On the reactions of Cu(II/I)ATP complexes with methyl radicals.

The CuI/IIATP react with methyl radicals to form methane and methanol, where CuIATP reacts with •CH3 in a process that is surprisingly slow. The low-rate constant of this process is attributed to the significant rearrangement of the chelating ligand required for the transient's formation. These results were corroborated by DFT calculations of the relevant compounds.

Mixed-Ligand gold nanoparticles based optical sensor array for the recognition and quantification of seven toxic metals.

Sensor arrays use pattern recognition for the identification and quantification of analytes. In the presented work, a gold nanoparticle (GNP) based optical sensor array was employed to classify and quantify seven toxic metals (arsenic, barium, cadmium, cerium, chromium, lead, and mercury). The sensor array receptors were GNPs functionalized by mercaptoundecanoic acid, 2-mercaptoethanesulfonate, and a 1:1 mixture of the two ligands. The mixed-ligand particle responds to the same analytes as the mono-ligand particles but in a distinctive way. This behavior demonstrates the high potential of mixed-ligand particles in the fabrication of sensor array receptors. The responses of the GNPs to different concentrations of the seven metal ions were analyzed, and a unique "classification trajectory" was produced for every metal. Samples of different metal concentrations were then measured and identified using the "classification trajectories". Once sample composition has been identified, a PLSR model, produced from the concatenated sensor array spectra of four calibration samples for each nanoparticle, was used to determine the metal concentration.

Reactions of methyl, hydroxyl and peroxyl radicals with the DOTA chelating agent used in medical imaging.

The mechanism of reaction of DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) with ·CH3, CH3O2· and ·OH radicals were studied. The radicals were formed in situ radiolytically. The methyl radicals react orders of magnitude slower with DOTA and with MIII(DOTA)- than the hydroxyl radicals. The various final products were identified and mechanisms for their formation are proposed. CH3O2· radicals do not react, or react too slowly to be observed, with DOTA and with MIII(DOTA)- as long as the central cation is not oxidized by the peroxyl radical. The results imply that synthesis of the MIII(DOTA)-(MIII = radioisotope) complexes in a water-organic solvent (ethanol or 2-propanol or acetonitrile) mixture is not only kinetically desired but the so formed complex also decreases the radiolytic decomposition of DOTA.

Oligomers Intermediates in Between Two New Distinct Homonuclear Uranium(IV) DOTP Complexes*.

Two new aqueous UIV complexes were synthesized by the interaction between the tetravalent uranium cation and the (1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid) (DOTP) macrocyclic ligand. Two distinct homonuclear complexes were identified; the first was characterized by X-ray crystallography as a unique "out-of-cage", [U(DOTPH6 )2 ] complex, in which the UIV cation is octa-coordinated to 4 phosphonic arms from each ligand in a square anti-prism geometry, with a C4 symmetry. The second is the "in-cage" [U(DOTPH4 )] complex, in which the tetravalent cation is located between the macrocycle O4 and N4 planes. With the help of UV-Vis absorption, 1 H/31 P NMR, ATR-IR, and MALDI-TOFMS analytical techniques, the chemical interchange between both species is presented. It is shown that the one-way transition is governed by the formation of a multiple number of soluble oligomeric species consisting of varied stoichiometric ratios of both characterized homonuclear complexes.

The Chemistry of Short-Lived α-Fluorocarbocations.

The present study of the chemistry of short-lived α-fluorocarbocations reveals that even inactive methyl carbons can serve as nucleophiles, attacking a cationic center. This, in turn, facilitates the synthesis of a cyclopropane ring in certain triterpene backbones. We report the synthesis of compounds similar to 2, containing a bridgehead cyclopropane, and compounds of type 3 with an 11 membered bicyclic ring consisting of two bridgehead double bonds (anti-Bredt) within a triterpene skeleton. The synthesis involves three unconventional chemical processes: (a) a methyl group serving as a nucleophile; (b) the unexpected and unprecedented synthesis of a strained system in the absence of an external neighboring trigger; and (c) the formation of an 11-membered bicyclic diene ring within a triterpenoid skeleton. An α-fluorocarbocation mechanism is proposed and supported by density functional theory calculations.

