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1.
Compared to the fluorescence spectra of warfarin in pure ethanol and in the presence of the nonionic surfactant Tergitol 15-S-7 after cloud point extraction (CPE), it can be seen that the fluorescence emission peak underwent an obvious red shift and the fluorescence intensity of warfarin was significantly increased in the presence of Tergitol 15-S-7. In order to confirm Tergitol 15-S-7-induced supramolecular effects, the investigations on the fluorescence quantum yields of warfarin in the micellar medium and pure ethanol were performed. The experimental results showed that the supramolecular interactions between Tergitol 15-S-7 and the warfarin excimers played a key role for improving the warfarin fluorescence properties.Based on these facts, a simple fluorometric method combined with CPE for the determination of trace warfarin was developed for the first time. Under optimized experimental conditions, the linear concentration range for warfarin was 3.0×1.0?9–1.0×10?6 mol L?1 and the detection limit was 3.3×10?10 mol L?1. And, the proposed method was approved to be appropriate for monitoring warfarin in actual pharmaceutical formulations and biological fluid samples by recovery test, in comparison with other reported methods being satisfactory.  相似文献   

2.
Time resolved spectroscopy was applied to a real time investigation of chemical reaction of quercetin (5.0 × 10? 5 mol L? 1) with various concentrations of sodium hydroxide (from 5.0 × 10? 3 to 1.0 mol L? 1). The UV–vis absorption spectra acquired first reveal that there was an intermediate product with an absorption band centered at 427 nm formed during the reaction. The rates of chemical changes for quercetin in basic medium are also first obtained by the present work. The transient spectral information obtained is valuable for understanding the molecular mechanism of the reaction between quercetin and sodium hydroxide.  相似文献   

3.
Using high-intensity ultrasound, in situ generated α-amylase nanoparticles (NPs) were immobilized on polyethylene (PE) films. The α-amylase NP-coated PE films have been characterized by E-SEM, FTIR, DLS, XPS and RBS. The PE was reacted with HNO3 and NPs of the α-amylase were also deposited on the activated PE. The PE impregnated with α-amylase (4 μg per 1 mg PE) was used for hydrolyzing soluble potato starch to maltose. The immobilization improved the catalytic activity of α-amylase at all the reaction conditions studied. The kinetic parameters, Km (5 and 4 g L?1 for the regular and activated PE, respectively) and Vmax (5 × 10?7 mol ml?1 min?1, almost the same numbers were obtained for the regular and activated PEs) for the immobilized amylase were found to slightly favor the respective values obtained for the free enzyme (Km = 6.6 g L?1, Vmax = 3.7 × 10?7 mol ml?1 min?1). The enzyme remained bound to PE even after soaking the PE in a starch solution for 72 h and was still found to be weakly active.  相似文献   

4.
This paper reports on a facile technique combined with a simple, sensitive and selective spectrofluorimetric method for the determination of hydrochlorothiazide. In methanol, at pH 8.3 and λex=340, hydrochlorothiazide can remarkably enhance the luminescence intensity of the Eu3+ ion doped in polymethylmethacrylate polymer (PMMA) matrix. This could be due to the energy transfer from hydrochlorothiazide to Eu3+ in the excited stated. At the optimized experimental conditions, the enhancement of the characteristic emission band (617 nm) of Eu3+ ion doped PMMA is directly proportional to the concentration of hydrochlorothiazide with a dynamic range of 5×10?8–1.0×10?5 mol L?1 and detection limit of 8.0×10?9 mol L?1. Application of the suggested method was successfully applied to the determination of hydrochlorothiazide in pharmaceutical preparations and human serum samples, with high percentage of recovery, good accuracy and precision.  相似文献   

