Direito

O presente artigo pretende analisar, tanto no novo texto legal quanto na doutrina, os fundamentos para decretar a prisao preventiva, principalmente os criterios para a garantia da ordem publica e da ordem economica, e sua relacao com a teoria decisionista de Carl Schmitt, que e considerado o grande jurista do regime nacional-socialista.

O Estado, sendo subsidiador dos direitos fundamentais, deve preservá-los para que assim a dignidade da pessoa humana e o mínimo existencial estejam garantidos. No que diz respeito aos direitos fundamentais prestacionais, como a previdência social, para que sejam garantidos é necessário que haja recursos econômicos para isso. A reserva do possível surge no Brasil como teoria limitadora da atividade prestacional do Estado, quando esse, alegando escassez de recursos, abstém-se de prestar os devidos serviços à sociedade. A partir da pesquisa bibliográfica se buscou conceituar os direitos fundamentais, o princípio da dignidade da pessoa humana, a reserva do possível e a respectiva atuação como limite na garantia dos direitos fundamentais, o mínimo existencial, a previdência social e seu financiamento e a aplicação da reserva do possível nesse âmbito. Ao final, verificou-se que o conceito de reserva do possível utilizado no Brasil não é o mesmo da sua origem, na Alemanha. Notou-se que ela é responsabilizada por enfraquecer a garantia dos direitos fundamentais, sendo que em algumas situações, como a previdência, sequer o mínimo existencial é resguardado.

Fast screening of low-MW compounds is performed by thin-layer chromatography (TLC) followed by direct onspot matrix-assisted laser desorption/ionization time-offlight mass spectrometry identification with nearly "matrixfree" mass spectra using an UV-absorbing ionic liquid matrix. Owing to minimal background ions from the proton donor triethylamine/r-cyano-4-hydroxycinnamic acid ionic liquid matrix, three arborescidine alkaloids, the anesthesics levobupivacaine and mepivacaine, and the antibiotic tetracycline were readily characterized most frequently by the MS detection of their protonated molecules. The technique is fast and sensitive, requires little sample preparation and manipulation, and is therefore suitable for fast screening with TLC separation and MS identification of low-MW compounds, with potential applications in areas such as phytochemistry, synthetic chemistry, and product manufacturing quality monitoring.

Mono-and dimethylation of hydroxylamine on nitrogen does not significantly affect rates of initial attack of NHMeOH and NMe 2 OH on bis(2,4-dinitrophenyl)phosphate (BDNPP), which is largely by oxygen phosphorylation. O-Methylation, however, blocks this reaction and NH 2 OMe then slowly reacts with BDNPP via N-attack at phosphorus and at the aryl group. With NHMeOH, the initial product of O-attack at phosphorus reacts further, either by reaction with a second NHMeOH or by a spontaneous shift of NHMe to the aryl group via a transient cyclic intermediate. There is a minor N-attack of NHMeOH on BDNPP in an S N 2(Ar) reaction. Reactions occurring via N-attack are blocked by N-dimethylation, and reaction of NMe 2 OH with BDNPP occurs via O-attack, generating a long-lived product. Reaction mechanisms have been probed, and intermediates identified, by using both NMR and MS spectroscopy, with the novel interception of key reaction intermediates in the course of reaction by electrospray ionization mass and tandem mass spectrometry.

This work describes the optimization of a cloud point extraction (CPE) method for casein proteins from cow milk samples. To promote phase separation, polyoxyethylene(8) isooctylphenyl ether (Triton ® X-114) and sodium chloride (NaCl) were used as nonionic surfactant and electrolyte, respectively. Using multivariate studies, four major CPE variables were evaluated: Triton ® X-114 concentration, sample volume, NaCl concentration, and pH. The results show that surfactant concentration and sample volume were the main variable affecting the CPE process, with the following optimized parameters: 1% (w/v) Triton ® X-114 concentration, 50 L of sample volume, 6% (w/v) NaCl concentration and extractions carried out at pH 7.0. At these conditions, 923 ± 66 and 67 ± 2 g mL −1 of total protein were found in the surfactant-rich and surfactant-poor phases, respectively. Finally, matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) was then used to evaluate those target proteins (␣ s1 -casein, ␣ s2 -casein and ␤-casein) separation as well as to check the efficiency of the extraction procedure, making a fingerprint of those target proteins possible.

Described are the first enantioselective total syntheses of (+)-arborescidine A ((+)-1), (-)arborescidine B ((-)-2), and (-)-arborescidine C ((-)-3), via routes that proceeded in five steps and 50% overall yield, eight steps and 61% overall yield, and nine steps and 51% overall yield, respectively, from 6-bromotryptamine . The syntheses feature the use of the Noyori catalytic asymmetric hydrogen-transfer reaction to introduce chirality in dihydro--carbolines 6 and 8. On the basis of an ample precedent from Noyori's work, the reduction produces dihydro--carbolines, and ultimately the natural products, possessing the R absolute configuration. The synthetic arborescidines displayed optical rotations that were opposite in sign those of the natural products, thereby supporting the S configuration for natural arborescidines A (1) and B (2) and the (3S,17S) configuration for natural arborescidine C (3). Our results are in agreement with the initial stereochemical assignment by Païs and co-workers, and are counter to their recently revised assignment.

