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Journal: Luminescence : the journal of biological and chemical luminescence

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The direct effect of the four catecholamines (adrenaline, noradrenaline, dopamine and isoproterenol) on superoxide anion radicals (O2-•) was investigated. The reaction between 18-crown-6-ether and potassium superoxide in dimethylsulfoxide was used as a source of O2-•. The reactivity of catecholamines with O2-• was examined using chemiluminescence, reduction of nitroblue tetrazolium and electron paramagnetic resonance spin-trapping techniques. 5,5-Dimethyl-1-pyrroline-N-oxide was included as the spin trap. The results showed that the four catecholamines were effective and efficient in inhibiting chemiluminescence accompanying the potassium superoxide/18-crown-6-ether system in a dose-dependent manner over the range 0.05-2 mm in the following order: adrenaline > noradrenaline > dopamine > isoproterenol, with, IC(50)  = 0.15 ± 0.02 mm 0.21 ± 0.03 mm, 0.27 ± 0.03 mm and 0.50 ± 0.04 mm, respectively. The catecholamines examined also exhibited a strong scavenging effect towards O2-• when evaluated this property by the inhibition of nitroblue tetrazolium reduction (56-73% at 1 m concentration). A very similar capacity of O2-• scavenging was monitored in the 5,5-dimethyl-1-pyrroline-N-oxide spin-trapping assay. The results suggest that catecholamines tested may involve a direct effect on scavenging O2- radicals. Copyright © 2013 John Wiley & Sons, Ltd.

Concepts: Redox, NADPH oxidase, Epinephrine, Superoxide, Chronic granulomatous disease, Dopamine, Norepinephrine, Potassium superoxide

26

Two simple, selective and accurate methods were developed and validated for the determination of brimonidine tartrate (BT) in pure state and pharmaceutical formulations. Both methods are based on the coupling of the drug with 4-chloro-7-nitro-2,1,3-benzoxadiazole in borate buffer (pH 8.5) at 70 °C and measurement of the reaction product spectrophotometrically at 407 nm (method I) or spectrofluorimetrically at 528 nm upon excitation at 460 nm (method II). The calibration graphs were rectilinear over the concentration ranges of 1.0-16.0 and 0.1-4.0 µg/mL with lower detection limits of 0.21 and 0.03, and lower quantification limits of 0.65 and 0.09 µg/mL for methods I and II, respectively. Both methods were successfully applied to the analysis of commercial ophthalmic solution with mean recovery of 99.50 ± 1.00 and 100.13 ± 0.71%, respectively. Statistical analysis of the results obtained by the proposed methods revealed good agreement with those obtained using a comparison method. The proposed spectrofluorimetric method was extended to a stability study of BT under different ICH-outlined conditions such as alkaline, acidic, oxidative and photolytic degradation. Furthermore, the kinetics of oxidative degradation of the drug was investigated and the apparent first-order reaction rate constants, half-life times and Arrhenius equation were estimated. The proposed methods are practical and valuable for routine applications in quality control laboratories for the analysis of BT. Copyright © 2014 John Wiley & Sons, Ltd.

Concepts: Scientific method, Pharmacology, Statistics, Chemical reaction, Measurement, PH, Reaction rate constant, Chemical kinetics

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The interaction of acid (PTCA) with cetyltrimethylammonium bromide (CTAB) has been studied by fluorescence spectroscopy. The fluorescence of PTCA can be greatly enhanced by the addition of CTAB, due to the formation a fluorescent supramolecular compound. Under optimum conditions, the enhancement intensity of fluorescence was proportional to the concentration of CTAB over a range of 0-4.5 µmol L(-1) . Its detection limit was 0.057 µmol L(-1) , which was lower than reported previously. Compared with other methods that have been reported to determine CTAB, this method has high sensitivity, stability and wide linear range and it can be used satisfactorily for the determination of CTAB in aqueous samples. Copyright © 2014 John Wiley & Sons, Ltd.

Concepts: Fluorescence, Spectroscopy, Oxygen, Function, Light, Fluorescence spectroscopy, Chemistry, Fluorometer

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The interaction of pepsin with chlorogenic acid (CHA) was investigated using fluorescence, UV/vis spectroscopy and molecular modeling methods. Stern-Volmer analysis indicated that the fluorescence quenching of pepsin by CHA resulted from a static mechanism, and the binding constant was 1.1846 × 10(5) and 1.1587 × 10(5) L/mol at 288 and 310 K, respectively. The distance between donor (pepsin) and acceptor (CHA) was calculated to be 2.39 nm and the number of binding sites for CHA binding on pepsin was ~ 1. The results of synchronous fluorescence and three-dimensional fluorescence showed that binding of CHA to pepsin could induce conformational changes in pepsin. Molecular docking experiments found that CHA bonded with pepsin in the area of the hydrophobic cavity with Van der Waals' forces or hydrogen bonding interaction, which were consistent with the results obtained from the thermodynamic parameter analysis. Furthermore, the binding of CHA can inhibit pepsin activity in vitro. Copyright © 2013 John Wiley & Sons, Ltd.

Concepts: Fluorescence, Spectroscopy, Oxygen, Hydrogen, Atom, Computational chemistry, Molecular modelling, Molecular mechanics

24

The pileus of Mycena chlorophos actively, spontaneously, and continuously emits green light. Molecular mechanisms underlying this bioluminescence remain unclear. We investigated light emitters in the pileus of M. chlorophos to determine the underlying mechanisms. High-performance liquid chromatography-fluorescence-photodiode array-mass detection analyses showed that actively luminescent gills in the pileus exclusively and abundantly possessed riboflavin, riboflavin 5'-monophosphate, and flavin adenine dinucleotide as green-fluorescent components. These components were localized in the bioluminescent region of the gills at the microscopic level. Fluorescence spectra of these green-fluorescent components and the gills were identical with the spectrum of gill bioluminescence (maximum emission wavelength, 525 nm). Thus, our results indicated that the possible light emitters in the pileus of M. chlorophos were riboflavin, riboflavin 5'-monophosphate, and/or flavin adenine dinucleotide. Copyright © 2016 John Wiley & Sons, Ltd.

