Flow‐injection chemiluminescence of the luminol–potassium periodate system enhanced by TGA–capped CdTe quantum dots for the determination of theophylline

The chemiluminescence (CL) behaviour of the luminol–potassium periodate system enhanced by CdTe quantum dots capped with thioglycolic acid (TGA–CdTe QDs) was studied using kinetic experiments, CL spectra, UV–vis absorption spectra and fluorescence spectra. The production of oxygen‐containing reactant intermediates (O₂^?? and OH^?) in the present CL system was verified by CL. The possible CL mechanism was discussed in detail. Furthermore, theophylline (THP) was determined based on its enhancement of the CL intensity of the CdTe QDs–luminol–potassium periodate system coupled with a flow‐injection technique. Under these optimized conditions, the linear range was found to be from 1.0 × 10^?8 to 1.0 × 10^?5 g/mL with a detection limit of 2.8 × 10^?9 g/mL (3σ). The recoveries for the determination of THP in tablets were from 98.2 to 99.6%.     

Flow injection chemiluminescence determination of 6‐mercaptopurine based on a new system of potassium permanganate–thioacetamide–sodium hexametaphosphate

A novel chemiluminescence method for the determination of 6‐mercaptopurine was established based on 6‐mercaptopurine inhibition of the chemiluminescence emission of potassium permanganate–thioacetamide–sodium hexametaphosphate system. The peak height was proportional to log 6‐mercaptopurine concentration in the range 7.0 × 10^?10 to 1.0 × 10^?7 g/mL and the detection limit was 1.9 × 10^?11 g/mL (S/N = 3). The relative standard deviation was 1.5% for the determination of 8.0 × 10^?8 g/mL 6‐mercaptopurine (n = 11). The proposed sensor was successfully applied to the analysis of 6‐mercaptopurine in human serum samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Study on the interaction between 2‐mercaptoethanol,dimercaprol and CdSe quantum dots

The interactions between 2‐mercaptoethanol, dimercaprol and CdSe quantum dots (QDs) in organic media have been investigated by spectral methods. The results showed that the fluorescence (FL) emission of CdSe QDs gradually decreased, with a slight red‐shift, after adding thiols to CdSe QDs solutions. With the increase of the concentrations of thiols, the resonance light scattering (RLS) signal of CdSe QDs had been strongly enhanced in the wavelength range 300–500 nm, which was confirmed by the formation of larger CdSe QDs particles. The effect of thiols on the FL emission of CdSe QDs could be described by a Stern–Volmer‐type equation with the concentration ranges 1.0 × 10^–6–7.5 × 10^–4 mol/L for 2‐mercaptoethanol and 1.0 × 10^–7–2.5 × 10^–5 mol/L for dimercaprol. The possible mechanism of the interaction was proposed according to the results of UV‐vis absorption and micro‐Raman spectroscopy. The results indicated that FL quenching was mainly attributable to the exchange of the QDs surface molecules. Copyright © 2008 John Wiley & Sons, Ltd.     

Application of a lanthanide composite nanoparticle‐sensitized luminescence method for the determination of salicylic acid in pharmaceutical formulations and human plasma

Terbium‐acetylacetone (Tb–acac) composite nanoparticles were synthesized using the ultrasonic method. The nanoparticles are water‐soluble, stable and have extremely narrow emission bands and high internal quantum efficiencies. They were used as fluorimetric probes in the determination of salicylic acid (SA), based on the fluorescence enhancement of nanoparticles through fluorescence resonance energy transfer (FRET). The influence of buffer solution was investigated. Under the optimum conditions, a linear calibration graph was obtained over the SA concentration range 5 × 10^–7–1 × 10^–4 mol/L. The limit of detection was found to be 2.5 × 10^–8 mol/L. The relative standard deviation (RSD) for six repeated measurements of 1 × 10^–4 mol/LSA was 1.75%. The method was applied to the determination of SA in pharmaceutical formulations and human plasma. We believe that the proposed approach has great potential for clinical purposes. Copyright © 2008 John Wiley & Sons, Ltd.     