5.
A novel 4-(2-dimethylaminoethyloxy)-N-octadecyl-1,8-naphthalimide (DON) has been synthesized as a spectrofluorimetric probe for the determination of proteins. Photophysics of DON in different solvents has been delineated in this paper. Progressive redshift with polarity of solvents in emission and absorption spectra hints at intramolecular charge transfer. The interactions of DON with serum albumins (i.e., human serum albumin (HSA) and bovine serum albumin (BSA)) were studied by fluorescence and absorption spectroscopy. Fluorescence data revealed that the quenching of HSA/BSA by DON were static quenching and the DON–HSA/BSA complexes were formed. The binding constant (Kb) for HSA and was found to be 8.44×10?4 and 60.26×10?4 M?1 and the number of binding sites (n) were 1.00 and 1.40, respectively. The thermodynamic parameters, ΔH and ΔS, for the DON–HSA system was calculated to be ?14.83 kJ mol?1 and 23.61 J mol?1 K?1, indicating the hydrogen bonds and hydrophobic interactions were the dominant intermolecular force. ΔH and ΔS for the binding of DON with BSA was ?60.08 kJ mol?1 and ?90.7441 mol?1 K?1, suggesting the hydrogen bonds and van der Waals force played the main role in the interaction. The results of displacement experiments showed that DON bound HSA/BSA occurred at the Trp-214 proximity, located in subdomain IIA of the serum albumin structure (the warfarin binding pocket). The effect of DON on the conformation of HSA was also analyzed by synchronous and three-dimensional fluorescence spectra. The fluorescence of DON could be quenched by HSA, based on which, a fluorometric method for the determination of microamount protein using DON in the medium of HCl?Tris buffer solution (pH=7.4) was developed. The linear range of the calibration curves was 0.1–10.0 μM for HSA, 0.1–11.2 μM for BSA and 0.2–9.7 μM for egg albumin (EA). The detection limit (3σ) for HSA was 1.12×10?10 M, for BSA it was 0.92×10?10 M and for EA it was 4.33×10?10 M. The effect of metal cations on the fluorescence spectra of DON in ethanol was also investigated. The method has been applied to detect the total proteins in human serum samples and the results were in good agreement with those reported by the hospital.  相似文献   

6.
The study is aimed to evaluate the efficiency of ultrasound-assisted extraction (UAE) as a simple strategy focused on sample preparation for metal determination in biological samples. The extraction of sodium and potassium extraction was carried out from swine feed followed by determination of the concentration of these metals by flame atomic emission spectrometry (FAES). The experiment was performed to cover the study of the variables influencing the extraction process and its optimal conditions (sample mass, particle size, acid concentration, sonication time and ultrasound power); the determination of these analytical characteristics and method validation using certified reference material; and the analysis of pre-starter diets. The optimal conditions established conditions were as follows: mass: 100 mg, particle size:<60 μm, acid concentration: 0.10 mol L?1 HCl, sonication time: 50 s and ultrasound power: 102 W. The proposed method (UAE) was applied in digestibility assays of those nutrients present in different piglet pre-starter feeds and their results proved to be compatible with those obtained from mineralized samples (P < 0.05). The ultrasound extraction method was demonstrated to be an excellent alternative for handless sampling and operational costs and the method also has the advantage of does not generating toxic residues that may negatively affect human health and contaminate the environment.  相似文献   

7.
The polymorphic forms of lactose in alcoholic suspensions have been determined by 13C CP-MAS NMR spectroscopy, employing hand-made glass inserts. Suspensions of alpha lactose monohydrate (Lα·H2O) with particle size between 2 and 200 μm were prepared by 24 h reflux or by storage for 28 d in anhydrous ethanol without agitation. These suspensions were compared to an ethanolic sub-micron lactose suspension provided by a 3 M Health Care (Loughborough). The 13C CP-MAS NMR spectra indicated that Lα·H2O dehydrated to stable anhydrous alpha lactose polymorph (LαS) whilst suspended in ethanol. In addition, strong ethanol 13C resonances were observed for some samples, indicating a liquid–solid interaction between the ethanol and lactose surface. Replacement of ethanol with anhydrous methanol, n-butanol and 3-methylbutan-2-ol implied that the solvent mediated dehydration of Lα·H2O to LαS occurs as a result of sterically controlled interactions.  相似文献   