Concepts: Fluorescence, Adenosine triphosphate, Light, Adenine, Luminescence, Bioluminescence, FAD, Riboflavin

22

A spectrofluorimetric method for the determination of eptifibatide is presented based on its native fluorescence. The type of solvent and the wavelength of maximum excitation and emission were carefully selected to optimize the experimental conditions. Under the specified experimental conditions, the linearities obtained between the emission intensity and the corresponding concentrations of eptifibatide were in the range 0.1-2.5 μg/ml for the calibration curve constructed for direct determination of eptifibatide in dosage form and 0.05-2.2 μg/ml for the calibration curve constructed in spiked human plasma with a good correlation coefficient (r > 0.99). The lower limit of quantification for the calibration curve constructed in human plasma was 0.05 μg/ml. Recovery results for eptifibatide in spiked plasma samples and in dosage form, represented as mean ± % RSD, were 95.17 ± 1.94 and 100.29 ± 1.33 respectively. The suggested procedures were validated according to the International Conference on Harmonization (ICH) guidelines for the direct determination of eptifibatide in its pure form and dosage form and United States Food and Drug Administration (US FDA) Guidance for Industry, Bioanalytical Method Validation for the assay of eptifibatide in human plasma.

22

An important form of carbon nanoparticles that are used for a wide range of applications, are carbon dots (CDs). In this study, a very easy, in expensive and green process was described for the preparation of CDs by using hydrothermal treatment of Tragacanth Gum (TG). A rapid assay for the determination of trace amounts of an anticancer medication doxorubicin (DOX) was developed, based on the quenching of the CDs derived from their aggregation. Electrostatic interaction between CDs and DOX could lead to fluorescence quenching. The optimized biosensor showed a detection range from 1 to 400 ng mL-1 and a limit of detection of 0.4 ng mL-1 . In the following, the synthesized CDs modified the Boehmite (Boh) mesoporous surface based on hydrogen bonding. The Boh has been used as supports and ideal hosts in this method, in which the particle size distribution of CDs in the pores of Boh is limited and they have controlled pore sizes. Accordingly, the surface-to-volume ratio and the presence of high-volume pores increased the longevity and sustainability of CDs; also prevented the aggregation of the CDs and improved their photo stability. The advantages of Boh are large pore volume, high surface area, and narrow size distribution. Variable factors influencing optical sensor response in DOX measurement were evaluated and optimized. In optimal conditions, the linear range was calculated from 1 to 500 ngmL-1 and the detection limit was 0.2 ng mL-1 . The sensors were used for measuring DOX in human blood plasma.

22

Abnormal lysosomal pH is closely associated with many diseases, and real-time monitoring of lysosomal pH is important for understanding the lysosome physiological nature. Here, we present a novel lysosome-targeting two-photon fluorescent probe (MP-lys) for monitoring pH changes in living cells. As a dual site-controlled probe, MP-lys employed morpholine and piperazine groups as the lysosome-targeting groups and pH response sites. MP-lys showed rapid, reversible and sensitive fluorescence response to pH. MP-lys possessed lysosome-targeting properties, and could be used for two-photon imaging of chloroquine-induced pH variation in living cells.

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The effects of Tm3+ concentration on upconversion emission and temperature-sensing behavior of Tm3+/Yb3+:Y2O3 nanocrystals were investigated. Blue and red emissions were observed under 980 nm excitation. Both upconversion emissions and the blue to red intensity ratio were found to decrease with increasing Tm3+ concentration. The temperature-sensing performances of the samples were studied, the fluorescence intensity ratio of 1G4(a)→3H6 (477 nm) and 1G4(b)→3H6 (490 nm) transitions from Tm3+ ions was chosen as the thermometric index. The results showed that the sensor sensitivity was sensitive to Tm3+ ion concentration. The maximum sensitivity of ~32 × 10-4 K-1 was obtained for 0.1%Tm3+/5%Yb3+:Y2O3 nanocrystals at 344 K. Moreover, a marked optical induced heating effect was also found in the nanocrystals. The prepared Tm3+/Yb3+:Y2O3 nanocrystals could be used in temperature-sensing probes and in optical heaters.

22

The radiation effect of luminescence emission of Ca-rich oxalate biogenic materials (gallbladder and renal calculi) and a commercial standard sample (CaC2 O4 ·H2 O) is reported. The samples were characterized by environmental scanning electron microscopy, energy dispersive X-ray spectroscopy, thermogravimetric and differential thermal analyses, display complex cathodoluminescence (CL) and thermoluminescence (TL) glow emissions. CL spectra (in the UV-infrared range) displayed non-well defined peaks, and exhibited emission at: (i) higher energies (300-490 nm) mainly associated with non-bridging oxygen hole centers, oxygen-deficient centers and peroxy intrinsic defects, regardless of the sample; and (ii) higher, narrow and sharp wavebands, in the red region, probably induced by the presence of traces of Sm3+ (4 G5/2 →6 H9/2 transition) and/or Tb3+ (5 D4 →7 F3 transition) only for mineral-like materials in the human body. The UV-blue TL emission showed low-intensity maxima in which it was possible to distinguish at least four groups of components in each sample.