Radicals in 'biologically relevant' concentrations behave differently: Uncovering new radical reactions following the reaction of hydroxyl radicals with DMSO.

Methyl radicals play key roles in various chemical and biological processes. Mechanistic studies of methyl radicals with their precursor, Dimethyl Sulfoxide (DMSO), were extensively studied. Though the involved mechanisms seemed to be clarified, essentially none of the studies have been performed at conditions relevant to both biological and catalytic systems, i.e. low steady state radical concentrations. A chain-like reaction, as an inverse function of the radicals concentrations ([•CH3]ss), increases the methyl radical yields. The nature of the additional products obtained differs from those commonly observed. Furthermore it is shown that methyl radicals abstract a methyl group from DMSO to yield ethane. Herein we report a novel mechanism relevant mainly at low steady state radical concentrations, which may change the understanding of certain reaction routes present in both biological systems and catalytic chemical systems. Thus the results point out that mechanistic studies have to be carried out at dose rates forming radicals at analogous concentrations to those present in the process of interest.

De que social somos feitos: discurso educativo e seus efeitos de verdade / From which social we are made of: educational discourse and its truth effects / De cual social somos hechos: discurso educativo y sus efectos de verdad

Este artigo apresenta alguns fundamentos teóricos acerca da relação dialética entre indivíduo e sociedade para discutir os efeitos de verdade das operações discursivas da escola na produção da subjetividade e na formação dos sintomas que têm expressão no campo escolar. Partimos de conceitos oriundos do campo da Sociologia - mais especificamente dos trabalhos de Pierre Bourdieu - estabelecendo um diálogo com a teoria psicanalítica acerca da constituição do sujeito e do laço com o outro pela via do discurso. A partir de nossa experiência, observamos uma relação não necessariamente linear entre os determinantes sociais, a saber: classe social, condições socioeconômicas e estrutura familiar, o lugar que a criança ocupa no discurso dos educadores e os efeitos subjetivos da experiência escolar para cada aluno. Para ilustrar esta hipótese, apresentamos fragmentos de duas situações de intervenção a partir do arcabouço teórico-técnico da Psicanálise com crianças de escolas públicas que apresentaram impasses em seu processo de escolarização.

This article presents some theoretical foundations about the dialectic relationship between individual and society to discuss the truth effects of the school discursive operations on the subjectivity production and the formation of scholar symptoms that has expression in the scholar field. We start by concepts from the sociology field - more specifically from the works of Pierre Bourdieu - establishing a dialogue with the psychoanalytic theory about the constitution of the subject and the bond with the other through the discourse. From our experience, we observed a non-linear relationship between social determinants (namely: social class, socioeconomic conditions and family structure) the child's place in educator's discourse and the subjective effects of the school experience for each student. To illustrate this hypothesis, we present two fragments of intervention situations from the psychoanalysis theoretical and technical framework with public school children who live impasses in their schooling process

Este artículo presenta algunos fundamentos teóricos sobre la relación dialéctica entre el individuo y sociedad para discutir los efectos de verdad de las operaciones discursivas de la escola en la producción de la subjetividad y en la formación de los síntomas que se expresan en el campo escolar. Partimos de conceptos oriundos del campo de la sociología - más específicamente de los trabajos de Pierre Bourdieu - estableciendo un diálogo con la teoría psicoanalítica acerca de la constitución del sujeto y del lazo con el otro por la vía del discurso. A partir de nuestra experiencia, se observó una relación no necesariamente lineal entre los determinantes sociales (clase social, el nivel socioeconómico y la estructura familiar), el lugar que ocupa el niño en el discurso de los educadores y los efectos subjetivos de la experiencia escolar para cada estudiante. Para ilustrar esta hipótesis, presentamos fragmentos de dos situaciones de intervención, a partir del marco teórico y técnico de la psicoanálisis con niños de escuelas publicas que presentaron impasses en su proceso de escolarización.