Determination of oxytetracycline hydrochloride in milk and egg white samples using Ru(bipy)32+–Ce(SO4)2 chemiluminescence

A novel, rapid and sensitive chemiluminescence (CL) method for the determination of oxytetracycline hydrochloride (OTCH) is described in this paper. The presented method was based on the fact that OTCH could immensely enhance the CL of the reaction of cerium sulfate and tris(2,2‐bipyridyl) ruthenium (II) in acidic medium. Under optimal experimental conditions, CL intensity was favorably linear for OTCH in the range 5.0 × 10^?7 to 5.0 × 10^?5 g/ml, with a detection limit of 1.5 × 10^?7 g/ml (S/N = 3). The relative standard detection was 4.76% for 5.0 × 10^?6 g/ml (n = 11). This method was successfully applied to the analysis of OTCH in milk and egg white samples. According to the results of the kinetic curves for OTCH in the Ru(bipy)₃²⁺–Ce(SO₄)₂ CL system, together with CL and ultraviolet (UV)–visible spectra, the possible mechanism of the CL reaction is discussed briefly.     

Nuclear fast red‐based colorimetric sensors for sensitive and selective detection of Ag ions

The reduction of nuclear fast red (NFR) stain by sodium tetrahydroboron was catalyzed in the presence of silver ions (Ag⁺). The fluorescence properties of reduced NFR differed from that of NFR. The product showed fluorescence emission at 480 nm with excitation at 369 nm. Furthermore, the fluorescence intensity of the mixture increased strongly in the presence of Ag⁺ and Britton–Robinson buffer at pH 4.78. There was a good linear relationship between increased fluorescence intensity (ΔI) and Ag⁺ concentration in the range 5.0 × 10^?9 to 5.0 × 10^?8 M. The correlation coefficient was 0.998, and the detection limit (3σ/k) was 1.5 × 10^?9 M. The colour of the reaction system changed with variation in Ag⁺ concentration over a wide range. Based on the colour change, a visual semiquantitative detection method for recognition and sensing of Ag⁺ was developed for the range 1.0 × 10^?8 to 5.0 × 10^?4 M, with an indicator that was visible to the naked eye. Therefore, a sensitive, simple method for determination of Ag⁺ was developed. Optimum conditions for Ag⁺ detection, the effect of other ions and the analytical application of Ag⁺ detection of synthesized sample were investigated.     

High quantum yield and well‐dispersed quantum dots luminescent composite through sodium carboxymethyl starch

It is a challenging task to prepare well‐dispersed and highly luminescent quantum dots (QDs) powder and a new strategy is reported in this article. Sodium carboxymethyl starch (CMS‐Na) was employed in this work to prepare the QDs–starch composite. Ultraviolet (UV) light shows that the blank starches had no fluorescence, while the QDs‐starches were highly luminescent. Scanning electron microscopy (SEM) observation shows that the QDs–starch composite has the typical particle morphology with the diameter around 200 nm. Energy dispersive X‐ray spectroscopy (EDX) results show that there are intensive tellurium (Te) and cadmium (Cd) element signals. Combined fluorescent lifetime and steady‐state spectrometer show that the QDs–starch quantum yields (QYs) increase when the QDs loading increases from 1 × 10^?6 mol/g to 2 × 10^?6 mol/g, but when the loadings further increase, the QYs decrease slightly. For the red colour (λ_em = 660 nm) QDs, the QYs can reach to as high as 28.2%, and for the other colour QDs they can also have the QYs above 22%. Time‐resolved photobleaching experiments show that the fluorescent QDs–starch composite has a half‐decay time of 40.23 s. These results indicate that the CMS‐Na is a promising QDs dispersant to obtain high QY QD composites.     

Two‐channel near‐infrared fluorescence Ag+ ion sensing of a new star‐shaped dendrimer

A new near‐infrared fluorescence sensor PDI‐PD for Ag⁺ ions was successfully prepared and its structure characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR and high‐resolution mass spectrometry; matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (HRMS MALDI‐TOF). The probe exhibited rapid, sensitive, and selective two‐channel fluorescence responses towards Ag⁺ ions and protons. The probe has a marked high binding affinity and high sensitivity for Ag⁺, with a detection limit of 1.4 × 10^?6 M. An approximately five‐fold enhanced core emission at 784 nm was attributed to fluorescence resonance energy transfer (FRET). The enhanced core emission of the probe with Ag⁺ ions based on photo‐induced electron transfer and FRET is discussed. In addition, the probe presented a visible colour change. All experimental results demonstrated that PDI‐PD is an efficient tool for the selective, sensitive and rapid detection of Ag⁺ ions and protons using two‐channel fluorescence responses.     

