Solvent-free microwave-assisted peroxidative oxidation of alcohols catalyzed by Iron(III)-TEMPO catalytic systems

The iron(III) complexes [H(EtOH)][FeCl2(L)(2)] (1), [H(2)bipy](1/2)[FeCl2(L)(2)].DMF (2) and [FeCl2(L)(2,2'-bipy)] (3) (L = 3-amino-2-pyrazinecarboxylate; H(2)bipy = doubly protonated 4,4'-bipyridine; 2,2'-bipy = 2,2'-bipyridine, DMF = dimethylformamide) have been synthesized and fully characterized by IR, elemental and single-crystal X-ray diffraction analyses, as well as by electrochemical methods. Complexes 1 and 2 have similar mononuclear structures containing different guest molecules (protonated ethanol for 1 and doubly protonated 4,4'-bipyridine for 2) in their lattices, whereas the complex 3 has one 3-amino-2-pyrazinecarboxylate and a 2,2'-bipyridine ligand. They show a high catalytic activity for the low power (10 W) solvent-free microwave assisted peroxidative oxidation of 1-phenylethanol, leading, in the presence of TEMPO, to quantitative yields of acetophenone [TOFs up to 8.1 x 10(3) h(-1), (3)] after 1 h. Moreover, the catalysts are of easy recovery and reused, at least for four consecutive cycles, maintaining 83 % of the initial activity and concomitant rather high selectivity. 3-Amino-2-pyrazinecarboxylic acid is used to synthesize three new iron(III) complexes which act as heterogeneous catalysts for the solvent-free microwave-assisted peroxidative oxidation of 1-phenylethanol.

Vanadium complexes: recent progress in oxidation catalysis

Oxidovanadium complexes and, to a less extent, some non-oxido ones, are widely used as catalysts or catalyst precursors for various oxidative catalytic reactions by H2O2, (BuOOH)-Bu-t or O-2 under mild conditions. Oxidation reactions (oxidation of alkanes and alcohols, epoxidation of alkenes and allylic alcohols, oxidative bromination, sulfoxidation and oxidative Strecker reactions) of organic compounds are the most relevant ones and are reviewed considering the recent advances in the last five years (2010-2014). The main types of both homogeneous and supported vanadium catalysts and the most efficient catalytic systems in the different reactions are presented and compared. The proposed mechanisms of various catalytic oxidation processes are also outlined. (C) 2015 Elsevier B.V. All rights reserved.

Y Trinuclear Cu-II structural isomers coordination, magnetism, electrochemistry and catalytic activity towards the oxidation of alkanes

The reaction of the Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) with copper(II) nitrate, acetate or metaborate has led to the isomeric complexes [Cu-3(L)(2)(MeOH)(4)] (1), [Cu-3(L)(2)(MeOH)(2)]2MeOH (2) and [Cu-3(L)(2)(MeOH)(4)] (3), respectively, in which the ligand L exhibits dianionic (HL2-, in 1) or trianionic (L3-, in 2 and 3) pentadentate 1O,O,N:2N,O chelation modes. Complexes 1-3 were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography, electrochemical methods and variable-temperature magnetic susceptibility measurements, which indicated that the intratrimer antiferromagnetic coupling is strong in the three complexes and that there exists very weak ferromagnetic intermolecular interactions in 1 but weak antiferromagnetic intermolecular interactions in both 2 and 3. Electrochemical experiments showed that in complexes 1-3 the Cu-II ions can be reduced, in distinct steps, to Cu-I and Cu-0. All the complexes act as efficient catalyst precursors under mild conditions for the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, leading to overall yields (based on the alkane) of up to 31% (TON = 1.55x10(3)) after 6 h in the presence of pyrazinecarboxylic acid.

Arylhydrazones of barbituric acid: synthesis, coordination ability and catalytic activity of their CoII, CoII/IIIand CuIIcomplexes toward peroxidative oxidation of alkanes

New ortho-substituted arylhydrazones of barbituric acid, 5-(2-(2-hydroxyphenyl)hydrazono) pyrimidine-2,4,6(1H,3H,5H)-trione (H4L1) and the sodium salt of 2-(2-(2,4,6-trioxotetra-hydropyrimidin-5(2H)-ylidene)hydrazinyl) benzenesulfonic acid (H4L2), [Na(H3L2)(mu-H2O)(H2O)(2)](2) (1), were used in the synthesis of Cu-II, Co-II and Co-II/III complexes, [Cu(H2L1)(H2O)(im)]center dot 3H(2)O (im = imidazole) (2), [Co(H2O)(6)] [Co(H2L1)(2)](2)center dot 8H(2)O (3), [Co(H2L2)(im)(3)] (4), [Cu(H2L2)(im)(2)]center dot H2O (5) and [Co(H2O)(6)][H3L2](2)center dot 8H(2)O (6). The complexes are water soluble and the mono-or di-deprotonated ligands display different coordination modes, depending on the synthetic conditions. The electrochemical behaviour of all the compounds was investigated by cyclic voltammetry and controlled potential electrolysis, revealing that the ligands are also redox active. All the compounds were evaluated as catalysts for the peroxidative (with H2O2) oxidation of cyclohexane at room temperature. The compounds 2 and 3 are the most active ones (yields up to 21% and TON up to 213 are achieved, in the presence of 3).

