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1.
A rapid and sensitive flow injection chemiluminescence (FI–CL) method is described for the determination of 2‐methoxyestradiol (2ME) based on enhancement of the CL intensity from a potassium ferricyanide–calcein system in sodium hydroxide medium. The optimum conditions for the CL emission were investigated. Under optimized conditions, a linear calibration graph was obtained over the range 1.0 × 10‐8 to 1.0 × 10‐6 mol/L (r = 0.998) 2ME with a detection limit (3σ) of 5.4 × 10‐9 mol/L. The relative standard deviation (RSD) for 5.0 × 10‐7 mol/L 2ME was 1.7%. As a preliminary application, the proposed method was successfully applied to the determination of 2ME in injection solutions and serum samples. The possible CL mechanism was also proposed. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

2.
Quenching effects of bergenin, based on the electrochemiluminescence (ECL) of the tris(2,2′‐bipyridyl)‐ruthenium(II) (Ru(bpy)32+)/tri‐n‐propylamine (TPrA) system in aqueous solution, is been described. The quenching behavior can be observed with a 100‐fold excess of bergenin over Ru(bpy)32+. In the presence of 0.1 m TPrA, the Stern–Volmer constant (KSV) of the ECL quenching is as high as 1.16 × 104 M?1 for bergenin. The logarithmic plot of the inhibited ECL versus logarithmic plot of the concentration of bergenin was linear over the range 3.0 × 10?6–1.0 × 10?4 mol/L. The corresponding limit of detection was 6.0 × 10?7 mol/L for bergenin (S/N = 3). In the mechanism of quenching it is believed that the competition of the active free radicals between Ru(bpy)32+/TPrA and bergenin was the key factor for the ECL inhibition of the system. Photoluminescence, cyclic voltammetry, coupled with bulk electrolysis, supports the supposition mechanism of the Ru(bpy)32+/TPrA–bergenin system. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

3.
An electrochemiluminescence (ECL) sensor based on reduced graphene oxide–CdTe quantum dots (RGO–CdTe QDs) composites for detecting copper ion (Cu2+) was proposed. The ECL behaviours of the RGO–CdTe QD modified electrode were investigated with H2O2 as the co‐reactant. Quantitative detection of Cu2+ was realized as Cu2+ could effectively quench the ECL signal of the RGO–CdTe QDs. A wide linear range of 1.00 × 10?14 to 1.00 × 10?4 M (R = 0.9953) was obtained under optimized conditions, and a detection limit (S/N = 3) was achieved of as low as 3.33 × 10?15 M. The proposed sensor also exhibited good stability and selectivity for the detection of copper ions. Finally, the analytical application of the proposed sensor was also evaluated using river water.  相似文献   

4.
The electrochemiluminescence (ECL) of tris(2,2‐bipyridyl)ruthenium [Ru(bpy)3]2+ has received much attention. By immobilizing [Ru(bpy)3]2+ on an electrode surface, solid‐state ECL has several advantages over solution‐phase ECL, such as reduced amounts of costly reagent and a simplified experimental design. Herein, different types of solid‐state ECL sensors were fabricated and the performances of paraffin oil and two ionic liquids (ILs) as the binders were compared for the construction of solid‐state ECL. Scanning electron microscopy (SEM), CCD camera, UV–vis, fluorescence spectroscopy, electrochemistry and ECL were applied to characterize and evaluate the performance of the solid‐state composites. According to the obtained results, Ru–graphite/IL octyl pyridinium hexaflurophosphate (OPPF6) was introduced as a new solid‐state ECL with excellent properties such as simple preparation, low background current, fast electron‐transfer rate and good reproducibility and stability. Moreover, for a study of the effect of carbon structure on the performance of the electrode, graphite was replaced by multi‐walled carbon nanotubes (MWCNTs) and Ru–MWCNT/OPPF6 was constructed and its efficiency was compared with Ru–graphite/OPPF6 composite electrode. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

