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1.
It was found that the fluorescence of Tb3+–epinephrine (E) complex can be enhanced by both bovine serum albumin (BSA) and sodium dodecylsulfate (SDS), and stabilized by ascorbic acid (AA). It is considered that the fluorescence enhancement of the Tb3+–E–BSA–AA–SDS system originates not only from the hydrophobic microenvironment provided by BSA–SDS, but also from the energy transfer from BSA to Tb3+ in this system. Therefore, a new fluorescence method for the determination of protein concentrations as low as 1.3 × 10?9 g mL?1 BSA is established using Tb3+–epinephrine complex as probe. The method has been applied for the determination of BSA and human serum albumin in actual samples, and the results obtained are satisfactory. Compared with other fluorescence methods, this method is simpler and more sensitive for the determination of protein. The mechanism of the fluorescence enhancement of the system is studied in detail. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

2.
A chemiluminescent method using flow injection (FI) was investigated for rapid and sensitive determination of enalapril maleate and atenolol, which are used in the treatment of hypertension. The method is based on the sensitizing effect of these drugs on the Ce(IV)–sulfite reaction. The different experimental parameters affecting the chemiluminescence (CL) intensity were carefully studied and incorporated into the procedure. The method permitted the determination of 0.01–3.0 µg mL?1 of enalapril maleate in bulk form with correlation coefficient r = 0.99993, lower limit of detection (LOD) 0.0025 µg mL?1 (S/N = 2) and lower limit of quantitation (LOQ) 0.01 µg mL?1. The linearity range of atenolol in bulk form was 0.01–2.0 µg mL?1 (r = 0.99989) with LOD of 0.0003 µg mL?1 (S/N = 2) and LOQ of 0.01 µg mL?1. In biological fluids the linearity range of enalapril maleate was 0.1–2.0 µg mL?1 in both urine and serum, and for atenolol the linearity range was 0.1–1.0 µg mL?1 in both urine and serum. The method was also applied to the determination of the drugs in their pharmaceutical preparations. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

3.
In this paper, a simple and highly sensitive spectrofluorimetric method was developed and validated for the determination of entacapone (ETC). The proposed method is based on forming a highly fluorescent product through the reduction of ETC with Zn/HCl. The produced fluorophore exhibits strong fluorescence at λem 345 nm after excitation at λex 240 nm. The use of fluorescence enhancers such as Tween‐80 and carboxy methyl cellulose (CMC) greatly enhanced the fluorescence of the produced fluorophore by 150% and 200%, respectively. Calibration curves showed good linear regression (r2 > 0.9998) within test ranges of 0.05–2.0 and 0.02–1.80 μg mL?1 with lower detection limits of 1.27 × 10?2 and 4.8 × 10?3 μg mL?1 and lower quantification limits of 4.21 × 10?2 and 1.61 × 10?2 μg mL?1 upon using Tween‐80 and or CMC, respectively. The method was successfully applied to the analysis of ETC in its pharmaceutical formulations (either alone or in presence of other co‐formulated drugs). The results were in good agreement with those obtained using the official method. The methods were further extended to determine the drug in human plasma samples, and to study the pharmacokinetics of ETC. The paper is the first report on the spectrofluorimetric determination of entacapone.  相似文献   

4.
Luminescent LaF3–Ce3+/Tb3+ nanocrystals have been successfully prepared via a simple wet chemical technique. For the next bioapplication, these nanoparticles dispersed in cyclohexane have also been functionalized with poly(St‐co‐MAA), based on a designed oil‐in‐water microemulsion system. These polymer‐coated nanospheres are water‐soluble and bioconjugable. Unlike semiconductor quantum dots, the as‐prepared lanthanum fluoride nanocrystals possess non‐size‐dependent emissions and completely stable photocycles. With functionalized LaF3 nanospheres as fluorescence probes, a fluorescence method was developed for the rapid quantitative analysis of DNA, due to the quenching effect of fluorescence by the DNA. Under optimum conditions, the fluorescence intensity was proportional to the concentration of the introduced DNA over the range 2.5–35 µg/mL for calf thymus DNA (ctDNA) and 2.5–30 µg/mL for fish sperm DNA (fsDNA), respectively. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