8.
Palladium/Iron (Pd/Fe) nanoparticles were prepared by using ultrasound strengthened liquid phase reductive method to enhance dispersion and avoid agglomeration. The dechlorination of 2,4-dichlorophenol (2,4-DCP) by Pd/Fe nanoparticles was investigated to understand its feasibility for an in situ remediation of contaminated groundwater. Results showed that 2,4-DCP was first adsorbed by Pd/Fe nanoparticles, then quickly reduced to o-chlorophenol (o-CP), p-chlorophenol (p-CP), and finally to phenol (P). The induction of ultrasound during the preparation of Pd/Fe nanoparticles further enhanced the removal efficiency of 2,4-DCP, as a result, the phenol production rates increased from 65% (in the absence of ultrasonic irradiation) to 91% (in the presence of ultrasonic irradiation) within 2 h. Our data suggested that the dechlorination rate was dependent on various factors including Pd loading percentage over Fe0, Pd/Fe nanoparticles availability, temperature, mechanical stirring speed, and initial pH values. Up to 99.2% of 2,4-DCP was removed after 300 min reaction with these conditions: Pd loading percentage over Fe0 0.3 wt.%, initial 2,4-DCP concentration 20 mg L?1, Pd/Fe dosage 3 g L?1, initial pH value 3.0, and reaction temperature 25 °C. The degradation of 2,4-DCP followed pseudo-first-order kinetics reaction and the apparent pseudo-first-order kinetics constant was 0.0468 min?1.  相似文献   

9.
Highly luminescent complexes of Eu and Tb ions with norfloxacin (NFLX) and gatifloxacin (GFLX) were prepared in sol–gel matrix. The red and green emissions of Eu and Tb ions were obtained by the energy transfer from the triplet state of (NFLX) and (GFLX) to the excited emitting states (5D0 and 5D4) of Eu and Tb, respectively. The intensity of the electric field emission bands (5D07F2, 617 nm and 5D47F5, 545 nm) of Eu and Tb ions were proportional to the concentration of (NFLX at pH 6.0) and (GFLX at pH 3.5) in acetonitrile with excitation wavelengths (λex) (340 and 395) and (370 and 350 nm) for Eu and Tb ions, respectively. The monitored luminescence intensity of the system showed a good linear relationship with the concentration of NFLX within a range of 5×10?9–5.8×10?6 and 5×10?8–1.0×10?6 mol L?1 with a correlation coefficient of 0.990, and for GFLX within a range of 2.4×10?9–3.2×10?5 and 5×10?8–8.0×10?6 mol L?1 with a correlation coefficient of 0.995. The detection limit (LOD) was determined as 3.0×10?9 and 1.0×10?8 mol L?1 for NFLX and 1.6×10?10 and 2.0×10?8mol L?1 for GFLX. The limit of quantification (LOQ) is 9×10?9 and 3.0×10?8 and 4.8×10?10 and 6.0×10?8 in case of Eu and Tb, respectively.  相似文献   

10.
The interactions of two high molecular weight polycarboxylic ligands [polyacrylic-co-maleic, MW = 70 kDa, and poly(methyl vinyl ether-co-maleic acid), MW = 15 kDa] with some polyamines [1,4-diaminobutane (or putrescine), histamine and poly(allyl)amine, MW = 15 kDa] were studied, at t = 25 °C and at low ionic strength (I = 0.015 mol L? 1) by potentiometric measurements. For all investigated systems, the formation of (am)(L)Hi species was found (am = amine, L = polycarboxylic ligand, i = 1…4); the stability of polyammonium–polycarboxylate complexes is fairly high and the formation percentage of most species reaches ~ 90% in the experimental conditions (mmolar concentration of reactants). The dependence on temperature and ionic strength of the stability of polyamine–polycarboxylate species was studied using some semiempirical equations and enthalpy data for the protonation of both components. The sequestering ability of polyelectrolytes towards amines was modeled by a sigmoid Boltzman type equation and was defined by calculating the parameter pL50 (the total ligand concentration, as ? log CL, able to bind 50% of cation); this parameter gives an objective representation of this ability. The dependence of pL50 on pH, ionic strength and temperature was studied too.  相似文献   