5.
The enteric methane conversion factor (Ym) is an important country‐specific value for the provision of precise enteric methane emissions inventory reports. The objectives of this meta‐analysis were to develop and evaluate the empirical Ym models for the national level and the farm level for tropical developing countries according to the IPCC's categorization. We used datasets derived from 18 in vivo feeding experiments from 1999 to 2015 of Zebu beef cattle breeds fed low‐quality crop residues and by‐products. We found that the observed Ym value was 8.2% gross energy (GE) intake (~120 g methane emission head?1 day?1) and ranged from 4.8% to 13.7% GE intake. The IPCC default model (tier 2, Ym = 6.5% ± 1.0% GE intake) underestimated the Ym values by up to 26.1% compared with its refinement of 8.4% ± 0.4% GE intake for the national‐level estimate. Both the IPCC default model and the refined model performed worse in predicting Ym trends at the farm level (root mean square prediction error [MSPE] = 15.1%–23.1%, concordance correlation coefficient [CCC] = 0.16–0.18, R2 = .32). Seven of the extant Ym models based on a linear regression approach also showed inaccurately estimated Ym values (root MSPE = 16.2%–36.0%, CCC = 0.02–0.27, R2 < .37). However, one of the developed models, which related to the complexity of the energy use efficiencies of the diet consumed to Ym, showed adequate accuracy at the farm level (root MSPE = 9.1%, CCC = 0.75, R2 = .67). Our results thus suggest a new Ym model and future challenges for estimating Zebu beef cattle production in tropical developing countries.  相似文献   

6.
A simple and sensitive electrochemiluminescence (ECL) method for the determination of etamsylate has been developed by coupling an electrochemical flow‐through cell with a tris(2,2'‐bipyridyl)ruthenium(II) (Ru(bpy)32+)–Nafion‐modified carbon electrode. It is based on the oxidized Ru(bpy)32+ on the electrode surface reacting with etamsylate and producing an excellent ECL signal. Under optimized experimental conditions, the proposed method allows the measurement of etamsylate over the range of 8–1000 ng/mL with a correlation coefficient of r = 0.9997 (n = 7) and a limit of detection of 1.57 ng/mL (3σ), the relative standard deviation (RSD) for 1000 ng/mL etamsylate (n = 7) is 0.96%. The immobilized Ru(bpy)32+ carbon paste electrode shows good electrochemical and photochemical stability. This method is rapid, simple, sensitive and has good reproducibility. It has been successfully applied to the determination of the studied etamsylate in pharmaceutical preparations with satisfactory results. The possible ECL reaction mechanism has also been discussed. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

7.
A highly sensitive and selective method for the determination of cholesterol is required to evaluate trace amounts of cholesterol in test samples. In this work, selected gold nanoparticles (AuNPs) and 5‐amino‐2‐mercapto‐1,3,4‐thiadiazole (AMT) were used and a thin film of three‐dimensional gold–AMT core–shell nanoparticles (p‐AMT–AuNPs) was prepared using an electrochemical method. Cholesterol oxidase was then bonded to the film surface to give a functional electrode. Based on catalysis by the electrode functionalized for cholesterol and a luminol–H2O2 electrochemiluminescence (ECL) system, a highly sensitive and selective ECL method was developed for the determination of cholesterol. Under optimized conditions, ECL intensity showed a good linear relationship with cholesterol over the concentration range 0.05–11.0 µg/ml, with a correlation coefficient of 0.999 and a limit of detection of 0.02 µg/ml. The proposed method was used to determine cholesterol in dairy products with a relative standard deviation of < 1.8% and recovery rates of 98.1–104%. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