Sensitive and selective detection of Cu(II) ion: A new effective 1,8‐naphthalimide‐based fluorescence ‘turn off’ sensor

The present study reports the development of a new 1,8‐naphthalimide‐based fluorescent sensor V for monitoring Cu(II) ions. The sensor exhibited pH independence over a wide pH range 2.52–9.58, and indicated its possible use for monitoring Cu(II) ions in a competitive pH medium. The sensor also showed high selectivity and sensitivity towards the Cu(II) ions over other competitive metal ions in DMSO–HEPES buffer (v/v, 1:1; pH 7.4) with a fluorescence ‘turn off’ mode of 79.79% observed. A Job plot indicated the formation of a 1:1 binding mode of the sensor with Cu(II) ions. The association constant and detection limit were 1.14 × 10⁶ M^–1 and 4.67 × 10^–8 M, respectively. The fluorescence spectrum of the sensor was quenched due to the powerful paramagnetic nature of the Cu(II) ions. Potential application of this sensor was also demonstrated when determining Cu(II) ion levels in two different water samples.     

A new benzimidazole‐based selective and sensitive ‘on–off’ fluorescence chemosensor for Cu2+ ions and application in cellular bioimaging

Two new twinborn benzimidazole derivates ( L and A ), which bonded pyridine via the ester space on the opposite and adjacent positions of the benzene ring of benzimidazole respectively, were designed and synthesized. Compound L displayed fluorescence quenching response only towards copper(II) ions (Cu²⁺) in acetonitrile solution with high selectivity and sensitivity. However, compound A presented ‘on–off’ fluorescence response towards a wide range of metal ions to different degrees and did not have selectivity. Furthermore, compound L formed a 1:1 complex with Cu²⁺ and the binding constant between sensor L and Cu²⁺ was high at 6.02 × 10⁴ M^?1. Job's plot, mass spectra, IR spectra, ¹H‐NMR titration and density functional theory (DFT) calculations demonstrated the formation of a 1:1 complex between L and Cu²⁺. Chemosensor L displayed a low limit of detection (3.05 × 10^?6 M) and fast response time (15 s) to Cu²⁺. The Stern–Volmer analysis illustrated that the fluorescence quenching agreed with the static quenching mode. In addition, the obvious difference of L within HepG2 cells in the presence and absence of Cu²⁺ indicated L had the recognition capability for Cu²⁺ in living cells.     

A terbium‐sensitized spectrofluorimetric method for determination of catecholamines in a serum sample with micelle medium

A terbium‐sensitized spectrofluorimetric method has been developed for determination of catecholamines such as norepinephrine (NE), epinephrine (EP) and dopamine (DA), using sodium dodecyl benzene sulphonate (SDBS). Fluorescence sensitization of terbium ions (Tb³⁺) by complexation with catecholamines in the presence of SDBS was observed. The fluorescence intensities of the Tb³⁺–catecholamine complexes were highly enhanced by introducing SDBS with an emission maximum at 545 nm after excitation at 290 nm. The conditions for the complex formation of Tb³⁺–catecholamine were investigated systematically and optimized to determine catecholamines in a serum sample. Under the optimum conditions, the fluorescence intensities of the Tb³⁺–catecholamine complexes were increased linearly with the concentration of NE, EP and DA over the ranges 2.5 × 10^–10–1.0 × 10^–8, 2.5 × 10^–10–1.0 × 10^–8 and 2.5 × 10^–9–1.0 × 10^–7 g/mL with correlation coefficients of 0.999, 0.999 and 0.9996, respectively. The limits of detection (3δ) of NE, EP and DA were found to be 4.6 × 10^–11, 7.8 × 10^–11 and 8.38 × 10^–10 g/mL, respectively. Precision of the method was tested at the concentration level of 1.2 × 10^?7 g/mL for five replicate measurements of NE, EP and DA, giving relative standard deviations (RSDs) of 1.41%, 1.23% and 1.89%, respectively. The interaction mechanism of the Tb³⁺–catecholamine complexes system was investigated and presented with ultraviolet absorption spectra. The proposed method has been applied for the quantitative determination of NE, EP and DA in a spiked serum sample and a pharmaceutical preparation sample. Copyright © 2011 John Wiley & Sons, Ltd.     

