904 resultados para NUCLEOPHILIC REACTIONS


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BACKGROUND: It is well known that there are specific peripheral activation patterns associated with the emotional valence of sounds. However, it is unclear how these effects adapt over time. The personality traits influencing these processes are also not clear. Anxiety disorders influence the autonomic activation related to emotional processing. However, personality anxiety traits have never been studied in the context of affective auditory stimuli. METHODS: Heart rate, skin conductance, zygomatic muscle activity and subjective rating of emotional valence and arousal were recorded in healthy subjects during the presentation of pleasant, unpleasant, and neutral sounds. Recordings were repeated 1 week later to examine possible time-dependent changes related to habituation and sensitization processes. RESULTS AND CONCLUSION: There was not a generalized habituation or sensitization process related to the repeated presentation of affective sounds, but rather, specific adaptation processes for each physiological measure. These observations are consistent with previous studies performed with affective pictures and simple tones. Thus, the measures of skin conductance activity showed the strongest changes over time, including habituation during the first presentation session and sensitization at the end of the second presentation session, whereas the facial electromyographic activity habituated only for the neutral stimuli and the heart rate did not habituate at all. Finally, we showed that the measure of personality trait anxiety influenced the orienting reaction to affective sounds, but not the adaptation processes related to the repeated presentation of these sounds.

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In the literature, some transition metal salts have been used as soft Lewis acids to activate alkynes toward nucleophilic attack. For example, Pt(II), Au(I) and Pd(II) catalysts can catalyze cycloisomerization reactions of alkynyl compounds to give a variety of cyclic products. In order to expand the scope of these reactions, in chapter 2 of this dissertation, several alkynyl epoxides were isomerized to cyclic allyl vinyl ethers using PtCl2 as the catalyst. Three of these allyl vinyl ethers were hydrolyzed to 2-hydroxymorpholine derivatives and two were converted to piperidine derivatives by thermal Claisen rearrangement. In order to find more benign and inexpensive catalysts for these types of reactions, in chapter 3 of this dissertation, BiCl3 was used to catalyze the isomerization of eight enynes to pyrrolidine derivatives. This reaction was normally catalyzed by expensive noble metal catalysts, such as Pd(II), Pt(II) and Au(I). All the cyclic products are valuable intermediates in the synthesis of bioactive molecules, these soft Lewis acid catalyzed cycloisomerization may find applications in the synthesis of bioactive molecules.

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OBJECTIVE: The objective of the study was to evaluate tissue reactions such as bone genesis, cartilage genesis and graft materials in the early phase of lumbar intertransverse process fusion in a rabbit model using computed tomography (CT) imaging with CT intensity (Hounsfield units) measurement, and to compare these data with histological results. MATERIALS AND METHODS: Lumbar intertransverse process fusion was performed on 18 rabbits. Four graft materials were used: autograft bone (n = 3); collagen membrane soaked with recombinant human bone morphogenetic protein-2 (rhBMP-2) (n = 5); granular calcium phosphate (n = 5); and granular calcium phosphate coated with rhBMP-2 (n = 5). All rabbits were euthanized 3 weeks post-operatively and lumbar spines were removed for CT imaging and histological examination. RESULTS: Computed tomography imaging demonstrated that each fusion mass component had the appropriate CT intensity range. CT also showed the different distributions and intensities of bone genesis in the fusion masses between the groups. Each component of tissue reactions was identified successfully on CT images using the CT intensity difference. Using CT color mapping, these observations could be easily visualized, and the results correlated well with histological findings. CONCLUSIONS: The use of CT intensity is an effective approach for observing and comparing early tissue reactions such as newly synthesized bone, newly synthesized cartilage, and graft materials after lumbar intertransverse process fusion in a rabbit model.

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Monoclonal antibodies have expanded our cancer-fighting armamentarium in both the United States and Europe. While in general, monoclonal antibodies are well tolerated and do not have significant overlapping side effects with traditional cytotoxic agents, severe infusion reactions (IRs)--sometimes severe enough to be life threatening--have been reported. The pathophysiology of severe infusion reactions associated with monoclonal antibodies is poorly understood, but mechanisms are beginning to be elucidated. Geographic differences in the incidence of IRs have become apparent. Understanding the risk, recognizing the signs and symptoms, and being ready to promptly manage severe IRs are key for the clinician to avoid unnecessarily discontinuing these effective anticancer agents and prevent potentially tragic consequences for their patients. To date, clinical trials have incorporated monoclonal antibodies into combinations with standard cytotoxic regimens; it is expected that in time clinical trials will be testing promising new combinations utilizing multiple targeted agents, resulting in improved toxicity profiles and efficacy for cancer patients.

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The solution phase parallel synthesis involving reactions of Baylis-Hillman products of 3-substituted-5-isoxazolecarbaldehydes with nucleophiles and their in vivo antithrombotic evaluations are described along with the results of in vitro platelet aggregation inhibition assay of a few compounds. Results of the detailed evaluation of one of the compounds as an inhibitor of platelet aggregation are also presented.

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The formation of substituted 2-pyrrolidinones and indoles by the reduction of the secondary nitro group in appropriate 3-aryl-2-methylene-4-nitroalkanoates afforded by Baylis-Hillman chemistry via different reducing agents is described. The 3-aryl-2-methylene-4-nitroalkanoate obtained from SN2 nucleophilic reaction between the acetate of Baylis-Hillman adducts and ethyl nitroacetate upon reduction with indium-HCl furnishes a mixture of cis and trans substituted phenyl-3-methylene-2-pyrrolidinones. In contrast, similar reductions of analogous substrates derived from nitroethane stereoselectively furnished only the trans substituted phenyl-3-methylene-2-pyrrolidinones. On the other hand the SnCl2.2H2O-promoted reductions of substrates derived from nitro ethylacetate give oxime derivatives while the ones obtained from nitroethane yield a mixture of cis and trans 4-aryl-3-methylene-2-pyrrolidinones. Alternatively, the SnCl2.2H2O-promoted reduction of substituted 2-nitrophenyl-2-methylene-alkanoate furnished from ethyl nitroacetate yields 3-(1-alkoxycarbonyl-vinyl)-1H-indole-2-carboxylate while indium-promoted reaction of this substrate leads to a complex mixture. Analogous reactions with SnCl2.2H2O of substituted 2-nitrophenyl-2-methylene-alkanoate obtained from nitroethane yield 4-alkyl-3-methylene-2-quinolones in moderate yields

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Acetylation and formylation of 3-phenyl-cycl[3.2.2]azine derivatives, in the presence of Lewis acids, have been Investigated. It has been found that the orientation of substitution in 2-carbomethoxy- 3-phenyl-cycl[3.2.2]azine for these two reactions, under Identical conditions, is different.