11.
The effects of ultraviolet radiation-B (UVBR) in apical segments of the red macroalgae Gracilaria domingensis (Kützing) Sonder ex Dickie were examined in vitro. Over a period of 21 days, the segments were cultivated and exposed to photosynthetically active radiation (PAR) at 80 μmol photons m?2 s?1 and PAR + UVBR at 1.6 W m?2 for 3 h per day. The samples were processed for electron microscopy, as well as histochemical analysis, and growth rate, photosynthetic pigment contents and photosynthetic performance were measured. Toluidine Blue reaction showed metachromatic granulations in vacuole and lenticular thickness, while Coomassie Brilliant Blue showed a higher concentration of cytoplasmic organelles, and Periodic Acid Schiff stain showed an increase in the number of floridean starch grains. UVBR also caused changes in the ultrastructure of cortical and subcortical cells, which included an increased number of plastoglobuli, changes in mitochondrial organization, destruction of chloroplast internal organization, and the disappearance of phycobilisomes. The algae cultivated under PAR-only showed growth rates of 6.0% day?1, while algae exposed to PAR + UVBR grew only 2.8% day?1. Compared with algae cultivated with PAR-only, the contents of photosynthetic pigments, including chlorophyll a, phycoerythrin, phycocyanin and allophycocyanin, decreased after exposure to PAR + UVBR, and significant differences were observed. Finally, analysis of these four photosynthetic parameters also showed reduction after exposure to PAR + UVBR: maximum photosynthetic rate, photosynthetic efficiency, photoinhibition and relative electron transport rate. Taken together, these findings strongly suggested that UVBR negatively affects the agarophyte G. domingensis.  相似文献   

12.
Local defects present in CeO2 ? x films result in a mixture of Ce3+ and Ce4+ oxidation states. Previous studies of the Ce 3d region with XPS have shown that depositing metal nanoparticles on ceria films causes further reduction, with an increase in Ce3+ concentration. Here, we compare the use of XPS and resonant photoemission spectroscopy (RESPES) to estimate the concentration of Ce3+ and Ce4+ in CeO2 ? x films grown on Pt (111), and the variation of this concentration as a function of Pd deposition. Due to the nature of the electronic structure of CeO2 ? x, resonant peaks are observed for the 4d–4f transitions when the photon energy matches the resonant energy; (hν = 121.0 eV) for Ce3+ and (hν = 124.5 eV) for Ce4+. This results in two discrete resonant photoemission peaks in valence band spectra. The ratio of the difference of these peaks with off-resonance scans gives an indication of the relative contribution of Ce3+. Results from RESPES indicate reduction of CeO2 ? x on deposition of Pd, confirming earlier findings from XPS studies.  相似文献   

13.
The two-photon absorption (TPA) characteristics of PMMA discs doped with three different dyes were studied using an fs-pulsed Ti-Sapphire laser as the pump source, and employing the open-aperture Z-scan technique. TPA cross-sections obtained for PMMA doped with the dyes PM597, DCM and rhodamine 6G–rhodamine B (co-doped) were found to be equal to 24.7, 33.3 and 32.3 GM, respectively (1 GM=10?50 cm4 s phot?1 mol?1). Furthermore, two-photon fluorescence was measured for the samples containing DCM and rhodamine 6G–rhodamine B (co-doped). Compared to the one-photon fluorescence spectrum, the peaks in the two-photon fluorescence spectrum were red shifted and the extent of red shift increased with increasing doping concentration. We have also observed that the red shift in the two-photon fluorescence peak of the samples in the solid form is much larger than that in the solution state. This phenomenon could be explained by a twisted intra-molecular charge transfer model.  相似文献   

