic analysis was proved. Taking into account the extraction yield, the cost and the time, we studied the effects of extraction variables on the yield of the above-mentioned compounds. Better results were obtained with MAE (50% v/v aqueous ethanol, two heating cycles of 5 min, 50 degrees C). On the basis of the ratio extraction yield/extraction time, we therefore propose MAE as the most efficient method. 相似文献
56.
Lucia Calucci Emanuela Grigiotti Guido Pampaloni Calogero Pinzino Piero Zanello 《Journal of organometallic chemistry》2006,691(5):829-836
The reaction of Cr(η6-CH3C6H5)2 with 1-benzoyl-6-hydroxy-6-phenyl fulvene, dbcpH, and with pentakis(methoxycarbonyl)cyclopentadiene, pcmcpH, proceeds with evolution of dihydrogen and the formation of the ionic derivatives [Cr(η6-CH3C6H5)2][X] ([X]− = 1,2-dibenzoylcyclopentadienyl, [dbcp]−, pentakis(methoxycarbonyl)cyclopentadienyl, [pcmcp]−), which have been characterized by IR and EPR spectroscopies, X-ray diffraction and electrochemical techniques. The sterically demanding anions do not affect the structural and electronic properties of the cations in solution but strongly influence crystal packing. In fact, a rare cis-eclipsed conformation of the toluene rings is found for [Cr(η6-CH3C6H5)2][dbcp] · THF, whereas two independent complexes are observed in the unit cell of [Cr(η6-CH3C6H5)2][pcmcp], one with toluene rings in a cis-eclipsed conformation and the other in a staggered conformation (projections of methyl groups form an angle of 151°). 相似文献
57.
Emanuela Bianchi Janetti Ishai Dror Monica Riva Alberto Guadagnini Xavier Sanchez-Vila Brian Berkowitz 《Transport in Porous Media》2013,97(3):295-315
We study the mobility and interaction under competing conditions observed for copper ( $\text{ Cu}^{2+}$ ) and zinc ( $\text{ Zn}^{2+}$ ) ions in the context of laboratory-scale experiments performed in natural soil columns. The experiments focus on the analysis of solute breakthrough curves (BTCs) obtained after injection of an aqueous solution containing similar concentrations of the two metal ions into a soil column fully saturated with double deionized water. Transport of the competing ions is tested for the same soil under aerobic and anaerobic conditions. Measurements show that the species with lower affinity for the soil, $\text{ Zn}^{2+}$ , migrates occupying all available adsorption sites, and is then progressively replaced by the ion with higher affinity, $\text{ Cu}^{2+}$ . The two ions are displaced in the system with different effective retardation. The slowest species replaces the sorbed ions, resulting in observed $\text{ Zn}^{2+}$ concentrations that display a non-monotonic behavior in time and which, for a certain period, are larger than the concentration supplied continuously at the inlet. In the absence of a complete geochemical characterization of the system, we show that the measured concentrations of both metals can be interpreted through simple models based on a set of coupled partial differential and algebraic equations, involving a small subset of aqueous and adsorbed species that are present in the system. Depending on the model considered, the relationship between aqueous and adsorbed ion concentrations is described at equilibrium by a Gaines–Thomas (GT) formulation, a competitive Sheindorf–Rebhun–Sheintuch (SRS) isotherm, or an Extended Langmuir (EL) isotherm, respectively. The GT formulation provides the best interpretation of the observed behavior among the models tested. We find that employing these simple models, which account only for the main governing reactive processes, allows reasonable estimation of the observed BTCs in experiments where only partial geochemical datasets are available. 相似文献
58.
59.
Cuoghi A Caiazzo M Bellei E Monari E Bergamini S Palladino G Ozben T Tomasi A 《Analytical and bioanalytical chemistry》2012,404(6-7):2097-2104
Chronic renal failure patients accumulate in the blood molecules that are normally excreted into the urine. p-Cresol Sulphate (pCS), the most representative retained toxin, shows a high level of toxicity. Therefore, its quantification could represent a prediction factor to determine the risk of endothelial dysfunction and cardiovascular complication and response to the haemodialysis treatment. The aim of this study was to evaluate the suitability of the multiple reaction monitoring (MRM) technique in order to improve the sensibility, the selectivity and the timing of pCS detection in a small amount of plasma. Deproteinized plasma of uremic patients was concentrated and dissolved in liquid chromatography (LC) mobile phase solution. pCS was quantified by LC coupled to tandem mass spectrometry (LC-MS/MS) on a triple-quadrupole mass spectrometer. Selective and sensitive detection of pCS was achieved by selecting the specific parent ion and monitoring two specific fragment ions. The MRM assay was carried out using the following transitions: m/z 187?→?80.00 and m/z 187?→?107.00. A good linearity was observed for each calibration curve. The intra-day and inter-day results showed a good precision and repeatability. The percentage recoveries indicate an optimal selectivity of the analytical method. The MRM assay to quantify pCS in a small amount of human plasma is rapid, highly sensitive, selective and with a good repeatability. 相似文献
60.