On the Aqueous Chemistry of the UIV -DOTA Complex.

The 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) aqueous complex of UIV with H2 O, OH- , and F- as axial ligands was studied by using UV/Vis spectrophotometry, ESI-MS, NMR spectroscopy, X-ray crystallography, and electrochemistry. The UIV -DOTA complex with either water or fluoride as axial ligands was found to be inert to oxidation by molecular oxygen, whereas the complex with hydroxide as an axial ligand slowly hydrolyzed and was oxidized by dioxygen to a diuranate precipitate. The combined data set acquired shows that, although axial substitution of fluoride and hydroxide ligands instead of water does not seem to significantly change the aqueous DOTA complex structure, it has an important effect on the electronic configuration of the complex. The UIV /UIII redox couple was found to be quasi-reversible for the complex with both axially bonded H2 O and hydroxide, but irreversible for the complex with axially bonded fluoride. Intriguingly, binding of the axial fluoride renders the irreversible one-electron UV /UIV oxidation of the [UIV (DOTA)(H2 O)] complex quasi-reversible, which suggests the formation of the short-lived pentavalent form of the complex, an aqueous non-uranyl chelated UV cation.

Direct Observation of Acyl Nitroso Compounds in Aqueous Solution and the Kinetics of Their Reactions with Amines, Thiols, and Hydroxamic Acids.

Acyl nitroso compounds or nitrosocarhonyls (RC(O)N═O) are reactive short-lived electrophiles, and their hydrolysis and reactions with nucleophiles produce HNO. Previously, direct detection of acyl nitroso species in nonaqueous media has been provided by time-resolved infrared spectroscopy demonstrating that its half-life is about 1 ms. In the present study hydroxamic acids (RC(O)NHOH) are oxidized electrochemically in buffered aqueous solutions (pH 5.9-10.2) yielding transient species characterized by their maximal absorption at 314-330 nm. These transient species decompose via a first-order reaction yielding mainly HNO and the respective carboxylic acid and therefore are ascribed to RC(O)N═O. The sufficiently long half-life of RC(O)N═O in aqueous solution allows for the first time the study of the kinetics of its reactions with various nucleophiles demonstrating that the nucleophilic reactivity follows the order thiolate > hydroxamate > amine. Metal chelates of CH3C(O)NHOH catalyze the hydrolysis of CH3C(O)N═O at the efficacy order of CuII > ZnII > NiII > CoII where only CuII catalyzes the hydrolysis also in the absence of the hydroxamate. Finally, oxidation of hydroxamic acids generates HNO, and the rate of this process is determined by the half-life of the respective acyl nitroso compound.

Núcleo de Educação Terapêutica: um espaço de invenção na clínica com crianças psicóticas / The Therapeutic Education Center: a place for invention in clinic services for psychotic children / Centre d’éducation thérapeutique: un espace d’invention dans la clinique avec des enfants psychotiques / Centro de Educación Terapéutica: un espacio de creación en la práctica clínica con niños psicóticos / Zentrum für Therapeutische Erziehung: Ein Ort der Kreativität in der Behandlung psychotischer Kinder / 理療教育中心：兒童精神病臨床实践的創造性空間 摘要

Este artigo tem o objetivo de transmitir a experiência de implementação do Núcleo de Educação Terapêutica no Instituto de Psicologia da USP. A constituição do NET inspira-se no desenvolvimento de um campo teórico-clínico denominado Educação Terapêutica que aproxima Psicanálise e Educação e enseja um conjunto de práticas de tratamento do autismo e da psicose infantil. Apresentaremos os fundamentos teórico-clínicos que sustentam essa prática e analisaremos, à luz de um caso clínico, os efeitos de mudança de posição subjetiva e reordenamento do gozo como frutos do ato analítico no tratamento de uma criança psicótica.

