32 resultados para Carbon Species
em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Dendritic nucleic acids are highly branched and ordered molecular structures, possessing numerous single-stranded oligonucleotide arms, which hold great promise for enhancing the sensitivity of DNA biosensors. This article evaluates the interfacial behavior and redox activity of nucleic acid dendrimers at carbon paste electrodes, in comparison to DNA. Factors influencing the adsorption behavior, including the adsorption potential and time, solution conditions, or dendrimer concentration, are explored. The strong adsorption at the anodically pretreated carbon surface is exploited for an effective preconcentration step prior to the chronopotentiometric measurement of the surface species. Coupled with the numerous guanine oxidation sites, such stripping protocol offers remarkably low detection limits (e.g., 3 pM or 2.4 femtomole of the I-layer dendrimer following a 15 min accumulation). The new observations bear important implications upon future biosensing applications of nucleic dendrimers.
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Phenolic resins when heat treated in inert atmosphere up to 1000 degreesC become glassy polymeric carbon (GPC), a chemically inert and biocompatible material useful for medical applications, such as in the manufacture of heart valves and prosthetic devices. In earlier work we have shown that ion bombardment can modify the surface of GPC, increasing its roughness. The enhanced roughness, which depends on the species, energy and fluence of the ion beam, can improve the biocompatibility of GPC prosthetic artifacts. In this work, ion bombardment was used to make a layer of implanted ions under the surface to avoid the propagation of microcracks in regions where cardiac valves should have pins for fixation of the leaflets. GPC samples prepared at 700 and 1500 degreesC were bombarded with ions of silicon. carbon, oxygen and gold at energies of 5, 6, 8 and 10 MeV, respectively, and fluences between 1.0 x 10(13) and 1.0 x 10(16) ions/cm(2). Nanoindentation hardness characterization was used to compare bombarded with non-bombarded samples prepared at temperatures up to 2500 degreesC. The results with samples not bombarded showed that the hardness of GPC increases strongly with the heat treatment temperature. Comparison with ion bombarded samples shows that the hardness changes according to the ion used, the energy and fluence. (C) 2002 Elsevier B.V. B.V. All rights reserved.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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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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Este trabalho apresenta o estudo de substâncias apolares obtidas a partir de plantas pertencentes ao gênero Paepalanthus Mart. (Eriocaulaceae). Hidrocarbonetos alifáticos de cadeias longas lineares foram identificados por CG-DIC e CG-EM. Os resultados indicam que as espécies de Paepalanthus subg. Platycaulon apresentam perfil homogêneo, com cadeias carbônicas de n-alcanos variando de C25 a C31, com a maioria das amostras apresentando freqüências maiores dos homólogos C27 e C29. As espécies do subgênero Paepalocephalus podem ser diferenciadas pela distribuição dos n-alcanos principais. P. macrocephalus, uma espécie da subseção Aphorocaulon, apresenta perfil com alcanos de cadeia ímpar, enquanto P. denudatus e P. polyanthus, espécies da seção Actinocephalus, apresentam perfil bem distinto, com grande número de cadeias mais curtas e alta freqüência de cadeias com número par de carbonos, especialmente P. polyanthus. Os resultados obtidos indicam que a distribuição de nalcanos pode ser útil como caráter taxonômico, assim como as substâncias mais polares, como os flavonóides glicosilados.
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An improved on-site characterization of humic-rich hydrocolloids and their metal species in aquatic environments was the goal of the present approach. Both ligand exchange with extreme chelators ( diethylenetetraaminepentaacetic acid ( DTPA), ethylendiaminetetraacetic acid ( EDTA)) and metal exchange with strongly competitive cations (Cu(II)) were used on-site to characterize the conditional stability and availability of colloidal metal species in a humic-rich German bogwater lake ( Venner Moor, Munsterland). A mobile time-controlled tangential-flow ultrafiltration technique (cut-off: 1 kDa) was applied to differentiate operationally between colloidal metal species and free metal ions, respectively. DOC ( dissolved organic carbon) and metal determinations were carried out off-site using a home-built carbon analyzer and conventional ICP-OES ( inductively-coupled plasma-optical emission spectrometry), respectively. From the metal exchange equilibria obtained on-site the kinetic and thermodynamic stability of the original metal species ( Fe, Mn, Zn) could be characterized. Conditional exchange constants K ex obtained from aquatic metal species and competitive Cu(II) ions follow the order Mn > Zn >> Fe. Obviously, Mn and Zn bound to humic-rich hydrocolloids are very strongly competed by Cu( II) ions, in contrast to Fe which is scarcely exchangeable. The exchange of aquatic metal species (e.g. Fe) by DTPA/EDTA exhibited relatively slow kinetics but rather high metal availabilities, in contrast to their Cu(II) exchange.
