985 resultados para Lanthanides(III) chelate complexes


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Class III skeletal malocclusion may present several etiologies, among which maxillary deficiency is the most frequent. Bone discrepancy may have an unfavorable impact on esthetics, which is frequently aggravated by the presence of accentuated facial asymmetries. This type of malocclusion is usually treated with association of Orthodontics and orthognathic surgery for correction of occlusion and facial esthetics. This report presents the treatment of a patient aged 15 years and 1 month with Class III skeletal malocclusion, having narrow maxilla, posterior open bite on the left side, anterior crossbite and unilateral posterior crossbite, accentuated negative dentoalveolar discrepancy in the maxillary arch, and maxillary and mandibular midline shift. Clinical examination also revealed maxillary hypoplasia, increased lower one third of the face, concave bone and facial profiles and facial asymmetry with mandibular deviation to the left side. The treatment was performed in three phases: presurgical orthodontic preparation, orthognathic surgery and orthodontic finishing. In reviewing the patient's final records, the major goals set at the beginning of treatment were successfully achieved, providing the patient with adequate masticatory function and pleasant facial esthetics.

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The effect of S,S-ethylenediaminedisuccinic acid (edds) on the quenching of metal-catalyzed (metal = Mn, Fe, Co, Ni, Cu, Zn) oxidation of ascorbic acid was tested in vitro via oxidation of the fluorescent probe 1,2,3-dihydrorhodamine dihydrochloride. The pro-oxidant activity of iron was not fully suppressed, even at a four-fold molar excess of the ligand. The effect of serum on the toxicity to peripheral blood mononuclear cells (PBMC) and K562 cells was investigated. The cytotoxic effect of Fe-edds was abrogated in the presence of Trolox or serum proteins. The probable pathways of cell toxicity were investigated through blocking of the monocarboxylate transporters (MCT) in association with cell cycle studies by flow cytometry. Cells treated with metal complexes and alpha-cyano-4-hydroxycinnamic acid, a known MCT inhibitor, showed recovery of viability, suggesting that MCT proteins may be involved in the internalization of metal-edds complexes. The free acid induced cell cycle arrest in G0/G1 (PBMC) and S (K562) phases, suggesting direct DNA damage or interference in DNA replication.

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In this work we have studied cyclooctene epoxidation with PhIO, using a new iron porphyrin, 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrinato iron(III), supported on silica matrices via eletrostatic interaction and / or covalent bonds as catalyst. These catalysts were obtained and immobilized on the solid supports propyltrimethylammonium silica (SiN+); propyltrimethylammonium and propylimidazole silica [SiN+(IPG)] and chloropropylsilica (CPS) via elestrostatic interactions and covalent binding. Characterization of the supported catalysts by UV-Vis spectroscopy and EPR (Electron paramagnetic resonance) indicated the presence of a mixture of FeII and FeIII species in all of the three obtained catalysts. In the case of (Z)-cyclooctene epoxidation by PhIO the yields observed for cis-epoxycyclooctane were satisfactory for the reactions catalyzed by the three materials (ranging from 68% to 85%). Such results indicate that immobilization of metalloporphyrins onto solid supports via groups localized on the ortho positions of their mesophenyl rings can lead to efficient catalysts for epoxidation reactions. The catalyst 1-CPS is less active than 1-SiN and 1-SiN(IPG), this argues in favour of the immobilization of this metalloporphyrin onto solids via electrostatic interactions, which is easier to achieve and results in more active oxidation catalysts. Interestingly, the activity of the supported catalysts remained the same even after three successive recyclings; therefore, they are stable under the oxidizing conditions.

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Herein, the immobilization of some Schiff base-copper(II) complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

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A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This À-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable À-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.

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A metal-free protocol was developed to synthesize indanes by ring contraction of 1, 2-dihydronaphthalenes promoted by PhI(OH)OTs (HTIB or Koser's reagent). This oxidative rearrangement can be performed in several solvents (MeOH, CH3CN, 2 , 2, 2-trifluoroethanol (TFE), 1 , 1, 1, 3, 3, 3-hexafluoroisopropanol (HFIP), and a 1:4 mixture of TFE:CH2Cl2) under mild conditions. The ring contraction diastereoselectively gives functionalized trans-1, 3-disubstituted indanes, which are difficult to obtain in synthetic organic chemistry