This article aims to present the experience of implementing the University of São Paulo’s Psychology Institute’s Therapeutic Education Center. The Center was inspired by a theoretical and clinical field called Therapeutic Education — a set of treatment and educational practices aimed at autism and childhood psychosis. We present the theoretical and clinical foundations that support this practice and analyze, in the light of a case report, the effects of change in the subjective position and in the reorganization of enjoyment as a result of analytic acts in the treatment of a psychotic child.

Cet article vise à transmettre l’expérience de la mise en œuvre du Centre d’éducation thérapeutique à l’Institut de psychologie de l’Université de São Paulo. La constitution du Centre d’éducation thérapeutique s’est inspirée du développement d’un champ théorique et clinique dénommé Éducation thérapeutique qui fait le rapprochement entre la psychanalyse et l’éducation et donne lieu à un ensemble de pratiques de traitement de l’autisme et de la psychose infantile. On présentera les fondements théoriques et cliniques soutenant cette pratique et on analysera, à la lumière d’un cas clinique, les effets de changement de position subjective et réordonnancement de la jouissance comme des fruits de l’acte analytique dans le traitement d’un enfant psychotique.

Este artículo tiene como objetivo transmitir la experiencia de la implementación del Centro de Educación Terapéutica en el Instituto de Psicología de la Universidad de São Paulo (USP). La constitución del Centro de Educación Terapéutica se inspira en el desarrollo de un campo teórico-clínico denominado Educación Terapéutica que realiza una aproximación entre el Psicoanálisis y la Educación, y que implica un conjunto de prácticas para el tratamiento del autismo y de la psicosis infantil. Presentaremos los fundamentos teóricos y clínicos que son la base de esta práctica y analizaremos, a la luz de un caso clínico, los efectos de cambio en la posición subjetiva y el reordenamiento del gozo como frutos del acto analítico en el tratamiento de un niño psicótico.

Dieser Artikel beschreibt die Erfahrungen, die anlässlich der Implementierung des Zentrum für Therapeutische Erziehung im Psychologischen Institut der Universität von São Paulo gemacht wurden. Das Zentrum für Therapeutische Erziehung basiert sich auf den Aufbau eines theoretisch-klinischen Arbeitsfeldes, dass Therapeutische Erziehung genannt wird und dessen Ziel es ist, die Erkenntnisse der Psychoanalyse auf die Erziehungswissenschaften anzuwenden. Es bietet daher verschiedene Verfahrensweisen zur Behandlung von Autismus und kindlicher Psychose. Wir stellen zunächst die theoretisch-klinischen Grundlagen dieser Praxis vor und analysieren dann anhand eines klinischen Falles die Ergebnisse einer Änderung der subjektiven Stellung und der Neuordnung des Genusses als Ergebnis des psychoanalytischen Aktes in der Behandlung eines psychotischen Kindes.

本文旨在傳達巴西圣保罗大学(USP) 心理學研究所下属的治療教育中心(NET)的实践經驗。NET的创立源於理療—教育領域的理論與臨床的發展，結合心理分析学與教育学，提供一系列针对自閉症和兒童精神病的治療方法。在此我們將介紹此做法之理論與臨床基礎，透過個案，分析治疗效果，这个案例是儿童精神病患者，通过心理医生的分析治疗，改变了病人的主观态度，和发泄方式，是治療教育中心的实践成果之一。.

