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1.
Ariana Posadaz Alicia Biasutti Csar Casale Jesús Sanz Francisco Amat‐Guerri Norman A. García 《Photochemistry and photobiology》2004,80(1):132-138
The Rose Bengal‐sensitized photooxidations of the dipeptides l ‐tryptophyl‐l ‐phenylalanine (Trp‐Phe), l ‐tryptophyl‐l ‐tyrosine (Trp‐Tyr) and l ‐tryptophyl‐l ‐tryptophan (Trp‐Trp) have been studied in pH 7 water solution using static photolysis and time‐resolved methods. Kinetic results indicate that the tryptophan (Trp) moiety interacts with singlet molecular oxygen (O2(1Δg)) both through chemical reaction and through physical quenching, and that the photooxidations can be compared with those of equimolecular mixtures of the corresponding free amino acids, with minimum, if any, influence of the peptide bond on the chemical reaction. This is not a common behavior in other di‐ and polypeptides of photooxidizable amino acids. The ratio between chemical (kr) and overall (kt) rate constants for the interaction O2(1Δg)‐dipeptide indicates that Trp‐Phe and Trp‐Trp are good candidates to suffer photodynamic action, with krlkt values of 0.72 and 0.60, respectively (0.65 for free Trp). In the case of Trp‐Tyr, a lower krlkt value (0.18) has been found, likely as a result of the high component of physical deactivation of O2(1Δg) by the tyrosine moiety. The analysis of the photooxidation products shows that the main target for O2(1Δg) attack is the Trp group and suggests a much lower accumulation of kynurenine‐type products, as compared with free Trp. This is possibly because of the occurrence of another accepted alternative pathway of oxidation that gives rise to 3a‐oxidized hydrogenated pyrrolo[2,3‐b]indoles. 相似文献
2.
Ariana Borges Souza Monique Rodrigues Moreira Carly Henrique Gambeta Borges Marília Rodrigues Simão Jairo Kenupp Bastos João Paulo Barreto de Sousa Sérgio Ricardo Ambrosio Rodrigo Cassio Sola Veneziani 《Biomedical chromatography : BMC》2013,27(3):280-283
The Copaifera species (Leguminoseae) are popularly known as ‘copaíba’ or ‘copaíva’ and are grown in the states of Amazonas, Pará and Ceará in northern Brazil. The oleoresins obtained from these species have been extensively used owing to their pharmacological potential and their application in cosmetic and pharmaceutical preparations. In the present study, the development and validation of a novel, rapid and efficient RP‐HPLC methodology for the analysis of the diterpene (?)‐copalic acid (CA), pointed out as the only chemical marker of the Copaifera genus, are described. The regression equation (Y = 26,707x ? 29,498) was obtained with good linearity (r2 = 0.9993) and the limits of quantification and detection were 9.182 and 3.032 µg/mL, respectively. The precision and the accuracy of the method were adequate (lower than 4%). Finally, the validation parameters evaluated were satisfactorily met, so the developed method represents a suitable tool for application in the quality control of such natural products. Further studies aiming to develop analytical methodologies for each Copaifera species using a more representative number of chemical markers should be performed. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
3.
Ariana Hudita Bianca Galateanu Marieta Costache Carolina Negrei Rodica-Mariana Ion Lorena Iancu Octav Ginghina 《Molecules (Basel, Switzerland)》2021,26(5)
Chronic neuropathic pain, particularly peripheral pain, is a cause of great concern for diabetic patients. Current treatments include numerous agents such as capsaicinoids, a known deterrent of neuropathic pain despite the inconvenience associated with local side effects. In this context, the current work aims to elucidate the potential mechanisms involved in cytotoxicity by capsaicin and proposes an efficient formulation of capsaicin in alginate microcapsules, which significantly reduces side effects from capsaicin topical administration. For this, human dermal fibroblast cells were treated with alginate-microencapsulated capsaicin extracts and screened for potential cytotoxic effects produced by the treatment. Cell viability and morphology were examined, as well as oxidative stress status and anti-inflammatory potential. Our results show that the alginate encapsulated formulation of capsaicin exerted lower cytotoxic effects on human dermal fibroblasts as measured by cell viability and reactive oxygen species (ROS) production. Furthermore, the expression profiles of inflammatory cytokines were significantly altered by the treatment as compared with the control culture. 相似文献
4.
Ariana O. Hall Se Ryeon Lee Andrea N. Bootsma Jacob W. G. Bloom Steven E. Wheeler Anne J. McNeil 《Journal of polymer science. Part A, Polymer chemistry》2017,55(9):1530-1535
Synthesizing conjugated polymers via catalyst‐transfer polymerization (CTP) has led to unprecedented control over polymer sequence and molecular weight. Yet many challenges remain, including broadening the monomer scope and narrowing the molecular weight dispersities. Broad polymer dispersities can arise from nonliving pathways as well as slow initiation. Previously, slow initiation was observed in Ni‐mediated CTP of phenylene monomers. Although precatalysts with faster initiation rates have been reported, the rates still do not exceed propagation. Herein a second‐ and third‐generation of reactive ligands are described, along with a simple method for measuring initiation rates. A precatalyst with an initiation rate that exceeds propagation is now reported, however, the resulting polymer samples still exhibit broad dispersities, suggesting that slow initiation is not the most significant contributing factor in Ni‐mediated phenylene polymerizations. In addition, initiation rates measured under authentic polymerization conditions revealed that both exogenous triphenylphosphine and an ortho‐trifluoroethoxy substituent on the reactive ligand have a strong influence. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1530–1535 相似文献
5.
