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111.
A classical system for the preparation of carbonyl compounds from alkenes relies upon ozonolysis of the double bond, followed by reductive cleavage of the ozonide so formed. Among the reagents of choice for such a reduction, triphenylphosphine certainly has enjoyed a widespread use.1 However, in spite of the simplicity of the method, often one can face problems in the purification of the carbonyl compound from unreacted triphenylphosphine, especially if the polarities of both products are very similar. We have encountered such a problem during the preparation of the (20 S)-6β -ethoxy-3 α, 5-cyclo-5α -pregnane-20-carbaldehyde 4 from the suitably protected stigmasterol32. In this case, when triphenylphosphine was used for reduction of ozonide we never could isolate the aldehyde 2 uncontaninated by tripherylphosphine. 相似文献
112.
Margherita Bernardeschi Patrizia Guidi Vittoria Scarcelli Giada Frenzilli Marco Nigro 《Analytical and bioanalytical chemistry》2010,396(2):619-623
Titanium dioxide is extensively used in a variety of products, including industrial materials and cosmetics. Studies mainly
performed on human cell lines and in vivo exposure on experimental animals have raised concern about the toxic effects of
ultrafine titanium dioxide; however, scarce information is available about its impact on aquatic life. The aim of this article
was to assess the genotoxic potential of TiO2 (anatase and rutile) on bottlenose dolphin leukocytes. Blood samples were obtained from four male and one female specimens
reared at the Adriatic SeaWorld “Oltremare” (Riccione, Italy). Leukocytes were isolated by the lyses procedure and in vitro
exposed to TiO2 in RPMI. Experimental solutions were sonicated immediately before dosing the cells. Three exposure times (4, 24 and 48 h)
and three doses (20, 50 and 100 μg/ml) were tested. Genotoxicity was detected by the single-cell gel electrophoresis (or comet
assay) at pH ≥ 13, assessing single/double-strand breaks and alkali-labile sites. Cytotoxicity was also detected by the Trypan
blue exclusion method. Results showed that both the crystalline forms of TiO2 were genotoxic for bottlenose dolphin leukocytes, with a statistically significant increase of DNA fragmentation after exposure
to 50 and 100 μg/ml for 24 and 48 h. Although preliminary, these are the first data regarding the genetic susceptibility of
toothed cetaceans toward an “emerging” pollutant, such as TiO2 particles. 相似文献
113.
Patrizia Di Gennaro Silvana Bernasconi Fulvia Orsini Erika Corretto Guido Sello 《Tetrahedron: Asymmetry》2010,21(15):1885-1889
The use of two oxidoreductases (an aldoketo reductase from Escherichia coli JM109 and an alcohol dehydrogenase from Lactobacillus brevis) has demonstrated that it is possible to prepare enatiomerically pure diols in a one-pot operation. The reactions were applied to the synthesis of (1R)-1-[3-(hydroxymethyl)phenyl]ethanol and (1S)-1-phenylethane-1,2-diol, using a two-step procedure. The yield is nearly quantitative and the enantiomeric purity is greater than 95%. A third step has been introduced by adding a cell biocatalyst showing dihydrodiol dehydrogenase activity from Pseudomonas fluorescens N3. This allows for the preparation of 3-[(1R)-1-hydroxyethyl]benzoic acid and (2S)-hydroxy(phenyl)ethanoic acid. 相似文献
114.
115.
Anna Goldberg Vitali Grinberg Irina Utepova Oleg Chupakhin Igor Eremenko 《Journal of organometallic chemistry》2011,696(13):2607-2610
New ionic complexes [ML2(MeCN)2]?2Otf (M = Co or Ni; L = 6-ferrocenyl-2,2′-bipyridyl) were synthesized and characterized by single-crystal X-ray diffraction. Cyclic voltammograms of the compounds [ML2(MeCN)2]?2Otf in CH2Cl2 show good cycle stability over 100 cycles in the quasi-reversible oxidation potential range (from −0.25 to 0.5 V). 相似文献
116.