Sulfonated Schiff base copper(ii) complexes as efficient and selective catalysts in alcohol oxidation: syntheses and crystal structures

The reaction between 2-aminobenzenesulfonic acid and 2-hydroxy-3-methoxybenzaldehyde produces the acyclic Schiff base 2-[(2-hydroxy-3-methoxyphenyl) methylideneamino] benzenesulfonic acid (H2L center dot 3H(2)O) (1). In situ reactions of this compound with Cu(II) salts and, eventually, in the presence of pyridine (py) or 2,2'-bipyridine (2,2'-bipy) lead to the formation of the mononuclear complexes [CuL(H2O)(2)] (2) and [CuL(2,2'-bipy)]center dot DMF center dot H2O (3) and the diphenoxo-bridged dicopper compounds [CuL(py)](2) (4) and [CuL(EtOH)](2)center dot 2H(2)O (5). In 2-5 the L-2-ligand acts as a tridentate chelating species by means of one of the O-sulfonate atoms, the O-phenoxo and the N-atoms. The remaining coordination sites are then occupied by H2O (in 2), 2,2'-bipyridine (in 3), pyridine (in 4) or EtOH (in 5). Hydrogen bond interactions resulted in R-2(2) (14) and in R-4(4)(12) graph sets leading to dimeric species (in 2 and 3, respectively), 1D chain associations (in 2 and 5) or a 2D network (1). Complexes 2-5 are applied as selective catalysts for the homogeneous peroxidative (with tert-butylhydroperoxide, TBHP) oxidation of primary and secondary alcohols, under solvent-and additive-free conditions and under low power microwave (MW) irradiation. A quantitative yield of acetophenone was obtained by oxidation of 1-phenylethanol with compound 4 [TOFs up to 7.6 x 10(3) h(-1)] after 20 min of MW irradiation, whereas the oxidation of benzyl alcohol to benzaldehyde is less effective (TOF 992 h(-1)). The selectivity of 4 to oxidize the alcohol relative to the ene function is demonstrated when using cinnamyl alcohol as substrate.

Aerobic bacteria, Chlamydia trachomatis, Pneumocystis carinii and Cytomegalovirus as agents of severe peneumonia in small infants

The authors studied 58 infants hospitalized for pneumonia in a semi-intensive care unit. Age ranged from 1 complete to 6 incomplete months. The infants were sent from another hospital in 20 cases and from home in a further 38. Pulmonary involvement, which was alveolar in 46 cases and interstitial in 12, was bilateral in 31 children. The investigation was carried out prospectively on the etiological agents associated with respiratory infection to look for evidence of aerobic bacteria (blood cultures), Chlamydia trachomatis and Cytomegalovirus (serology), and Pneumocystis carinii (direct microscopy of tracheal aspirated material). The following infectious agents were diagnosed in 21 children (36.2%): Aerobic bacteria (8), Chlamydia trachomatis (5), Pneumocystis carinii (3), Cytomegalovirus (3), Cytomegalovirus and Chlamydia trachomatis (1), Aerobic bacteria and Cytomegalovirus (1). Seven cases of infection by Chlamydia trachomatis and/or Cytomegalovirus were diagnosed out of the 12 cases with pulmonary interstitial involvement.

The removal of xenobiotic compounds from wastewater through the use of biological processes and advanced oxidation technologies

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química e Bioquímica pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Decavanadate interactions with actin: cysteine oxidation and vanadyl formation

Dalton Trans., 2009, 7985–7994

Effects of Aerobic Exercise on Anxiety Disorders: A Systematic Review

Anxiety disorders are the most common psychiatric disorders observed currently. It is a normal adaptive response to stress that allows coping with adverse situations. Nevertheless, when anxiety becomes excessive or disproportional in relation to the situation that evokes it or when there is not any special object directed at it, such as an irrational dread of routine stimuli, it becomes a disabling disorder and is considered to be pathological. The traditional treatment used is medication and cognitive behavioral psychotherapy, however, last years the practice of physical exercise, specifically aerobic exercise, has been investigated as a new non-pharmacological therapy for anxiety disorders. Thus, the aim of this article was to provide information on research results and key chains related to the therapeutic effects of aerobic exercise compared with other types of interventions to treat anxiety, which may become a useful clinical application in a near future. Researches have shown the effectiveness of alternative treatments, such as physical exercise, minimizing high financial costs and minimizing side effects. The sample analyzed, 66.8% was composed of women and 80% with severity of symptoms anxiety as moderate to severe. The data analyzed in this review allows us to claim that alternative therapies like exercise are effective in controlling and reducing symptoms, as 91% of anxiety disorders surveys have shown effective results in treating. However, there is still disagreement regarding the effect of exercise compared to the use of antidepressant symptoms and cognitive function in anxiety, this suggests that there is no consensus on the correct intensity of aerobic exercise as to achieve the best dose-response, with intensities high to moderate or moderate to mild.