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Oitenta e quatro espécies são registradas para o Estado do Maranhão: Prioninae (uma), Disteniinae (uma), Cerambycinae (49) e Lamiinae (33). O número total de espécies assinaladas para o Estado eleva-se a 367. Nove novas espécies são descritas em Cerambycinae: Chlorida inexpectata sp. nov. (Bothriospilini); Jupoata germana sp. nov. (Cerambycini); Eburodacrys separatus sp. nov. e Eburodacrys cincora sp. nov. (Eburiini); Ectenessa affinis sp. nov. (Ectenessini); Minibidion bicolor sp. nov. (Ibidionini, Tropidiina); Compsibidion maculatum sp. nov. e Compsibidion ytu sp. nov. (Ibidionini,Ibidionina); Ideratus beatus sp. nov. (Ideratini). Três espécies são descritas em Lamiinae: Aerenea gibba sp. nov. (Compsosomatini); Mimasyngenes barbozai sp. nov. (Desmiphorini); Cacostola exilis sp. nov. (Onciderini). Uma variação no colorido de Adesmus paradiana Galileo & Martins, 2004 é observada. Corrigenda de Piruana pulchra Martins et al., 2009 para Piruauna pulchra (Desmiphorini).

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Oxyommata Zajciw, 1970 e O. collaris (Audinet-Serville, 1833) são redescritos e comentados. Um novo gênero proveniente da divisão de Xenocrasis Bates, 1873 é descrito e três espécies alocadas nele: X. fulvicollis(Lacordaire, 1868); X. pubipennis (Fisher, 1952); e X. vestitipennis Zajciw, 1963. É apresentada chave para as espécies do novo gênero.

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Novas espécies da Guiana Francesa são descritas e figuradas: Trestonia bilineta sp. nov. (Onciderini); Ischnolea odettae sp. nov. (Desmiphorini); Oreodera mageia sp. nov. (Acanthoderini) e Icupima ampliata sp. nov. (Hemilophini). Faz-se um novo registro de Plocaederus fragosoi (Cerambycini) para a Guiana Francesa.

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São discriminados em chave os gêneros semelhantes a Anoreina Bates, 1861, Trichoanoreina Julio & Monné, 2005 e Pyrianoreina gen. nov. Espécies novas descritas: Pyrianoreina piranga sp. nov. do Equador; P. hovorei sp. nov. da Bolívia; do Brasil Anoreina piara sp. nov. (Pará) e A. pinimaiuba sp. nov. (Amazonas); A. ayri sp. nov. do Equador.

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It was evaluated the effects of levels of digestible lysine and chelate zinc combined in the diet for laying on the egg quality. It was used 720 birds, from 48 to 60 weeks of age, distributed in a completely randomized design in a 3 × 5 factorial scheme with three levels of zinc and five levels of lysine, applied into six replicates in the experimental units of eight birds per plot. The levels were: 137, 309 and 655 ppm zinc and 0.482, 0.527, 0.582, 0.644 and 0.732% digestible lysine. It was not observed any interaction among digestible lysine and zinc for the primary variables of fractions and egg composition. Levels of zinc reduced egg weight, suggesting the lowest efficiency in nutrient intake. At the highest dietary concentration of zinc, the addition of digestible lysine coincided with a linear increase in shell weight. However, zinc addition, regardless of lysine level in the diet, resulted in the reduction of egg weight and of the percentage of mineral matter in the yolk, limiting the efficiency of mineral deposition in this fraction of the egg. Concentration of zinc that produced the best results was 137 ppm inasmuch as higher quantities limit the use of digestible lysine, with effects harming composition and egg quality. The study indicates the following requirement for digestible lysine: 0.639% from the 48th to the 52nd week, 0.679% from the 52nd to 56th week, and 0.635% from the 56th to the 60th week. Considering the total period from 48th to the 60th week, the level 0.638% of lysine or the daily intake of 707 mg of the amino acid met the requirement for egg quality of semi-heavy layers used in this study.

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We carried out a first-principles investigation on the microscopic properties of nickel-related defect centers in diamond. Several configurations, involving substitutional and interstitial nickel impurities, have been considered either in isolated configurations or forming complexes with other defects, such as vacancies and boron and nitrogen dopants. The results, in terms of spin, symmetry, and hyperfine fields, were compared with the available experimental data on electrically active centers in synthetic diamond. Several microscopic models, previously proposed to explain those data, have been confirmed by this investigation, while some models could be discarded. We also provided insights into the microscopic structure of several of those centers.