5.
In this work we investigate a mesoporous silica (MS) decorated with dipyridyl‐pyridazine (dppz) ligands and further grafted with a mixture of Eu3+/Tb3+ ions (28.45%:71.55%), which was investigated as a potential thermometer in the 10–360 K temperature range. The MS material was prepared employing a hetero Diels–Alder reaction: 3,6‐di(2‐pyridyl)‐1,2,4,5‐tetrazine was reacted with the double bonds of vinyl‐silica (vSilica) followed by an oxidation procedure. We explore using the dppz‐vSilica material to obtain visible emitting luminescent materials and for obtaining a luminescent thermometer when grafted with Eu3+/Tb3+ ions. For the dppz‐vSilica@Eu,Tb material absolute sensitivity Sa of 0.011 K?1 (210 K) and relative sensitivity Sr of 1.32 %K?1 (260 K) were calculated showing good sensing capability of the material. Upon temperature change from 10 K to 360 K the emission color of the material changed gradually from yellow to red.  相似文献   

6.
Two complexes of Tb3+, Gd3+/Tb3+ and one heteronuclear crystal Gd3+/Tb3+ with phenoxyacetic acid (HPOA) and 2,4,6‐tris‐(2‐pyridyl)‐s–triazine (TPTZ) have been synthesized. Elemental analysis, rare earth coordination titration, inductively coupled plasma atomic emission spectrometry (ICP‐AES) and thermogravimetric analysis‐differential scanning calorimetry (TG‐DSC) analysis show that the two complexes are Tb2(POA)6(TPTZ)2·6H2O and TbGd(POA)6(TPTZ)2·6H2O, respectively. The crystal structure of TbGd(POA)6(TPTZ)2·2CH3OH was determined using single‐crystal X‐ray diffraction. The monocrystal belongs to the triclinic system with the P‐1 space group. In particular, each metal ion is coordinately bonded to three nitrogen atoms of one TPTZ and seven oxygen atoms of three phenoxyacetic ions. Furthermore, there exist two coordinate forms between C6H5OCH2COO and the metal ions in the crystal. One is a chelating bidentate, the other is chelating and bridge coordinating. Fluorescence determination shows that the two complexes possess strong fluorescence emissions. Furthermore, the fluorescence intensity of the Gd3+/Tb3+ complex is much stronger than that of the undoped complex, which may result from a decrease in the concentration quench of Tb3+ ions, and intramolecular energy transfer from the ligands coordinated with Gd3+ ions to Tb3+ ions. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

7.
The title compound of 3‐benzothiazole‐9‐ethyl carbazole was synthesized by the reaction of 3‐aldehyde‐9‐ethyl carbazole and 2‐aminothiophenol. The compound was characterized by 1H nuclear magnetic resonance (NMR) and mass spectrometry (MS). Its crystal structure was obtained and determined by single crystal X‐ray diffraction. The results showed that the crystal belongs to the orthorhombic crystal system and the cell parameters of space group P2(1)2(1)2(1) were a = 5.6626 (12) Å, b = 12.606 (3) Å, c = 22.639 (5) Å, α = 90°, β = 90°, γ = 90°, V = 1616.0 (6) Å3, Z = 4, Dc = 1.350 mg/m3. The UV–vis and fluorescence spectra were also studied preliminarily. The fluorescence spectra of the title compound with bovine serum albumin (BSA) showed that BSA could be marked with the compound and the stability constant between them was 0.82 × 107 M?1. Meanwhile, the crystal and molecule were theoretically surveyed by density functional tight‐binding (DFTB). The results showed that there was an orbital overlap for lowest unoccupied molecular orbital (LUMO) between the neighbouring molecules for the crystal, which is different from the molecule structure. It was also showed that the crystal structure is a non‐conductor. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

8.
A highly sensitive method for the detection of 6‐mercaptopurine (MP) by resonance Rayleigh light scattering (RLS) method was developed. Gold nanoparticles (AuNPs) were synthesized by a modified seed method and characterized using transmission electron microscopy (TEM). AuNPs were bound to MP via covalent bonding to form the MP–AuNPs complex, which increased the RLS intensity of MP at 347 nm (increased by 65.7%). Under optimum conditions, the magnitude of the enhanced RLS intensity for MP–AuNPs was proportional to MP concentration in the range 0.0681–1.702 μg mL?1. The linear regression equation was represented as follows: ΔI RLS = 9.31 + 82.42c (r  = 0.9948). The limit of detection (LOD, 3σ) was 3.32 ng mL?1. The system was applied successfully to detect MP in pharmaceuticals. MP recoveries were 99.9–101.7% with a relative standard deviation (RSD) (n  = 5) of 0.59–0.77% for three synthetic samples, and 97.5–110.0% with an RSD of 0.98–2.10% (n =  5) for tablet samples.  相似文献   

