980 resultados para 5-AMINOLEVULINIC ACID-DERIVATIVES


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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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This paper describes 2 alternative methodologies for the determination of selected aldehydes (formaldehyde, acetaldehyde, propionaldehyde, acrolein, and benzaldehyde) by capillary electrophoresis (CE), the first approach is based on the formation of aldehyde-bisulfite adducts and employs free solution CE with reversed electroosmotic flow and indirect detection, using 10 mmol/L 3,5-dinitrobenzoic acid (pH 4.5) containing 0.2 mmol/L cetyltrimethylammonium bromide as the electrolyte. This novel methodology showed a fairly good sensitivity to concentration, with detection limits with respect to a single aldehyde on the order of 10-40 mu g/L, a reasonable analysis time (separation was achieved in <8 min), and no need for sample manipulation. A second approach was proposed in which 2,4-dinitrophenylhydrazine derivatives of the aldehydes were detected in a micellar electrolyte medium (20 mmol/L berate buffer containing 50 mmol/L sodium dodecyl sulfate and 15 mmol/L beta-cyclodextrin). This latter methodology included a laborious sample preconcentration step and showed much poorer sensitivity (0.5-2 mg/L detection limit, with respect to a single aldehyde), despite the use of sodium chloride to promote sample stacking. Both methodologies proved adequate to evaluate aldehyde levels in vehicular emissions. Samples from the tailpipe exhaust of a passenger car vehicle without a catalytic converter and operated with an ethanol-based fuel were collected and analyzed; the results showed high levels of formaldehyde and acetaldehyde (0.41-6.1 ppm, v/v). The concentrations estimated by the 2 methodologies, which were not in good agreement, suggest the possibility of striking differences in sample collection efficiency, which was not the concern of this work.

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From a hexane extract of stems and roots of Aristolochia pubescens, the new neolignans (2S,3S,1'R,2'R)- and (2S,3S, 1'S,2'R)-2,3-dihydro-5-(1',2'-dihydroxypropyl)-2-(4-hydroxy-3-methylbenzofuran) and (2S,3S,1'R,2'R)- and (2S,3S,1'S,2'R)-2,3-dihydro-5-(1',2'-dihydroxypropyl)-2-(3,4-dimethoxyphenyl)-7-methoxy-3-methyl-benzofuran were isolated, together with the known neolignan licarin A, and its bisnor-neolignan aldehyde and acid derivatives. In addition, sitosterol, 8R,9R-oxide-beta-caryophyllene, kobusone, ent-kauran-16 alpha, 17-diol, vanillin, vanillic acid, (+)-sesamin, (+)eudesmin, and (-)-cubebin were isolated. The structures of the new compounds have been elucidated by spectroscopic methods and by chemical transformation using Mosher's acid chloride. (C) 1999 Elsevier B.V. Ltd. All rights reserved.

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The effects of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) on the central nervous system (CNS) were studied in rats. Behavioural and neurochemical studies were performed. Results show that acute and oral administration of dimethylamine 2,4-D was able to decrease locomotion and rearing frequencies and to increase immobility duration of rats observed in an open-field test. Treatment of rats with p-chlorophenylalanine (PCPA) was unable to change rat's open-field behaviour; 5-hydroxytryptophan (5-HTP) administration not only increased locomotion and rearing frequences but also decreased immobility duration. Pretreatment of the rats with PCPA and 5-HTP decreased and increased dimethylamine 2,4-D effects, respectively. The herbicide was not able to change the striatal levels of dopamine and homovanilic acid but decreased the striatal levels of serotonin (5-HT), as observed for the doses of 100 and 200 mg/kg and increased those of 5-hydroxyindoleacetic acid (5-HIAA) as measured after the 200 mg/kg dose treatment. When the levels of serotonin and 5-HIAA were measured at the brain stem level, only those of 5-HIAA were modified, being increased by diethylamine 2,4-D (60; 100 and 200 mg/kg); this increment on 5-HIAA levels was observed even 1 hr after pesticide administration. Further analysis showed that 2,4-D concentrations chromatographycally detected both in serum and brain of the intoxicated animals were dose-dependent, being found as early as 1 hr after the smaller dose of the herbicide used (10 mg/kg). The results suggest that diethylamine 2,4-D modify 5-HT functional activity within the CNS. Thus, the effects of the herbicide on open-field behaviour of rats could be attributed to a direct or indirect pesticide action on serotoninergic systems.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Lanthanide compounds of general formula [Ln2(2,5-tdc) 3(dmf)2(H2O)2] ·2dmf·H2O (Ln = Eu(III) (1), Tb(III) (2), Gd(III) (3) and Dy(III) (4), dmf = N,N′-dimethylformamide and 2,5-tdc2- = 2,5-thiophedicarboxylate anion) were synthesized and characterized by elemental analysis, X-ray powder diffraction patterns, thermogravimetric analysis and infrared spectroscopy. Phosphorescence data of Gd(III) complex showed that the triplet states (T1) of 2,5-tdc2- ligand have higher energy than the main emitting states of Eu(III), Tb(III) and Dy(III), indicating that 2,5-tdc2- ligand can act as intramolecular energy donor for these metal ions. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal energy transfer. The high value of experimental intensity parameter Ω2 for the Eu(III) complex indicate that the europium ion is in a highly polarizable chemical environment. The emission quantum efficiency (η) of the 5D0 emitting level of Eu(III) was also determined. The complexes act as possible light conversion molecular devices (LCMDs). © 2013 Elsevier B.V. All rights reserved.