14.
In this study, the synthesis of Ce0.8Sm0.2O1.9 (SDC) solid electrolyte by the ultrasound assisted co-precipitation method was accomplished to explore the effects of ultrasound power, ultrasound pulse ratio and probe type upon the ionic conductivity of SDC as well as the lattice parameter, the microstructure and the density. Fine powders of uniform crystallite sizes (average 11.70 ± 0.62 nm) were obtained, needing lower sintering temperature. The SDC powders were successfully sintered to a relative density of over 95% at 1200 °C (5 °C min?1) for 6 h. The micrograph of SDC pellets showed non-agglomerated and well-developed grains with average size of about 200 nm. X-ray diffraction analysis showed that the lattice parameter increased with increasing acoustic intensity and reached a maximum for the 14.94 W cm?2. Further, a linear relationship was detected between the lattice parameter and the ionic conductivity, inspiring a dopant like effect of US on the electrolyte properties. The highest ionic conductivity as σ800°C = 3.07 × 10?2 S cm?1 with an activation energy Ea = 0.871 kJ mol?1 was obtained with pulsed ultrasound for an acoustic intensity of 14.94 W cm?2, using 19 mm probe and 8:2 pulse ratio.  相似文献   

15.
The heterogeneous catalytic reaction of H2O2 with iron oxides is an important reaction for the environment since both H2O2 and iron oxides are common constituents of natural and atmospheric waters. In this work, three ferrihydrites, labeled Fh-1, -2 and -3, were prepared by different procedures. Fh-1 was prepared by adding alkali solution to ferric solution under stirring. In the preparation of Fh-2, the mixing procedure of the two solutions was reversed. Fh-3 was obtained by adding alkali solution and ferric solution simultaneously into a certain amount of water. The heterogeneous catalytic reaction of H2O2 with three ferrihydrites in aqueous solution was investigated in detail. The results demonstrated that the apparent reaction rate was affected by the preparation procedure of ferrihydrite besides pH, temperature and the dose of catalyst. The activation energy of the decomposition reaction of H2O2 was determined to be 76.13, 59.41 and 68.05 kJ mol?1 for Fh-1, -2 and -3, respectively. The activation enthalpy of the reaction were determined to be 73.59, 56.56 and 65.76 kJ mol-1 and the activation entropy of the reaction were determined to be ?69.65, ?119.67 and ?90.58 J mol?1 K?1, respectively.  相似文献   

16.
A novel flow injection method for detection of l-proline was proposed in the presence of CdTe quantum dots (QDs). This method is based on the enhanced anodic electrochemiluminescence (ECL) emission of CdTe QDs l-proline in aqueous system. CdTe QDs were modified with thioglycolic acid to obtain stable water-soluble QDs and intensive anodic ECL emission in Na2CO3–NaHCO3 buffer solution at an indium tin oxide (ITO) electrode, which was used for the sensitive detection of ECL enhancement using our homemade flow cell. Under the optimal conditions, the ECL intensity was correlated linearly with the concentration of l-proline over the range of 1.0×10?8?1.0×10?4 g mL?1 (r=0.9996) and the detection limit was 5.0×10?9 g mL?1. The relative standard deviation was 1.12% for 6.0×10?5 g mL?1 l-proline (n=11). The possible mechanism was discussed. This method put forward a new efficient ECL methodology for enhancement-related determination of l-proline successfully.  相似文献   