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Chemical reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam, fac-[Ru(NO)Cl(2)(kappa(3)N(4),N(8),N(11)(1-carboxypropyl)cyclam)]Cl center dot H(2)O ((1-carboxypropyl) cyclam = 3-(1,4,8,11-tetraazacyclotetradecan-1-yl) propionic acid)), (I) are described. Chloride ligands do not undergo aquation reactions (at 25 degrees C, pH 3). The rate of nitric oxide (NO) dissociation (k(obs-NO)) upon reduction of I is 2.8 s(-1) at 25 +/- 1 degrees C (in 0.5 mol L(-1) HCl), which is close to the highest value found for related complexes. The uncoordinated carboxyl of I has a pK(a) of similar to 3.3, which is close to that of the carboxyl of the non coordinated (1-carboxypropyl) cyclam (pK(a) = 3.4). Two additional pK(a) values were found for I at similar to 8.0 and similar to 11.5. Upon electrochemical reduction or under irradiation with light (lambda(irr) = 350 or 520 nm; pH 7.4), I releases NO in aqueous solution. The cyclam ring N bound to the carboxypropyl group is not coordinated, resulting in a fac configuration that affects the properties and chemical reactivities of I, especially as NO donor, compared with analogous trans complexes. Among the computational models tested, the B3LYP/ECP28MDF, cc-pVDZ resulted in smaller errors for the geometry of I. The computational data helped clarify the experimental acid-base equilibria and indicated the most favourable site for the second deprotonation, which follows that of the carboxyl group. Furthermore, it showed that by changing the pH it is possible to modulate the electron density of I with deprotonation. The calculated NO bond length and the Ru/NO charge ratio indicated that the predominant canonical structure is [Ru(III)NO], but the Ru-NO bond angles and bond index (b.i.) values were less clear; the angles suggested that [Ru(II)NO(+)] could contribute to the electronic structure of I and b.i. values indicated a contribution from [Ru(IV)NO(-)]. Considering that some experimental data are consistent with a [Ru(II)NO(+)] description, while others are in agreement with [Ru(III)NO], the best description for I would be a linear combination of the three canonical forms, with a higher weight for [Ru(II)NO(+)] and [Ru(III)NO].

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Background: Spinal muscular atrophy (SMA) is an autosomal recessive disorder that affects the motoneurons of the spinal anterior horn, resulting in hypotonia and muscle weakness. The disease is caused by deletion or mutation in the telomeric copy of SMN gene (SMN1) and clinical severity is in part determined by the copy number of the centromeric copy of the SMN gene (SMN2). The SMN2 mRNA lacks exon 7, resulting in a production of lower amounts of the full-length SMN protein. Knowledge of the molecular mechanism of diseases has led to the discovery of drugs capable of increasing SMN protein level through activation of SMN2 gene. One of these drugs is the valproic acid (VPA), a histone deacetylase inhibitor. Methods: Twenty-two patients with type II and III SMA, aged between 2 and 18 years, were treated with VPA and were evaluated five times during a one-year period using the Manual Muscle Test (Medical Research Council scale-MRC), the Hammersmith Functional Motor Scale (HFMS), and the Barthel Index. Results: After 12 months of therapy, the patients did not gain muscle strength. The group of children with SMA type II presented a significant gain in HFMS scores during the treatment. This improvement was not observed in the group of type III patients. The analysis of the HFMS scores during the treatment period in the groups of patients younger and older than 6 years of age did not show any significant result. There was an improvement of the daily activities at the end of the VPA treatment period. Conclusion: Treatment of SMA patients with VPA may be a potential alternative to alleviate the progression of the disease.

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Context. To study the evolution of Li in the Galaxy it is necessary to observe dwarf or subgiant stars. These are the only long-lived stars whose present-day atmospheric chemical composition reflects their natal Li abundances according to standard models of stellar evolution. Although Li has been extensively studied in the Galactic disk and halo, to date there has only been one uncertain detection of Li in an unevolved bulge star. Aims. Our aim with this study is to provide the first clear detection of Li in the Galactic bulge, based on an analysis of a dwarf star that has largely retained its initial Li abundance. Methods. We performed a detailed elemental abundance analysis of the bulge dwarf star MOA-2010-BLG-285S using a high-resolution and high signal-to-noise spectrum obtained with the UVES spectrograph at the VLT when the object was optically magnified during a gravitational microlensing event (visual magnification A similar to 550 during observation). The Li abundance was determined through synthetic line profile fitting of the (7)Li resonance doublet line at 670.8 nm. The results have been corrected for departures from LTE. Results. MOA-2010-BLG-285S is, at [Fe/H] = -1.23, the most metal-poor dwarf star detected so far in the Galactic bulge. Its old age (12.5 Gyr) and enhanced [alpha/Fe] ratios agree well with stars in the thick disk at similar metallicities. This star represents the first unambiguous detection of Li in a metal-poor dwarf star in the Galactic bulge. We find an NLTE corrected Li abundance of log epsilon(Li) = 2.16, which is consistent with values derived for Galactic disk and halo dwarf stars at similar metallicities and temperatures. Conclusions. Our results show that there are no signs of Li enrichment or production in the Galactic bulge during its earliest phases. Observations of Li in other galaxies (omega Cen) and other components of the Galaxy suggest further that the Spite plateau is universal.