Plantão institucional: uma modalidade de intervenção face ao mal-estar contemporâneo na educação

O Plantão Institucional é um serviço oferecido pelo Serviço de Psicologia Escolar do Instituto de Psicologia (USP) para grupos de profissionais que trabalham na interface da Psicologia com os campos da Educação, Saúde Mental e Assistência Social. Nossa hipótese de trabalho é de que a oferta de um espaço de fala e de interlocução para esses profissionais promove a mobilização do desejo implicado na ação educativa, um reposicionamento do sujeito diante das questões suscitadas pelo trabalho e a ampliação do repertório de estratégias criadas para o enfrentamento das dificuldades que emergem no campo educativo.(AU)

The Institutional Duty is a service provided by the Service of School Psychology of IPUSP for groups of professionals working at the interface of Psychology with the fields of Education, Mental Health and Social Welfare. Our working hypothesis is that providing a space for talks and dialogue for these professionals promotes the mobilization of the desire involved in the educational action, a repositioning of the subject towards the issues raised by work and the expansion of the repertoire of strategies created to cope with the difficulties that emerge in the educational field.(AU)

El atendimiento institucional es un servicio proporcionado por el Servicio de Psicología Escolar del IPUSP para grupos de profesionales que trabajan en la interfase de la psicología con las áreas de Educación, Salud Mental y el Bienestar Social. Nuestra hipótesis de trabajo es que proporcionar un espacio de habla y diálogo para estos profesionales favorece la movilización del deseo hacia las actividades educativas, un reposicionamiento del sujeto sobre las cuestiones planteadas por el trabajo y la ampliación del repertorio de estrategias diseñadas para hacer frente a las dificultades que surgen en el campo educativo.(AU)

Plantão institucional: uma modalidade de intervenção face ao mal-estar contemporâneo na educação

O Plantão Institucional é um serviço oferecido pelo Serviço de Psicologia Escolar do Instituto de Psicologia (USP) para grupos de profissionais que trabalham na interface da Psicologia com os campos da Educação, Saúde Mental e Assistência Social. Nossa hipótese de trabalho é de que a oferta de um espaço de fala e de interlocução para esses profissionais promove a mobilização do desejo implicado na ação educativa, um reposicionamento do sujeito diante das questões suscitadas pelo trabalho e a ampliação do repertório de estratégias criadas para o enfrentamento das dificuldades que emergem no campo educativo...

The Institutional Duty is a service provided by the Service of School Psychology of IPUSP for groups of professionals working at the interface of Psychology with the fields of Education, Mental Health and Social Welfare. Our working hypothesis is that providing a space for talks and dialogue for these professionals promotes the mobilization of the desire involved in the educational action, a repositioning of the subject towards the issues raised by work and the expansion of the repertoire of strategies created to cope with the difficulties that emerge in the educational field...

El atendimiento institucional es un servicio proporcionado por el Servicio de Psicología Escolar del IPUSP para grupos de profesionales que trabajan en la interfase de la psicología con las áreas de Educación, Salud Mental y el Bienestar Social. Nuestra hipótesis de trabajo es que proporcionar un espacio de habla y diálogo para estos profesionales favorece la movilización del deseo hacia las actividades educativas, un reposicionamiento del sujeto sobre las cuestiones planteadas por el trabajo y la ampliación del repertorio de estrategias diseñadas para hacer frente a las dificultades que surgen en el campo educativo...

A escrita e a psicose na criança: uma proposta de tratamento / La escritura y la psicosis en los niños: una propuesta de tratamiento / Writing and psychosis in childhood: a treatment proposal

A clínica com crianças com graves comprometimentos psíquicos põe à prova a hipótese de que a posição da criança frente à castração - e frente à linguagem - determina o modo como ela se relaciona com o conhecimento e, em especial, com a escrita. Esse artigo apresenta a fundamentação teórica e recortes clínicos do trabalho desenvolvido no Grupo da Escrita, criado em 2002 no Lugar de Vida. De natureza interdisciplinar, o trabalho no grupo tem como objetivo oferecer atividades variadas de leitura e escrita que coloquem em ação a organização cognitiva das crianças como uma possibilidade de reordenação do campo simbólico(AU)