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A new, versatile, and simple method for quantitative analysis of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry is described. These metals can be quantified by direct dissolution of fuel ethanol in water and subsequent voltammetric measurement after the accumulation step. A maximum limit of 20% (v/v) ethanol in water solution was obtained for voltammetric measurements without loss of sensitivity for metal species. Chemical and operational optimum conditions were analyzed in this study; the values obtained were pH 2.9, a 4.7-mum thickness mercury film, a 1,000-rpm rotation frequency of the working electrode, and a 600-s pre-concentration time. Voltammetric measurements were obtained using linear scan (LSV), differential pulse (DPV), and square wave (SWV) modes and detection limits were in the range 10(-9)-10(-8) mol L-1 for these metal species. The proposed method was compared with a traditional analytical technique, flame atomic absorption spectrometry (FAAS), for quantification of these metal species in commercial fuel ethanol samples.
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A highly sensitive amperometric biosensor for determination of carbamate pesticides directly in water, fruit and vegetable samples has been evaluated, electrochemically characterized and optimized. The biosensor strip was fabricated in screen printed technique on a ceramic support using silver-based paste for reference electrode, and platinum-based paste for working and auxiliary electrodes. The working electrode was modified by a layer of carbon paste mixed with cobalt(II) phthalocyanine and acetylcellulose. Cholinesterase (ChE) enzymes with low enzymatic charge were immobilized on this layer. The operational simplicity of the biosensor consists in that a small drop (similar to 50 mu l) of substrate or sample is deposited on a horizontally positioned biosensor strip representing the microelectrochemical cell. The working potential of the biosensor was 370 mV versus Ag/AgI on a ship reference electrode preventing the interference of electroactive species which are oxidable at more positive potentials. The biosensor was applied to investigate the degradation of two reference ChE inhibitors in freeze dried water under different storage conditions and for direct determination of some N-methylcarbamates (NMCs) in fruit and vegetable samples at ppb concentration levels without any sample pretreatment. A comparison of the obtained results for the total carbamate concentration was done against those obtained using HPLC measurements. (C) 1999 Elsevier B.V. B.V. All rights reserved.
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The free mycolic acid fraction from Rhodococcus lentifragmentus was derivatized to methyl esters and further fractionated into saturated (F-0), monounsaturated (F-1) and diunsaturated (F-2) species using argentation-TLC. Methyl esters fractions F-0, F-1 and F-2, accounting for approximately 7.4%, 53.1% and 39.5%, respectively, were analyzed by electron impact (EI) and chemical ionization (CI) mass spectrometries. According to EI-MS, peaks observed for M(+)-18, that were prominent compared to those representing M(+)-32 and M(+)-(18 + 32), indicated that the carbon chain size ranged from C-36 to C-48. The pyrolytic cleavage of methyl mycolates (R(2)-CHOH-CH(R(1))-COOCH3), following the McLafferty rearrangement released fragment ions corresponding to, (a) the alpha-subunit, representing the fatty acid methyl ester (R(1)-CH2-COOCH3), methyl hexadecanoate, methyl tetradecanoate and methyl dodecanoate in decreasing order of relative intensity of peaks, and (b) the beta-subunit, representing the meroaldehyde moiety (R(2)-CHO). The saturated meroaldehyde species exhibited peaks representing meroaldehyde minus 18 mass units in which R(2) ranged from C19H39 to C31H63. The monunsaturated species exhibited peaks representing the meroaldehyde in which R(2) ranged from C19H37 to C31H61; peaks corresponding to meroaldehyde minus 18 mass units appeared only in the most abundant components, C29H57CHO, C27H53CHO, C25H49CHO and C31H61CHO, in a decreasing order of relative abundance. The diunsaturated species exhibited peaks essentially corresponding to meroaldehyde in which R(2) corresponded to C31H59 and C29H55; the latter displayed a relative intensity that was about one-half compared to that of the former. Fractions F-0, F-1 and F-2 showed a more intense pyrolytic fragmentation under CI-MS in contrast to results found under EI-MS. Therefore, peaks representing the alpha-subunit and the beta-subunit were more prominent than the ones representing the fragmentation of the hydrocarbon chain. Moreover, the beta-subunit of saturated species exhibited peaks corresponding to meroaldehyde plus hydrogen, and no dehydration of the beta-subunit occurred in this case. In turn, the beta-subunit of monounsaturated and diunsaturated species showed peaks representing both the meroaldehyde plus hydrogen and its dehydration product plus hydrogen. Thus, the presence of unsaturation in the meroaldehyde subunit of methyl mycolate facilitates appearance of dehydration fragment ions under chemical ionization procedure.
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A highly sensitive adsorptive stripping procedure for trace measurement of the anticancer drug tamoxifen is described. The method is based on controlled adsorptive accumulation of the drug at an electrochemically treated glassy carbon electrode, followed by chronopotentiometric measurement of the surface species. The chronopotentiometric operation effectively addresses the large background contribution inherent to the glassy carbon electrode to yield a detection limit of 4 x 10(-10) M after 4 min preconcentration. The adsorptive stripping response is evaluated with respect to electrode type and conditioning, accumulation potential and lime, stripping current, pH, drug concentration, potential interferences, and other variables. Applicability to urine samples is illustrated. (C) 1997 Elsevier B.V. B.V.