8.
A tris(2,2‐bipyridyl)ruthenium(II) (Ru(bpy)32+)‐based electrochemiluminescence (ECL) detection coupled with capillary electrophoresis (CE) method has been established for the sensitive determination of ephedrine for the first time. Under the optimized conditions [ECL detection at 1.15 V, 25 mmol/L phosphate buffer solution (PBS), pH 8.0, as running buffer, separation voltage 12.5 kV, 5 mmol/L Ru(bpy)32+ with 60 mmol/L PBS, pH 8.5, in the detection cell] linear correlation (r = 0.9987) between ECL intensity and ephedrine concentration was obtained in the range 6.0 × 10–8–6.0 × 10–6 g/mL. The detection limit was 4.5 × 10–9 g/mL (S:N = 3). The developed method was successfully applied to the analysis of ephedrine in human urine and the investigation of its interactions with three proteins, including bovine serum albumin (BSA), cytochrome C (Cyt‐C) and myoglobin (Mb). The number of binding sites and the binding constants between ephedrine and BSA, Cyt‐C and Mb were 8.52, 12.60, 10.66 and 1.55 × 104 mol/L, 6.58 × 103 mol/L and 1.59 × 104 mol/L, respectively. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

9.
We established cell suspension cultures derived from leaf, stem, and root calli of Pueraria candollei var. candollei and P. candollei var. mirifica using liquid Murashige and Skoog (MS) medium supplemented with 0.56 μM 6-benzyladenine (BA) and 4.52 μM 2,4-dichlorophenoxyacetic acid (2,4-D). Growth of the cell suspension cultures progressed to the stationary phase within 15–24 days. Methanolic extracts of cell suspension cultures of both varieties of P. candollei were analyzed using a validated HPLC protocol. All cell lines derived from leaf, stem, and root explants produced four major isoflavonoids: daidzein, daidzin, genistein, and genistin; these isoflavonoids were detected only in the roots of intact plants. Furthermore, the isoflavonoid contents of the cell suspension cultures were higher than those of intact plants. Thus, cell suspension culture of both varieties of P. candollei may be an effective tool for isoflavonoid production.  相似文献   

10.
Based on the strong enhancement effect of procaterol hydrochloride on the electrochemiluminescence (ECL) of Ru(bpy)32+ (bpy = 2,2′‐bipyridine) in an alkaline H3PO4–NaOH buffer solution on a bare Pt electrode, a simple, rapid and sensitive method was developed for the determination of procaterol hydrochloride. The optimum conditions for the enhanced ECL have been developed in detail in this work. Under optimum conditions, the logarithmic ECL enhancement vs. the logarithmic concentration of procaterol hydrochloride is linear over a wide concentration range of 2.0 × 10?7 to 2.0 × 10?4 M (r =  0.9976), with a limit of detection of 1.1 × 10?8 M (S/N =  3), and a relative standard deviation of 2.1% (n =  7, c =  5.0 × 10?6 M). The proposed method was applied to the determination of this drug in tablets with recoveries of 89.7%–98.5%. In addition, a possible mechanism for the enhanced ECL of Ru(bpy)32+, which is caused by ProH, has also been proposed.  相似文献   

11.
This study describes the quenching effects of p‐aminobenzenesulfonic acid (p‐ABSA) based on electrochemiluminescence (ECL) of the tris (2,2‐bipyridyl)‐ruthenium(II)(Ru(bpy)32+)/tri‐n‐propylamine (TPrA) system in aqueous solution. Quenching behaviours were observed with a 200‐fold excess of p‐ABSA over Ru(bpy)32+. In the presence of 0.1 M TPrA, the Stern‐Volmer constant (KSV) of ECL quenching was as high as 1.39 × 104 M‐1 for p‐ABSA. The logarithmic plot of inhibited ECL versus concentration of p‐ABSA was linear over the range of 6.0 × 10‐6 ‐3.0 × 10‐4 mol/L. The corresponding limit of detection was 1.2 × 10‐6 mol/L for p‐ABSA (S/N = 3). The mechanism of quenching is believed to involve an energy transfer from the excited‐state luminophore to a dimer of p‐ABSA and the adsorption of free radicals of p‐ABSA at the electrode surface that impeded the oxidation of the Ru(bpy)32+/TPrA system. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