Among the various outstanding properties exhibited by ionic liquids (ILs), two of the most peculiar are their very low vapor pressure [1] and pronounced supramolecular self-organization both in the condensed and gas phases. This unique set of properties make ionic liquids very attractive alternatives to classical organic solvents and water, opening also a wealth of [*] Dr.

Efficient detection of aflatoxins B 1 , B 2 , G 1 , and G 2 has been performed by matrix-assisted laser desorption/ ionization time-of-flight mass spectrometry using a UVabsorbing ionic liquid matrix to obtain "matrix-free" mass spectra and addition of NaCl to enhance sensitivity via Na + cationization. Using ionic r-cyano-4-hydroxycinnamic acid (Et 3 N-r-CHCA) as the matrix, matrix-free mass spectra in the m/z range of interest are acquired, and the B 1 , B 2 , G 1 , and G 2 aflatoxins are readily detected with an LOD as low as 50 fmol. The technique is fast, requires little sample preparation and no derivatization or chromatographic separation, and seems therefore to be suitable for high-throughput aflatoxin screening. It should be easily extended to other micotoxins and provide an attractive technique to control the quality of major crops subjected to huge world commercial trades such as peanuts, corn, and rice as well as to monitor bioterrorism threats by micotoxin poisoning.

Electrospray ionization mass spectrometry (ESI-MS) is found to gently and efficiently transfer small to large as well as singly to multiply charged [X+]n[A−]m supramolecules of imidazolium ion (X+) ionic liquids to the gas phase, and to reveal “magic numbers” for their most favored assemblies. Tandem mass spectrometric experiments (ESI-MS/MS) were then used to dissociate, via low-energy collision activation, mixed and loosely bonded [A- - - -X- - - -A′]− and [X- - - -A- - - -X′]+ gaseous supramolecules, as well as their higher homologues, and to estimate and order via Cooks' kinetic method (CKM) and B3LYP/6-311G(d,p) calculations the intrinsic solvent-free magnitude of hydrogen bonds. For the five anions studied, the relative order of intrinsic hydrogen-bond strengths to the 1-n-butyl-3-methylimidazolium ion [X1]+ is: CF3CO2− (zero) > BF4− (−3.1) > PF6− (−10.0) > InCl4− (−16.4) and BPh4− (−17.6 kcal mol−1). The relative hydrogen-bond strength for InCl4− was measured via CKM whereas those for the other anions were calculated and used as CKM references. A good correlation coefficient (R=0.998) between fragment ion ratios and calculated hydrogen-bond strengths and an effective temperature (Teff) of 430 K demonstrate the CKM reliability for measuring hydrogen-bond strengths in gaseous ionic liquid supramolecules. Using CKM and Teff of 430 K, the intrinsic hydrogen-bond strengths of BF4− for the three cations investigated is: 1-n-butyl-3-methyl-imidazolium ion (0) > 1,3-di-[(R)-3-methyl-2-butyl]-imidazolium ion (−2.4) > 1,3-di-[(R)-α-methylbenzyl]-imidazolium ion (−3.0 kcal mol−1). As evidenced by “magic” numbers, greater stabilities are found for the [(X1)2(BF4)3]− and [(X1)5A4]+ supramolecules (A≠InCl4−).

Recently, it has been proposed (M. Claeys et al., Science 2004; 303: 1173) that the atmospheric OHradical-mediated photooxidation of isoprene is a source of two major secondary organic aerosol (SOA) components, that is, 2-methylthreitol and 2-methylerythritol. These diastereoisomeric tetrols, which were characterized for the first time in the fine size fraction (<2.5 mm aerodynamic diameter) of aerosols collected in the Amazon rain forest during the wet season, were proposed to enhance the capability of the aerosols to act as cloud-condensation nuclei. In the present study, we performed the oxidation of isoprene in aqueous solution under conditions that attempted to mimic atmospheric OH-radical-induced photooxidization, and monitored and characterized on-line the reaction products via electrospray ionization mass (and tandem mass) spectrometry in the negative ion mode. The results show that the reaction of isoprene with photo-or chemically generated hydroxyl radicals indeed yields 2-methyltetrols. Other polyols were also detected, and they may therefore be considered as plausible SOA components eventually formed in normal or more extreme OH-radicalmediated photooxidation of biogenic isoprene.