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The color characteristics and the phenolic composition related to color of young red wines elaborated with the hybrid grape cultivar BRS Violeta, developed for its adaptation to sub-tropical climates in Brazil, have been studied. These wines are characterized with a deep red-purplish color, reaching color intensity averaging 24 units. In spite of being young red wines elaborated with short maceration time, their content in total polyphenols was very high (around 3692. mg/L, as gallic acid equivalents), especially when compared to similar Vitis vinifera young red wines. Within polyphenols, anthocyanins predominated (around 2037. mg/L, as malvidin 3,5-diglucoside equivalents) and they were almost exclusively anthocyanidin 3,5-glucosides (ca. 97%), mainly built from B-ring tri-substituted anthocyanidins (delphinidin. >. petunidin. ≈. malvidin) and having high proportion of p-coumaroylated derivatives (ca. 28%) that confer higher stability. The content of hydroxycinnamic acid derivatives was also remarkable (ca. 95. mg/L, as caffeic acid equivalents) and unknown glucose derivatives of p-coumaric acid accounted for ca. 42% of total HCAD. Finally, these found flavonols were mainly based on myricetin whereas kaempferol derivatives were missing, their total content being within the ranges usually found for V. vinifera wines, but reaching their top values (ca. 91. mg/L, as quercetin 3-glucoside equivalents). All the aforementioned data suggest that Violeta wine could be considered an important dietary source of healthy polyphenols with a moderate alcoholic content (ca. 11.6%). © 2013 Elsevier Ltd.

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The grape is considered a major source of phenolic compounds when compared to other fruits and vegetables, however, there are many cultivars with distinct characteristics directly linked to phenolic profile. Thus, the present study aimed to identify and quantify, for the first time and in detail, the phenolic compounds present in the skin, flesh and seeds of BRS Violeta grape berry using combination of SPE methodologies and analytical HPLC-DAD-ESI-MS/MS. The study was extended to the different berry parts and the most important grape and wine phenolic families, and has revealed interesting features. Violeta grape has a very thick skin (46% of grape weight) that accumulated the most of grape phenolic compounds: great amount of anthocyanins (3930. mg/kg, as malvidin 3,5-diglucoside), together with also important amounts of flavonols (150. mg/kg, as quercetin 3-glucoside), hydroxycinnamic acid derivatives (HCAD; 120. mg/kg, as caftaric acid), and proanthocyanidins (670. mg/kg, as (+)-catechin); in contrast, it seems to be a low resveratrol producer. Violeta grape seeds accounted for similar proportions of low molecular weight flavan-3-ols (mainly monomers; 345. mg/kg, as (+)-catechin) and proanthocyanidins (480. mg/kg, as (+)-catechin). Violeta grape is a teinturier cultivar, but it only contained traces of anthocyanins and low amounts of all the other phenolic types in its red-colored flesh. The anthocyanin composition of Violeta grape was dominated by anthocyanidin 3,5-diglucosides (90%). Within flavonols, myricetin-type predominated and kaempferol-type was missing. In addition to expected hydroxycinnamoyl-tartaric acids, several isomeric esters of caffeic and p-coumaric acids with hexoses were tentatively identified, accounting for relevant proportions within the pool of HCAD. Although pending of further confirmation over successive vintages, the aforementioned results suggest that BRS Violeta grape cultivar could be considered an interesting candidate for the elaboration of highly colored and antioxidant-rich grape juices and wines. © 2013 Elsevier Ltd.

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The novel coordination polymer with the formula {[Nd2(2,5-tdc)3(dmf)2(H2O)2].dmf.H2O}n (2,5-tdc2-=2,5-thiophedicarboxylate anion and dmf=dimethylformamide) has been synthesized and characterized by thermal analysis (TG/DTA), vibrational spectroscopy (FTIR) and single crystal X-ray diffraction analysis (XRD). Structure analysis reveals that Nd(III) ions show dicapped trigonal prism coordination geometry. The 2,5-tdc2- ligands connect four Nd(III) centers, adopting (κ1 - κ1) - (κ1 - κ1) - μ4 coordination mode, generating an interesting 6-connected uninodal 3D network. Photophysical properties were studied using diffuse reflectance spectroscopy (DR) and excitation/emission spectra. The photoluminescence data show the near infrared emission (NIR) with the characteristic 4F3/2→4IJ (J=9/2, 11/2 and 13/2) transitions of Nd(III) ion, indicating that 2,5-tdc2- is able to act as a sensitizer for emission in NIR region. © 2013 Elsevier B.V.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Pós-graduação em Química - IQ