9.
Er3+‐doped germanate glasses with superior thermal stability were prepared. Judd–Ofelt intensity parameters and important spectroscopic properties were discussed in detail. Upon 800 nm and 980 nm LD pumping, 2.7 µm fluorescence characteristics were investigated and it was found that the effective 2.7 µm emission bandwidth can reach to 101.79 nm in prepared glasses. The tunability of the 2.7 µm emission band can be realized by adjusting the Er3+ content. Moreover, a high‐emission cross‐section (11.09 ×10‐21 cm2), large gain bandwidth (772.30 ×10‐28 cm3) and gain coefficient (6.72 cm‐1) were obtained in the prepared sample. Hence, Er3+‐doped germanate glass might be a promising mid‐infrared material for tunable amplifiers or lasers. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

10.
Single crystals of KCl doped with Ce3+,Tb3+ were grown using the Bridgeman–Stockbarger technique. Thermoluminescence (TL), optical absorption, photoluminescence (PL), photo‐stimulated luminescence (PSL), and thermal‐stimulated luminescence (TSL) properties were studied after γ‐ray irradiation at room temperature. The glow curve of the γ‐ray‐irradiated crystal exhibits three peaks at 420, 470 and 525 K. F‐Light bleaching (560 nm) leads to a drastic change in the TL glow curve. The optical absorption measurements indicate that F‐ and V‐centres are formed in the crystal during γ‐ray irradiation. It was attempted to incorporate a broad band of cerium activator into the narrow band of terbium in the KCl host without a reduction in the emission intensity. Cerium co‐doped KCl:Tb crystals showed broad band emission due to the d–f transition of cerium and a reduction in the intensity of the emission peak due to 5D37Fj (j = 3, 4) transition of terbium, when excited at 330 nm. These results support that energy transfer occurs from cerium to terbium in the KCl host. Co‐doping Ce3+ ions greatly intensified the excitation peak at 339 nm for the emission at 400 nm of Tb3+. The emission due to Tb3+ ions was confirmed by PSL and TSL spectra. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

11.
In this work, carbon dots (CDs) with a high quantum yield (22.3%) were easily prepared by hydrothermal pyrolysis of acid fuchsin 6B and hydrogen peroxide at 180°C for 10 h. The resultant CDs possess a narrow size distribution in the range of 2.6 to 3.2 nm and emit blue fluorescence. Interestingly, the absorption band of metronidazole (MTZ) centered at 318 nm can complementary overlap with the excitation band of the as‐prepared CDs centered at 320 nm, resulting in an inner filter effect (IFE) in high efficiency. In fact, the fluorescence quenching of the CDs depends on the concentration of MTZ. Therefore, a simple method for the detection of MTZ can be established using the CDs‐based sensor via the IFE. The linear range of the proposed method was 0–10 μg mL?1 with the limit of detection as low as 0.257 μg mL?1. This CDs‐based sensor had been applied for the detection of MTZ in honey and MTZ tablets with the recoveries in the range of 98.0% to 105.1% and 95.7% to 106.5%, respectively. Therefore, the as‐prepared CDs have a potential to be developed as a MTZ sensor with high selectivity, sensitivity and accuracy.  相似文献   

12.
Eight novel 1,2,4‐triazolo[3,4‐b]‐1,3,4‐thiadiazol derivatives have been designed and synthesized, and their corresponding Tb3+ complexes were also prepared successfully. The fluorescence properties and fluorescence quantum yields of the target complexes were investigated, the results showed that the ligands were an efficient sensitizer for Tb3+ luminescence, and the target complexes exhibited characteristic fluorescence emissions of Tb3+ ion. The fluorescence intensity of the complex substituted by chlorine was stronger than that of other complexes. The substituents' nature has a great effect upon the electrochemical properties of the target complexes. The results showed that the introduction of the electron‐withdrawing groups tended to decrease the oxidation potential and highest occupied molecular orbital energy levels of the target Tb3+ complexes; however, introduction of the electron‐donating groups can increase the corresponding complexes' oxidation potential and highest occupied molecular orbital energy levels. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