High performance liquid chromatography (HPLC), ultraviolet spectroscopy (UV), and total organic carbon (TOC) analyses show that caffeine is quickly and completely degraded under the oxidative conditions of the UV/H 2 O 2 , TiO 2 / UV, and Fenton systems but that the organic carbon content of the solution decreases much more slowly. Continuous on-line and real-time monitoring by electrospray ionization mass (ESI-MS) and tandem mass spectrometric experiments (ESI-MS/MS) as well as high accuracy MS measurements and gas chromatography-mass spectrometry analysis show that caffeine is first oxidized to N-dimethylparabanic acid likely via initial OH insertion to the C4dC8 caffeine double bond. A second degradation intermediate, di(N-hidroxymethyl)parabanic acid, has been identified by ESI-MS and characterized by ESI-MS/MS and high accuracy mass measurements. This polar and likely relatively unstable compound, which is not detected by offline GC-MS analysis, is likely formed via further oxidation of N-dimethylparabanic acid at both of its N-methyl groups and constitutes an unprecedented intermediate in the degradation of caffeine.

Electrospray ionization (ESI) mass spectrometry (MS) and tandem mass spectrometry (MS/MS) were used to monitor the oxidation of phenol by a novel heterogeneous Fenton system based on a Fe0/Fe3O4 composite and H2O2. On-line ESI-MS(/MS) shows that this heterogeneous system promotes prompt oxidation of phenol to hydroquinone, which is subsequently oxidized to quinone, other cyclic poly-hydroxylated intermediates and an acyclic carboxylic acid. A peroxide-type intermediate, probably formed via an electrophilic attack of HOO. on the phenol ring, was also intercepted and characterized. ESI-MS(/MS) monitoring of the oxidation of two other model aromatic compounds, benzene and chlorobenzene, indicates the participation of analogous intermediates. These results suggest that oxidation by the heterogeneous system is promoted by highly reactive HO. and HOO. radicals generated from H2O2 on the surface of the Fe0/Fe3O4 composite via a classical Fenton-like mechanism. Copyright © 2006 John Wiley & Sons, Ltd.

Scheme 3. The single Baylis-Hillman intermediate so far isolated and characterized by X-ray crystallography. Scheme 4. Baylis-Hillman reactions monitored by ESI(+)-MS/MS. Reagents and conditions: a) DABCO (1 a), methyl acrylate (2 a), MeOH, RT. Scheme 5. Baylis-Hillman reaction of methyl acrylate and aldehydes catalyzed by DABCO. The protonated species expected to be intercepted and structurally characterized by ESI(+)-MS/MS, with their respective m/z ratios.

A teoria do Labelling Approch baseia-se por indivíduos caracterizados como pessoas especiais (desviantes), mas que a própria sociedade os define como tal no estabelecimento de regras cuja infração constitui a desviação. A teoria da interação simbólica concebida por Herbert Blumer, diz que as relações sociais surgem como abertas e dependendo de constante aprovação em comum. As pessoas só tornam-se sociais no processo de interação com as outras pessoas, incorporadas a perspectivas dos outros em suas próprias. Leis foram criadas para conter condutas existentemente problemáticas nas quais não são aceitas por determinado grupo, que de um ponto de vista mais social são empregadas para reprimir os movimentos transformando pessoas comuns em criminosos. O Labelling desloca o problema criminológico do plano da ação para o da reação, fazendo com que a verdadeira característica dos delinquentes seja a resposta de audiências de controle. A explicação interacionista caracterisa-se por incidir sobre a chamada delinquência secundaria, isto é, a delinquência que resulta do processo causal, desencadeado pela estigmatização. O princípio geral e quando outras pessoas decidem que determinada pessoa é non grata, perigosa, não confiável, moralmente repugnante, tomando atitudes desagradáveis, atitudes que demonstram rejeição e a humilhação, de um controle que controlara sua liberdade e que o tornara um desviante secundário seguindo a carreira criminal. Em resumo, se um dado ato é desviante ou não, vai depender em parte da natureza do ato (isto é, se ele viola ou não uma regra imposta pela sociedade) e em parte como decorrência do que as outras pessoas vão fazer em face daquele ato.

A história da infância e da adolescência institucionalizada no Brasil permanece como objeto de estudo de pesquisadores em razão de existirem muitas questões a serem desmistificadas, desmembradas e revisitadas. Do período da Roda dos Expostos até hoje, vigente a Constituição Federal de 1988 e o Estatuto da Criança e do Adolescente de 1990, a institucionalização ainda é um método frequente, mesmo que a legislação a trate como excepcional. O texto defende a possibilidade de trabalhar dentro desses ambientes em perspectiva educacional, apoiando-se na pedagogia social, enquanto teoria e metodologia, e no educador social, enquanto profissional que acompanha as crianças e adolescentes em situação de medida protetiva. Para tanto, apresenta resultados de investigação (em andamento) fundada em pesquisa bibliográfica sobre os temas em questão e que fundamentaram a investigação empírica realizada durante a elaboração da dissertação intitulada “A educação social e a autonomia de adolescentes em ...