12.
A sensitive electrochemiluminescence (ECL) detection of etimicin at Tris(2,2′‐bipyridyl)ruthenium(II) [Ru(bpy)32+]–Nafion modified carbon paste electrodes was developed. The immobilized Ru(bpy)32+ shows good electrochemical and photochemical activities. Electrochemical and electrochemiluminescence characterizations of the modified carbon electrodes were made by means of cyclic voltammetry and electrochemical impendence spectroscopy. The modified electrode showed an electrocatalytic response to the oxidation of etimicin, producing a sensitized ECL signal. The ECL sensor showed a linear response to etimicin in the range of 8.0–160.0 ng mL?1 with a detection limit of 6.7 ng mL?1. This method for etimicin determination possessed good sensitivity and reproducibility with a coefficient of variation of 5.1% (n = 7) at 100 ng mL?1. The ECL sensor showed good selectivity and long‐term stability. Its surface could be renewed quickly and reproducibly by a simple polish step. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

13.
In our present work, it was found that the electrooxidation of folic acid (FA) was accompanied by electrogenerated chemiluminescence (ECL) emission. Out of the four inorganic salts, NaNO3 solution was found to be a suitable supporting electrolyte for the ECL emission of FA. Coupled with high‐performance liquid chromatography separation, this simple ECL method was used for post‐column determination of FA. Under the optimal conditions, the ECL intensity has a linear relationship with the concentration of FA in the range of 1.0 × 10?7 to 1.0 × 10?5 g/mL and the detection limit was 5 × 10?8 g/mL (signal‐to‐noise ratio = 3). Application of the present method to the analysis of FA in human urine proved feasible. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

14.
There is a growing demand to realize low-cost miniaturized point-of-care testing diagnostic devices capable of performing many analytical assays. To fabricate such devices, three-dimensional printing (3DP)-based fabrication techniques provide a turnkey approach with marked precision and accuracy. Here, a 3DP fabrication technique was successfully utilized to fabricate closed bipolar electrode-based electrochemiluminescence (ECL) devices using conductive graphene filament. Furthermore, using these ECL devices, Ru(bpy)32+/TPrA- and luminol/H2O2-based electrochemistry was leveraged to sense dopamine and choline respectively. For ECL signal capture, two distinct approaches were used, first a smartphone-based miniaturized platform and the second with a photomultiplier tube embedded with the internet of things technology. Choline sensing led to a linear range 5–700 μM and 30–700 μM with a limit of detection (LOD) of 1.25 μM (R2 = 0.98, N = 3) and 3.27 μM (R2 = 0.97, N = 3). Furthermore, dopamine sensing was achieved in a linear range 0.5–100 μM with an LOD = 2 μM (R2 = 0.99, N = 3) and LOD = 0.33 μM (R2 = 0.98, N = 3). Overall, the fabricated devices have the potential to be utilized effectively in real-time applications such as point-of-care testing.  相似文献   

15.
Flexible thin film dielectric capacitors with high energy storage density and a fast charging–discharging rate have attracted increasing attention as the development of microelectronics progresses toward flexibility and miniaturization. In this work, an all‐inorganic thin film dielectric capacitor with a multilayer structure based on (Na0.8K0.2)0.5Bi0.5TiO3 and Ba0.5Sr0.5(Ti0.97Mn0.03)O3 is designed and synthesized on a mica substrate. By optimizing the periodic number (N), concomitantly enhanced breakdown strength and large polarization difference are achieved in the film with N = 6, which contributes to the large energy density (Wrec) of 91 J cm?3, high efficiency (η) of 68%, and fast discharging rate of 47.6 µs. The obtained energy density is the highest value up to now in flexible dielectric capacitors, including lead‐free and lead‐based inorganic films as well as organic dielectric films. Moreover, no obvious deterioration of the energy storage performance is observed in the wide ranges of working temperature (?50–200 °C), operating frequency (500 Hz to 30 kHz), and fatigue cycles (1–108). Besides, the Wrec and η are ultra‐stable under various bending radii (R = 12–2 mm) and even after 104 bending cycles at R = 4 mm, demonstrating an outstanding mechanical bending endurance. This excellent performance will allow the capacitor thrive in flexible microenergy storage systems.  相似文献   