Aerobic Exercise Does Not Predict Brain Derived Neurotrophic Factor And Cortisol Alterations in Depressed Patients

The pathophysiology of depression is related to neurobiological changes that occur in the monoamine system, hypothalamic-pituitary-adrenal axis, neurogenesis system and the neuroimmune system. In recent years, there has been a growing interest in the research of the effects of exercise on brain function, with a special focus on its effects on brainderived neurotrophic factor (BDNF), cortisol and other biomarkers. Thus, the aim of this study is to present a review investigating the acute and chronic effects of aerobic exercise on BDNF and cortisol levels in individuals with depression. It was not possible to establish an interaction between aerobic exercise and concentration of BDNF and cortisol, which may actually be the result of the divergence of methods, such as type of exercises, duration of the sessions, and prescribed intensity and frequency of sessions.

Comparison Among Aerobic Exercise and Other Types of Interventions to Treat Depression: A Systematic Review

Depression is a common and disabling disease that affects over 100 million people worldwide and can have a significant impact on physical and mental health, reducing their quality of life. Thus, the aim of this article was to provide information on research results and key chains related to the therapeutic effects of chronic aerobic exercise compared with other types of interventions to treat depression, which may become a useful clinical application in a near future. Researches have shown the effectiveness of alternative treatments, such as physical exercise, minimizing high financial costs and minimizing side effects. In this review, the data analyzed allows us to claim that alternative therapies, such as exercise, are effective on controlling and reducing symptoms. 69.3% of the studies that investigated the antidepressant effects of exercise on depressive were significant, and the other 30.7% of the studies improved only in general physiological aspects, such as increased oxygen uptake, increased use of blood glucose and decreased body fat percentage, with no improvement on symptoms of depression. From the sample analyzed, 71.4% was composed of women, and regarding the severity of symptoms, 85% had mild to moderate depression and only 15% had moderate to severe depression. However, there is still disagreement regarding the effect of exercise compared to the use of antidepressants in symptomatology and cognitive function in depression, this suggests that there is no consensus on the correct intensity of aerobic exercise as to achieve the best dose-response, with intensities high to moderate or moderate to mild.

Effects of Aerobic Exercise Associated with Abdominal Microcurrent: A Preliminary Study

Objective: To analyze the short- and long-term effects of microcurrent used with aerobic exercise on abdominal fat (visceral and subcutaneous). Methods: Forty-two female students from a university population were randomly assigned into five group: intervention group (IG) 1 (n=9), IG2 (n=9), IG3 (n=7), IG4 (n=8), and placebo group (PG) (n=9). An intervention program of 10 sessions encompassing microcurrent and aerobic exercise (performed with a cycloergometer) was applied in all groups, with slightly differences between them. In IG1 and IG2, microcurrent with transcutaneous electrodes was applied, with different frequency values; 30-minute exercise on the cycloergometer was subsequently performed. IG3 used the same protocol as IG1 but with different electrodes (percutaneous), while in IG4 the microcurrent was applied simultaneously with the cycloergometer exercise. Finally, the PG used the IG1 protocol but with the microcurrent device switched off. All groups were evaluated through ultrasound and abdominal perimeter measurement for visceral and subcutaneous abdominal fat assessment; through calipers for skinfolds measurement; through bioimpedance to evaluate weight, fat mass percentage, and muscular mass; and through blood analyses to measure cholesterol, triglyceride, and glucose levels. Results: After intervention sessions, visceral fat decreased significantly in IG1 compared with the PG. Subcutaneous fat was reduced significantly in all groups compared with the PG. After 4 weeks, almost all results were maintained. Conclusion: The addition of microcurrent to aerobic exercise may reduce fat more than does aerobic exercise alone.

Electrochemical characterization of Dps, a DNA-protecting protein

Dissertação para obtenção do Grau de Mestre em Biotecnologia

Fsp27/CIDEC is a CREB target gene induced during fasting and regulated by fatty acid oxidation rate

Dissertação para obtenção do Grau de Mestre em Biotecnologia

The mechanism of formate oxidation by metal-dependent formate dehydrogenases

J Biol Inorg Chem (2011) 16:1255–1268 DOI 10.1007/s00775-011-0813-8