Silvestro L Gheorghe M Iordachescu A Ciuca V Tudoroniu A Rizea Savu S Tarcomnicu I 《Analytical and bioanalytical chemistry》2011,401(3):1023-1034
A new sensitive and fast quantitative analytical method for the simultaneous determination of clopidogrel, its main metabolite
clopidogrel carboxylic acid, and the newly described acyl glucuronide metabolite, in human plasma samples, is presented. The
analytical procedures (plasma storage, handling, and extract storage in the autosampler) were optimized in order to avoid
back-conversion; a known drawback in measurements of clopidogrel. Clopidogrel acyl glucuronide was confirmed as a major source
of back-conversion to the parent drug in the presence of methanol, and thorough stability experiments were carried out to
find the most appropriate conditions for an accurate analysis of clopidogrel and the two metabolites. The method was validated
by assessing selectivity, sensitivity, linearity, accuracy, and precision for all three analytes, in accordance to Food and
Drug Administration guidelines. Spiked quality controls in plasma as well as incurred samples were used to verify back-conversion
in the selected conditions, with results meeting European Medicines Agency acceptance criteria (concentrations within 80–120%
of the first reading). The method was then applied to a pharmacokinetic study, and for the first time, a pharmacokinetic curve
of clopidogrel acyl glucuronide in human plasma is presented. The concentrations ranged up to 1,048.684 ng/mL, with a mean
of 470.268 ng/mL, while clopidogrel had a mean C
max of 1.348 ng/mL; these orders of magnitude show how much the back-conversion of this metabolite may influence clopidogrel
quantification if it is not properly controlled. 相似文献
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7.
Culzoni MJ Goicoechea HC Ibañez GA Lozano VA Marsili NR Olivieri AC Pagani AP 《Analytica chimica acta》2008,614(1):46-57
Multivariate curve resolution coupled to alternating least-squares (MCR-ALS) has been employed to model kinetic-spectroscopic second-order data, with focus on the achievement of the important second-order advantage, under conditions of extreme spectral overlapping among sample components. A series of simulated examples shows that MCR-ALS can conveniently handle the studied analytical problem unlike other second-order multivariate calibration algorithms, provided matrix augmentation is implemented in the spectral mode instead of in the usual kinetic mode. The approach has also been applied to three experimental examples, which involve the determination of: (1) the antiparkinsonian carbidopa (analyte) in the presence of levodopa as a potential interferent, both reacting with cerium (IV) to produce the fluorescent species cerium (III) with different kinetics; (2) Fe(II) (analyte) in the presence of the interferent Zn(II), both catalyzing the oxidation of methyl orange with potassium bromate; and (3) tartrazine (analyte) in the presence of the interferent brilliant blue, both oxidized with potassium bromate, with the interferent leading to a product with an absorption spectrum very similar to tartrazine. The results indicate good analytical performance towards the analytes, despite the intense spectral overlapping and the presence of unexpected constituents in the test samples. 相似文献
8.
We describe the occurrence of computational artifacts when the principal layer method is used in combination with the cluster approximation for the calculation of electronic transport properties of nanostructures. For a one-dimensional gold chain, we observe an unphysical band in the band structure. The artificial band persists for large principal layers and for large buffer sizes. We demonstrate that the assumption of equality between Hamiltonian elements of neighboring layers is no longer valid and that a discontinuity is introduced in the potential at the layer transition. The effect depends on the basis set. When periodic boundary conditions are imposed and the k-space sampling is converged, the discontinuity disappears and the principal layer method can be correctly applied by using a linear combination of atomic orbitals as basis set. 相似文献
9.
Ariana Gonzalez Lissette Estala Michelle Gaines Frank A. Gomez 《Electrophoresis》2016,37(12):1685-1690
A novel microfluidic thread/paper‐based analytical device (μTPAD) to detect glucose through a colorimetric assay is described. The μTPAD was fabricated from nylon thread trifurcated into three channels terminating at analysis sites comprised of circular zones of chromatography paper, which have previously been spotted with glucose of different concentrations. A solution of glucose oxidase (GOx), horseradish peroxidase (HRP), and potassium iodide (KI) is transported via capillary action to the analysis sites where a yellow‐brown color is observed indicating oxidation of iodide to iodine. The device was then dried, scanned, and analyzed yielding a correlation between yellow intensity and glucose concentrations. Both a flat platform constructed mainly of tape, and a cone platform constructed from tape and polyvinyl chloride, are described. Studies to quantitate glucose in artificial urine showed good correlation using the μTPAD. 相似文献
10.