16.
Streamside measurements of critical thermal maxima (Tcrit), swimming performance (Ucrit), and routine (Rr) and maximum (Rmax) metabolic rates were performed on three populations of genetically distinct redband trout Oncorhynchus mykiss in the high‐desert region of south‐eastern Oregon. The Tcrit values (29·4 ± 0·1° C) for small (40–140 g) redband trout from the three streams, and large (400–1400 g) redband trout at Bridge Creek were not different, and were comparable to published values for other salmonids. At high water temperatures (24–28° C), large fish incurred higher metabolic costs and were more thermally sensitive than small fish. Ucrit(3·6 ± 0·1 LF s?1), Rr(200 ± 13 mg O2 kg?0·830 h?1) and metabolic power (533 ± 22 mg O2 kg?0·882 h?1) were not significantly different between populations of small redband trout at 24° C. Rmax and metabolic power, however, were higher than previous measurements for rainbow trout at these temperatures. Fish from Bridge Creek had a 30% lower minimum total cost of transport (Cmin), exhibited a lower refusal rate, and had smaller hearts than fish at 12‐mile or Rock Creeks. In contrast, no differences in Ucrit or metabolism were observed between the two size classes of redband trout, although Cmin was significantly lower for large fish at all swimming speeds. Biochemical analyses revealed that fish from 12‐mile Creek, which had the highest refusal rate (36%), were moderately hyperkalemic and had substantially lower circulating levels of free fatty acids, triglycerides and albumin. Aerobic and anaerobic enzyme activities in axial white muscle, however, were not different between populations, and morphological features were similar. Results of this study: 1) suggest that the physiological mechanisms that determine Tcrit in salmonids are highly conserved; 2) show that adult (large) redband trout are more susceptible to the negative affects of elevated temperatures than small redband trout; 3) demonstrate that swimming efficiency can vary considerably between redband trout populations; 4) suggest that metabolic energy stores correlate positively with swimming behaviour of redband trout at high water temperatures; 5) question the use of Tcrit for assessing physiological function and defining thermal habitat requirements of stream‐dwelling salmonids like the redband trout.  相似文献   

17.
The influence of 2‐methoxyestradiol (2‐ME) was investigated on cell numbers, morphology, cell cycle progression, and apoptosis induction in an oesophageal carcinoma cell line (WHCO3). Dose‐dependent studies (1 × 10?9M–1 × 10?6M) revealed that 2‐ME significantly reduced cell numbers to 60% in WHCO3 after 72 h of exposure at a concentration of 1 × 10?6M compared to vehicle‐treated cells. Morphological studies entailing light‐, fluorescent‐, as well as transmission electron microscopy (TEM) confirmed 2‐ME's antimitotic effects. These results indicated hallmarks of apoptosis including cell shrinkage, hypercondensation of chromatin, cell membrane blebbing, and apoptotic bodies in treated cells. Flow cytometric analyses demonstrated an increase in the G2/M‐phase after 2‐ME exposure; thus preventing cells from proceeding through the cell cycle. β‐tubulin immunofluorescence revealed that 2‐ME caused spindle disruption. In addition, increased expression of death receptor 5 protein was observed further supporting the proposed mechanism of apoptosis induction via the extrinsic pathway in 2‐ME‐exposed oesophageal carcinoma cells. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