17.
During the manufacturing process in the cement industry, raw materials of different levels of natural radioactivity are utilized. In this study we present the radiological impact of cements as a building material and the different raw materials used in their manufacture. A total of 218 samples of raw materials and their end product cements were collected from the cement industry of Macedonia (The Former Yugoslav Republic) during the period 2005–2007. The specific activities, evaluated by gamma spectrometry analysis, showed the highest mean specific activity in fly ash (226Ra, 107 ± 45 Bq kg?1; 232Th, 109 ± 30 Bq kg?1; 40K, 685 ± 171 Bq kg?1), which is used as a raw material. However, the final cement product usually has relatively lower activity compared with the activity of the raw material and the mean specific activity of the final cement products were lower (226Ra, 42 ± 10 Bq kg?1; 232Th, 28 ± 6 Bq kg?1; 40K, 264 ± 50 Bq kg?1). The radium equivalent activity and the hazard index were calculated for each sample to assess the radiation hazard. The mean annual effective dose originating from the cements was found to be 111 ± 22 μSv y?1, which is below the recommended EC limit of 300 μSv y?1.  相似文献   

18.
The influence of concentration of oxygen on the oxidation rates of 5 anthracite chars is investigated at gas temperatures ranging from 1223 K to 1673 K. Reaction orders and kinetic parameters are determined with a multivariable optimization method in which modeled burnout profiles are fitted to experimental burnout profiles from a 4 m isothermal plug flow reactor operating at industrially realistic heating rates, i.e., 104–105 K/s. The determined reaction orders are compared to reaction orders of 10 bituminous coal chars investigated at similar conditions in a previous study. The results show that the optimized reaction order of the anthracite chars is zero, while the reaction order of the bituminous coal char is one. The difference in the reaction orders cannot be explained by using the two semi-global oxidation reactions: C(O) + O2  CO/CO2 and C(O)  CO. However, by also considering 2C(O)  CO2 + C as a possible reaction step, the reaction order difference between the anthracite chars and the bituminous coal chars can be explained. In addition, a first attempt to apply the same multivariable optimization method to determine the reaction order for a biomass char is presented.  相似文献   

19.
A simple and sensitive spectrofluorimetric method was developed to determine trace amounts of bilirubin (BR) using yttrium (Y3+)–norfloxacin (NFLX) complex as a fluorescence (FL) probe. NFLX can form a stable binary complex with Y3+ and markedly enhances the weak FL signal of the NFLX. The FL intensity of the Y3+–NFLX complex decreased significantly in the presence of BR in a buffer solution at pH=7.2. Under optimal conditions, the FL intensity decreased according to the BR concentration and showed a good linear relationship in the range of 0.03–2.3 μg mL?1 of BR with a correlation coefficient of 0.9988. The limit of detection for the determination of BR was 2.8 ng mL?1 with a relative standard deviation (RSD) of 1.55% for five replicate determination of 0.05 μg mL-1 BR. The presented method offers higher sensitivity with simple instrumentation and was applied successfully in detecting BR at low concentrations.  相似文献   

20.
A new spectroflurometric method for the determination of adenosine disodium triphosphate (ATP) is developed. Fluorometric interaction between ATP and enoxacin (ENX)–Eu3+ complex was studied using UV–vis and fluorescence spectroscopy. Weak luminescence spectra of Eu3+ were enhanced after complexation with ENX at 589 nm and 614 nm upon excitation at 395 nm due to energy transfer from the ligand to the lanthanide ion. It was observed that luminescence spectrum of Eu3+ was strongly enhanced further at 614 nm after incorporation of ATP into the ENX–Eu3+ complex. Under optimal conditions, the enhancement of luminescence at 614 nm was responded linearly with the concentration of ATP. The linearity was maintained in the range of 1.5×10?10–1.15×10?8 M (R=0.9973) with the limit of detection (3σ) of 4.71×10?11 M. The relative standard deviation (RSD) for 9 repeated measurements of 1×10?9  M ATP was 1.25%. Successful determinations of ATP in soil, milk, and a pharmaceutical formulation with the proposed method were demonstrated.  相似文献   

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