13.
A novel series of imidazole‐linked thiazolidinone hybrid molecules were designed and synthesized through a feasible synthetic protocol. The molecules were characterized with Fourier transform infrared (FT‐IR), 1H nuclear magnetic resonance (NMR), 13C NMR and high‐resolution mass spectrometry (HRMS) techniques. In vitro susceptibility tests against Gram‐positive (S. aureus and B. subtilis ) and Gram‐negative bacteria (E. coli and P. aeruginosa ) gave highly promising results. The most active molecule (3e) gave a minimal inhibitory concentration (MIC) value of 3.125 μg/mL which is on par with the reference drug streptomycin. Structure–activity relationships revealed activity enhancement by nitro and chloro groups when they occupied meta position of the arylidene ring in 2‐((3‐(imidazol‐1‐yl)propyl)amino)‐5‐benzylidenethiazolidin‐4‐ones. DNA‐binding study of the most potent molecule 3e with salmon milt DNA (sm‐DNA) under simulated physiological pH was probed with UV–visible absorption, fluorescence quenching, gel electrophoresis and molecular docking techniques. These studies established that compound 3e has a strong affinity towards DNA and binds at DNA minor groove with a binding constant (Kb) 0.18 × 102 L mol?1. Molecular docking simulations predicted strong affinity of 3e towards DNA with a binding affinity (ΔG) ‐8.5 kcal/mol. Van der Waals forces, hydrogen bonding and hydrophobic interactions were predicted as the main forces of interaction. The molecule 3e exhibited specific affinity towards adenine–thiamine base pairs. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

14.
In this paper, a novel fluorescent sensor 1 for selective and sensitive detection of cysteine was developed based on a complex between bi‐8‐carboxamidoquinoline derivative ligand ( L ) and Cu2+. The interaction of Cu2+ with the ligand causes a dramatic fluorescence quenching most likely due to its high affinity towards Cu2+ and a ligand–metal charge transfer (LMCT) process. The in situ generated L–Cu 2 complex was utilized as a chemosensing ensemble for cysteine. In the presence of cysteine, the fluorophore, L , was released from L–Cu 2 complex because of the strong affinity of cysteine to Cu2+ via the Cu–S bond, leading to the fluorescence recovery of the ligand. The proposed displacement mechanism was confirmed by the results of mass spectrometry (MS) study. Under optimized conditions, the recovered fluorescence intensity is linear with cysteine concentrations in the range 1 × 10?6 mol/l to 8 × 10?6 mol/l. The detection limit for cysteine is 1.92 × 10?7 mol/l. Furthermore, the established method showed a highly sensitive and selective response to cysteine among the 20 fundamental α‐amino acids used as the building blocks of proteins, after Ni2+ was used as a masking agent to eliminate the interference of His. The proposed sensor is applicable in monitoring cysteine in practical samples with good recovery rate.  相似文献   

15.
We investigated the effects of zinc or lead on growth and on exudation of fluorescent dissolved organic matter (FDOM) by the marine toxic dinoflagellate Alexandrium catenella (Whedon & Kofoid) Balech. The species was exposed to increasing free zinc (1.34 × 10?7 M–3.98 × 10?6 M) or lead (5.13 × 10?9 M–1.82 × 10?7 M) concentra‐tions. Low metal levels ([Zn2+] = 1.34 × 10?7 M; [Pb2+] = 5.13 × 10?9 M) had no effect on cell growth. Toxic effects were observed from higher metal contamination ([Zn2+] = 3.98 × 10?6 M; [Pb2+] = 6.54 × 10?8 M), as a conversion of vegetative cells into cysts. Analysis of the released FDOM by three‐dimensional (3‐D) fluorescence spectroscopy was achieved, using the parallel factor analysis (PARAFAC). The PARAFAC modeling revealed four components associated with two contributions: one related to the biological activity; the other linked to the organic matter decomposition in the culture medium. The C1 component combined a tryptophan peak and characteristics of humic substances, whereas the C2 component was considered as a tryptophan protein fluorophore. The two others C3 and C4 components were associated with marine organic matter production. Relea‐sed fluorescent substances were induced by low ([Zn2+]= 1.34 × 10?7 M; [Pb2+] = 5.13 × 10?9 M) and moderate ([Zn2+] = 6.21 × 10?7 M; [Pb2+] = 2.64× 10?9 M) metal concentrations, suggesting the activation of cellular mechanisms in response to metal stress, to exudate FDOM that could complex metal cations and reduce their toxicity toward A. catenella cells.  相似文献   