The treatment of children with severe psychological problems tests the hypothesis that their position front castration - linked to language - determines the way that they relate to general learning and writing skills. This article presents the theoretical foundation and clinical observations of the work developed by the Writing Group, created in 2002 at Lugar de Vida. Based on a multi-disciplinary approach, the group's objective is to offer activities linked to reading and writing, which set in motion children's cognitive skills in order to reorganize their symbolic field(AU)

La clínica con niños con serios comprometimentos psíquicos da muestras del supuesto de que la posición del niño frente a castración - y frente a la lengua - no es sin efecto para la manera como se relaciona con el conocimiento y, en especial con la escritura. Este artículo presenta los fundamentos teóricos e fragmentos clínicos del trabajo del "Grupo da Escrita", creado en 2002 en el Lugar de Vida. El trabajo tiene como objetivo a ofrecer actividades variadas de la lectura y de la escritura que pueden poner en la acción la organización cognitiva de los niños como posibilidad de ordenanza del campo simbólico(AU)

A escrita e a psicose na criança: uma proposta de tratamento / La escritura y la psicosis en los niños: una propuesta de tratamiento / Writing and psychosis in childhood: a treatment proposal

A clínica com crianças com graves comprometimentos psíquicos põe à prova a hipótese de que a posição da criança frente à castração - e frente à linguagem - determina o modo como ela se relaciona com o conhecimento e, em especial, com a escrita. Esse artigo apresenta a fundamentação teórica e recortes clínicos do trabalho desenvolvido no Grupo da Escrita, criado em 2002 no Lugar de Vida. De natureza interdisciplinar, o trabalho no grupo tem como objetivo oferecer atividades variadas de leitura e escrita que coloquem em ação a organização cognitiva das crianças como uma possibilidade de reordenação do campo simbólico.

The treatment of children with severe psychological problems tests the hypothesis that their position front castration - linked to language - determines the way that they relate to general learning and writing skills. This article presents the theoretical foundation and clinical observations of the work developed by the Writing Group, created in 2002 at Lugar de Vida. Based on a multi-disciplinary approach, the group's objective is to offer activities linked to reading and writing, which set in motion children's cognitive skills in order to reorganize their symbolic field.

La clínica con niños con serios comprometimentos psíquicos da muestras del supuesto de que la posición del niño frente a castración - y frente a la lengua - no es sin efecto para la manera como se relaciona con el conocimiento y, en especial con la escritura. Este artículo presenta los fundamentos teóricos e fragmentos clínicos del trabajo del "Grupo da Escrita", creado en 2002 en el Lugar de Vida. El trabajo tiene como objetivo a ofrecer actividades variadas de la lectura y de la escritura que pueden poner en la acción la organización cognitiva de los niños como posibilidad de ordenanza del campo simbólico.

Uso profilatico de antagonista de leucotrieno no controle de pacientes com asma grave / Prophylactic use of leukotriene antagonists in control of patients with gravis asthma

A incidencia da asma esta aumentando no mundo, assim como o numero de casos, graves, de dificil controle clinico. As causas estao associadas a urbanizacao das populacoes, que conduziu ao aumento das infeccoes das vias aereas e ao aumento da poluicao ambiental. No sentido de reduzir a morbi-mortalidade desse grupo, sao recomendadas a terapeutica precoce das crises bronco-oclusivas, com beta 2 adrenergicos e corticosteroides, assim como a promocao de...

Apresentacao clinica da tuberculose em hospital geral pediatrico / Clinical profile of tuberculosis at a pediatric general hospital

Os autores descrevem a apresentacao clinica dos pacientes com diagnostico de tuberculose, durante o periodo de 1994 a 1998, da Divisao de Pediatria do Hospital Universitario da USP...

Apresentacao clinica e radiografica de cinco casos de tuberculose em hospital geral pediatrico / Clinical and radiological profile of five tuberculous cases at a pediatric general hospital

Os autores descrevem cinco diferentes formas de apresentacao clinica da tuberculose que foram observadas no Servico de Pronto Atendimento do HU-USP...