Summary In the present paper we develop a systematic analysis of the dispersion and dissipation effects on internal gravity waves
in fluids of geophysical interest. Dissipation induces a cut-off in the short wavelengths, leading to an admissible range
of waves. Defining a suitable criterion for detection of waves, an observable wave range results, in which the frequency dispersion
is nearly the same as for the inviscid case, whereas the amplitude is damped. The peculiar behaviour displayed by the dispersion
relationship for Prandtl number equal to one is discussed. 相似文献
117.
G. Berchiesi G. Rafaiani G. Vitali F. Farhat 《Journal of Thermal Analysis and Calorimetry》1995,44(6):1313-1319
The behavior of the molten system acetamide-electrolyte, including the peculiarity of the structure and the consequent relevant properties, such as the megavalue of the dielectric constant, was reported earlier. The probable structure is a micellar system composed of salt micelles dispersed in an amorphous solvent. The present paper reports measurements in a related system: fluoroacetamide-sodium trifluoroacetate. The phase diagram, the ultrasonic absorption of both longitudinal and shear waves, and the longitudinal relaxation time of the nuclear magnetic momentum were measured at different temperatures. The most importnat result was thatT 1 (NMR relaxation time) on the19F nucleus shows that the amide and salt participate in different environments. The amide environment is less rigid; this proves that the system must be considered microheterogeneous. Moreover, the present system exhibited: 1) a less extended concentration area where supercooling phenomena occur; 2) a much broader curve of the real part of the mechanical impedance versus frequency; 3) a higher bulk viscosity in comparison with the CH3CONH2?CF3COONa supercapacitive system. 相似文献
118.
Giovanni Bottiroli Anna Cleta Croce Patrizia Vaghi 《Photochemistry and photobiology》1990,51(2):169-174
Photofrin II is the hematoporphyrin-derivative fraction enriched in covalently-linked oligomers, characterized by a high degree of folding. Interaction with hydrophobic structures, such as biomolecules and cell structures, results in a modification of the equilibria among the different species, as a consequence of an unfolding effect exerted towards the electrostatic aggregates. The effect of esterase activity was evaluated, taking into account the nature suggested for the covalent linkage of the oligomers (ether and/or ester). The study was performed in Photofrin II aqueous solution by means of absorption and fluorescence spectral analysis. The results showed that the esterase is active only towards the unfold oligomers: that is, in Photofrin II solution supplemented with albumin. In these conditions, spectral analysis revealed the presence of a monomerization process, which is clearly evident during the first four hours of incubation. The monomerization effect induced by the enzyme was also proven by both equilibrium-dialysis measurements and zinc ion complexation. Zinc ion complexes with high affinity for monomeric species, giving rise to a very distinct emission band at 580 nm. The amount of ester linkage shown in the oligomers through enzyme hydrolysis appeared to be less than might have been expected, owing to the inhibiting effect of the monomer produced on the enzyme. The results are a step toward clarifying the intracellular and intratissue turnover of the drug observed after administration. 相似文献
119.
Shiri Artstein-Avidan Omer Friedland Vitali Milman Sasha Sodin 《Israel Journal of Mathematics》2006,156(1):141-155
We present a quantitative form of the result of Bai and Yin from [2], and use to show that the section of ℓ
1
(1+δ)n
spanned byn random independent sign vectors is with high probability isomorphic to euclidean with isomorphism constant polynomial in
δ−1.
Partially supported by BSF grant 2002-006.
Supported by the National Science Foundation under agreement No. DMS-0111298.
Supported in part by the Israel Science Academy. 相似文献
120.
Patrizia Cafarelli Adriana De Stefanis Giorgio Perez Anthony A.G. Tomlinson 《Reaction Kinetics and Catalysis Letters》2005,86(1):163-169
Summary Pillared clays have been monitored for catalytic destruction of halocarbons. In comparison with HZSM-5 zeolites, the catalysts tested give higher chlorohydrocarbons destruction with polymers formation. Fluorochlorohydro-carbons are destroyed as well. 相似文献