16.
The formation of metal chelates with various ligands may lead to the production of fluorescent chelates or enhance the fluorescence of the chelating agent. This paper describes two sensitive, selective and computer‐solved methods, namely, zero order (SF) and second‐derivative synchronous spectrofluorimetry (SDSFS) for nano‐quantitation of two carbapenems; meropenem (MP) and ertapenem (EP). The methods are based on the chelation of MP with Tb3+ and EP with Zr4+ in buffered organic medium at pH 4.0 to produce fluorescent chelates. In the zero order method, the relative synchronous fluorescence intensity is measured at 327.0 nm at Δλ = 70.0 and 100.0 nm for MP and EP, respectively. The second method utilizes a second‐derivative technique to enhance the method selectivity and emphasize a stability‐indicating approach. The peak amplitudes (2D) of the second‐derivative synchronous spectra were estimated to be 333.06 and 330.06 nm for MP and EP, respectively. The proposed synchronous spectrofluorimetric methods were validated according to the International Conference on Harmonization (ICH) guidelines and applied successfully for the analysis of MP and EP in pure forms, pharmaceutical vials and in synthetic mixtures with different degradants of both drugs. Under optimum conditions, the mole‐ratio method was applied and the co‐ordination ratios of MP–Tb3+ and EP–Zr4+chelates were found to be 1:1 and 1:3. The formation constants for the chelation complexes were evaluated using the Benesi–Hildebrand's equation; the free energy change (ΔG) was also calculated. The results indicated that EP–Zr4+ was more stable than the MP–Tb3+ chelate. Moreover, the developed methods were found to be selective and inexpensive for quantitative determination of both drugs in quality control laboratories at nano‐levels.  相似文献   

17.
It was found that meloxicam could enhance the chemiluminescence (CL) of the tris(2,2'‐bipyridine) ruthenium(II)–Ce(IV) system in the medium of sulfate acid. Based on this phenomenon a new flow‐injection system with chemiluminescent detection has been proposed for determination of meloxicam. Under optimum conditions, meloxicam had a good linear relationship with the CL intensity in the concentration range of 6.0  10?4 to 1.0 µg/mL and the detection limit was 3.7 × 10?4 µg/mL. The proposed method was applied to detect meloxicam in tablets and a satisfactory recovery was obtained. The possible mechanism for this CL system is also discussed in this paper. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

18.
A highly sensitive fluorogenic probe for tiopronin was proposed. 2,4‐Dinitrobenzenesulfonyl‐fluorescein (I) is an almost nonfluorescent compound. Upon mixing with tiopronin in aqueous solution, the 2,4‐dinitrobenzenesulfonyl group of I was efficiently removed and its parent dye fluorescein was released, hence leading to dramatic increases in both fluorescence and absorbance of the reaction mixture. Under optimal conditions, the fluorescence increase is linear with tiopronin concentration in the range 5.0–600 ng mL?1, with a detection limit of 1.5 ng mL?1 (3σ). The proposed method has been successfully applied to tiopronin determination in pharmaceutical preparations and in spiked human urine samples. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

19.
Twelve lanthanide complexes with cinnamate (cin) and 1,10‐phenanthroline (phen) were synthesized and characterized. Their compositions were assumed to be RE(cin)3phen (RE3+ = La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Tm3+, Yb3+, Lu3+). The interaction mode between the complexes and DNA was investigated by fluorescence quenching experiment. The results indicated the complexes could bind to DNA and the main binding mode is intercalative binding. The fluorescence quenching constants of the complexes increased from La(cin)3phen to Lu(cin)3phen. Additionally, the antibacterial activity testing showed that the complexes exhibited excellent antibacterial ability against Escherichia coli, and the changes of antibacterial ability are in agreement with that of the fluorescence quenching constants. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

20.
A fluorescent probe was developed and characterized, it consisted of terbium(III) with 3‐ally‐salicylohydrazide in ethanol, in which the 1:2 [Tb3+:S1] molar ratio was the best stoichiometric ratio for the probe. The ligand 3‐ally‐salicylohydrazide (S1) was synthesized, then was confirmed by IR, CHN, LC–MS and 1H NMR. The sensitivity of the probe's fluorescence spectra towards the presence of eight organophosphorus pesticides in ethanolic solution was studied, in which the probe showed marked sensitivity towards dichlorvos pesticide. A tangible enhancement of the probe's fluorescence intensity was observed as a consequence of the gradual addition of dichlorvos pesticide. The calculated limit of detection (LOD) was 1.183 μM and limit of quantitation (LOQ) was 3.94 μM. Further characterization of the nature of forces acting in the interaction of the probe with dichlorvos was performed by calculation of binding constants at different temperatures according to the Benesi ? Hildebrand equation, and the thermodynamic parameters ΔH, ΔS and ΔG. In order to assess the analytical applicability of the method, the influence of various potentially interfering anion and cations that naturally occur in water and soil were calculated.  相似文献   

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