18.
In a series of experiments on the growth and nutrition of copper-limited birch (Betula pendula Roth) plants, growth was controlled by the relative addition rate of copper, RCu (d–1). This was 0·05, 0·10, 0·15 or 0·20 d–1 with free access to all other nutrients. An additional treatment provided free access to all nutrients. The pH in the nutrient solution was ≈ 4·5 and conductivity was 100 μS cm–1. At steady-state growth, there was a linear relationship between the relative growth rate, RG, and RCu. The [Cu] of the plants ranged from 2·4 to 2·7 μg g–1 dry mass (DM) in all treatments with limiting RCu and was ≈ 28 μg g–1 in the free access treatment. The plants showed specific copper deficiency symptoms at limitation. Total non-structural carbohydrate concentrations and the fraction of plant DM partitioned to roots was much less at copper limitation than at free access. The uptake rate of copper per unit root growth rate, dCu/dWr (μmol g–1 root DM) was unaffected by the copper supply. Low rates of plant growth at copper limitation were associated with high values of specific leaf area (SLA; 47 m2 kg–1) and leaf area ratio (LAR; 28 m2 kg–1 plant DM) but lower values of net assimilation rate (NAR; 2·5 kg m–2 leaf DM d–1) than were found at free access, 28 m2 kg–1 (SLA), 17 m2 kg–1 DM (LAR) and 14 kg m–2 leaf DM d–1 (NAR), respectively. It is not obvious from the present data how the growth response can help alleviate copper limitation in the field.  相似文献   

19.
Introduction – Centrifugal partition chromatography (CPC), as a continuous liquid–liquid partition chromatography with no solid support matrix, combined with evaporative light scattering detection (ELSD) was employed for systematic separation and purification of weak‐chromophoric saponins from a highly valued and important traditional Chinese herbal medicine, Panax notoginseng. Objective – To separate and isolate high‐purity saponins from extract of Panax notoginseng using CPC‐ELSD with a simple and low toxicity solvent system. Methodology – Samples were preparaed by extracting the root material with acetone, treated with n‐butanol and then freeze‐dried. CPC‐ELSD was applied in the separation and detection of notoginsenoside and ginsenosides from extract of Panax notoginseng using a solvent system composed of ethyl acetate–n‐butanol–water (1:1:2, v/v/v). The saponins were analysed and identified by their retention time with high‐performance liquid chromatography (HPLC) coupled with ELSD, as well as electrospray ionisation tandem mass spectrometry (ESI‐MSn ) in the negative and positive ion modes with the authentic standards. Results – A total of 9.6 mg of notoginsenoside R1, 67.8 mg of ginsenoside Rg1, 2.3 mg of Re and 286.5 mg of Rb1 were purified from 487.2 mg of n‐butanol extract of P. notoginseng. The purities of obtained saponins in a single run were assessed to be over 98% by HPLC‐ELSD. Conclusion – CPC‐ELSD was proved to be a very fast and efficient tool for separation of high‐purity dammarane saponins. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

20.
Earlier cross‐sectional studies found that a single magnetic resonance imaging (MRI) slice predicts total visceral and subcutaneous adipose tissue (VAT and SAT) volumes well. We sought to investigate the accuracy of trunk single slice imaging in estimating changes of total VAT and SAT volume in 123 overweight and obese subjects who were enrolled in a 24‐week CB‐1R inverse agonist clinical trial (weight change, ?7.7 ± 5.3 kg; SAT change, ?5.4 ± 4.9 l, VAT change, ?0.8 ± 1.0 l). VAT and SAT volumes at baseline and 24 weeks were derived from whole‐body MRI images. The VAT area 5–10 cm above L4—L5 (A+5–10) (R2 = 0.59–0.70, P < 0.001) best predicted changes in VAT volume but the strength of these correlations was significantly lower than those at baseline (R2 = 0.85–0.90, P < 0.001). Furthermore, the L4—L5 slice poorly predicted VAT volume changes (R2 = 0.24–0.29, P < 0.001). Studies will require 44–69% more subjects if (A+5–10) is used and 243–320% more subjects if the L4—L5 slice is used for equivalent power of multislice total volume measurements of VAT changes. Similarly, single slice imaging predicts SAT loss less well than cross‐sectional SAT (R2 = 0.31–0.49 vs. R2 = 0.52–0.68, P < 0.05). Results were the same when examined in men and women separately. A single MRI slice 5–10 cm above L4—L5 is more powerful than the traditionally used L4—L5 slice in detecting VAT changes, but in general single slice imaging poorly predicts VAT and SAT changes during weight loss. For certain study designs, multislice imaging may be more cost‐effective than single slice imaging in detecting changes for VAT and SAT.  相似文献   

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