This work aims to show, in the phenomenology of Husserl, the relevance to seek the elements that give epistemological legitimacy and validity to the conceptualization that brings psychoanalytic theory to account for p...This work aims to show, in the phenomenology of Husserl, the relevance to seek the elements that give epistemological legitimacy and validity to the conceptualization that brings psychoanalytic theory to account for processes whose explanation necessarily imply to clarify that psychoanalysis, in contrast to psychological treatments, is not based on the effects of a relationship between the participants but in the positioning that each of them occupies relative to the other, particularly when having in mind the concept of transference and recognizing in it the position from which the analyst can give conditions of possibility--through his interventions--for which the patient may realize, analyze, and rethink his own position on what constitutes his discomfort. Husserl recaptures the Cartesian base from which opens philosophical reflection to a new area of research ＂in＂ consciousness where it is allowed to understand the relationship between subject and object from a new perspective that enables establishing an epistemology that substantiates the rigorous analysis of human subjectivity. Husserl＇s proposal introduces us to an epistemic field in which it can be shown and, that the psychoanalytic method which enables its effects is precisely the position of the analyst, while by his presence and intervention leads to the other in question, without having to abide by an alien desire, be able to position himself before his own desire. This analysis regarding the desire of oneself is indispensable to understand the elements at play in contemporary psychopathology, as in the present context the intensity of the demands generated in the economic apparatus, are experienced by the subject as arising from himself, erasing traces of his desire that is superseded by social imperatives that crushed and fragmented him.展开更多
Recently we reported Pd-catalyzed decarboxylative cross-coupling of cyanoacetate salts with aryl halides and triflates. This reaction shows good functional group tolerance and is useful for the synthesis of-aryl nitri...Recently we reported Pd-catalyzed decarboxylative cross-coupling of cyanoacetate salts with aryl halides and triflates. This reaction shows good functional group tolerance and is useful for the synthesis of-aryl nitriles. To elucidate the mechanism for this reaction, we now carry out a density functional theory study on the cross-coupling of potassium cyanoacetate with bromobenzene. Our results show that the decarboxylation transition state involving the interaction of Pd with the-carbon atom has a very high energy barrier of +34.5 kcal/mol and therefore, must be excluded. Decarboxylation of free ion (or tight-ion-pair) also causes a high energy increase and should be ruled out. Thus the most favored decarboxylation mechanism corresponds to a transition state in which Pd interacts with the cyano nitrogen. The energy profile of the whole catalytic cycle shows that decarboxylation is the rate-determining step. The total energy barrier is +27.5 kcal/mol, which is comprised of two parts, i.e. the energy barrier for decarboxylation and the energy cost for transmetallation.展开更多
文摘This work aims to show, in the phenomenology of Husserl, the relevance to seek the elements that give epistemological legitimacy and validity to the conceptualization that brings psychoanalytic theory to account for processes whose explanation necessarily imply to clarify that psychoanalysis, in contrast to psychological treatments, is not based on the effects of a relationship between the participants but in the positioning that each of them occupies relative to the other, particularly when having in mind the concept of transference and recognizing in it the position from which the analyst can give conditions of possibility--through his interventions--for which the patient may realize, analyze, and rethink his own position on what constitutes his discomfort. Husserl recaptures the Cartesian base from which opens philosophical reflection to a new area of research ＂in＂ consciousness where it is allowed to understand the relationship between subject and object from a new perspective that enables establishing an epistemology that substantiates the rigorous analysis of human subjectivity. Husserl＇s proposal introduces us to an epistemic field in which it can be shown and, that the psychoanalytic method which enables its effects is precisely the position of the analyst, while by his presence and intervention leads to the other in question, without having to abide by an alien desire, be able to position himself before his own desire. This analysis regarding the desire of oneself is indispensable to understand the elements at play in contemporary psychopathology, as in the present context the intensity of the demands generated in the economic apparatus, are experienced by the subject as arising from himself, erasing traces of his desire that is superseded by social imperatives that crushed and fragmented him.
基金supported by the National Natural Science Foundation of China (20972148)CASNECT (08-0519)
文摘Recently we reported Pd-catalyzed decarboxylative cross-coupling of cyanoacetate salts with aryl halides and triflates. This reaction shows good functional group tolerance and is useful for the synthesis of-aryl nitriles. To elucidate the mechanism for this reaction, we now carry out a density functional theory study on the cross-coupling of potassium cyanoacetate with bromobenzene. Our results show that the decarboxylation transition state involving the interaction of Pd with the-carbon atom has a very high energy barrier of +34.5 kcal/mol and therefore, must be excluded. Decarboxylation of free ion (or tight-ion-pair) also causes a high energy increase and should be ruled out. Thus the most favored decarboxylation mechanism corresponds to a transition state in which Pd interacts with the cyano nitrogen. The energy profile of the whole catalytic cycle shows that decarboxylation is the rate-determining step. The total energy barrier is +27.5 kcal/mol, which is comprised of two parts, i.e. the energy barrier for decarboxylation and the energy cost for transmetallation.