DNA‐binding activity and cytotoxic and cell‐cycle arrest properties of some new coumarin derivatives: a multispectral and computational investigation

Coumarins are the most important class of natural compounds found widely in various plants. Many coumarin derivatives with different biological and pharmacological activities have been synthesized. In this study, the antiapoptotic and cytotoxic effects and DNA‐binding properties of some synthetic coumarin derivatives (4b, 4d, 4f, 4 g (DBP‐g), 4 h and 4j) against K562 cell lines were investigated using different techniques. MTT assay indicated that the DBP‐g compound was more active than other derivatives, with a IC₅₀ value of 55 μM, and therefore this compound was chosen for further investigation. Apoptosis induction was assessed using acridine orange/ethidium bromide double‐staining and cell‐cycle analysis. In addition, in vitro DNA‐binding studies were carried out using ultraviolet–visible light absorption and fluorescence spectroscopy, as well as viscosity measurement and molecular modelling studies. In vitro results indicated that DBP‐g interacted with DNA through a groove‐binding mode with a binding constant (K_b) of 1.17 × 10⁴ M^?1. In agreement with other experimental data, molecular docking studies showed that DBP‐g is a minor groove binder. Overall, it can be concluded that DBP‐g could be used as an effective and novel chemotherapeutic agent.     

Selective determination of human immunoglobulin G by flow‐injection chemiluminescence

A novel flow‐injection chemiluminescence method was developed for the selective determination of human immunoglobulin G (IgG) in the presence of thiomersal by changing the flow rates of peristaltic pump. The study was based on the independence and additivity of the CL signals of human IgG and thiomersal in the galangin–potassium permanganate–polyphosphoric acid system. In meantime, two equations relating to the concentrations of mixing solutions of human IgG and thiomersal vs the CL intensity were established and solved, on the basis of which the content of thiomersal included in samples was simultaneously determined too. The enhanced CL intensity was in proportion to concerntrations in the range 8.0 × 10^?7 to 8.0 × 10^?5 g/mL for human IgG and 1.0 × 10^?7 to 2.0 × 10^?6 g/mL for thiomersal with the detection limits of 5.0 × 10^?7 g/mL for human IgG and 6.0 × 10^?8 g/mL for thiomersal, respectively. The relative standard deviation for 1.0 × 10^?5 g/mL human IgG was 0.8% and for 2.0 × 10^?7 g/mL thiomersal it was 2.0% (n = 10). The proposed method was applied to determine three synthetic samples with recoveries of 91.5–109.5%. In addition, the possible chemiluminescence mechanisms are discussed as well. Copyright © 2010 John Wiley & Sons, Ltd.     

Flow‐injection determination of cysteine in pharmaceuticals based on luminol–persulphate chemiluminescence detection

A flow injection (FI) method is reported for the determination of l‐ cysteine, based on its enhancement on chemiluminescence (CL) emission of luminol oxidized by sodium persulphate in alkaline solution. The calibration graph was linear over the range 1.0 × 10^–9–5.0 × 10^–7 mol/L (r² = 0.9992), with relative standard deviations (RSDs) in the range 1.1–2.3% (n = 4). The limit of detection (3σ blank) was 5.0 × 10^–10 mol/L with a sample throughput of 120/h. The method was applied to pharmaceuticals and the results obtained were in reasonable agreement with the amount labelled. The proposed method was also applied to cysteine in synthetic amino acid mixtures. Calibration graphs of N‐acetylcysteine and glutathione over the range 1.0–50 × 10^–8 and 0.5–7.5 × 10^–7 mol/L were also established (r² = 0.998 and 0.9986) with RSDs in the range 1.0–2.0% (n = 4), and the limits of detection (3σ blank) were 5.0 × 10^–9 and 1.0 × 10^–8 mol/L, respectively. Copyright © 2008 John Wiley & Sons, Ltd.     

Rapid determination of gatifloxacin in biological samples and pharmaceutical products using europium‐sensitized fluorescence spectrophotometry

A europium‐sensitized fluorescence spectrophotometry method using an anionic surfactant, sodium dodecyl benzene sulphonate (SDBS), was developed for the determination of gatifloxacin (GFLX). The GFLX–Eu³⁺–SDBS system was studied and it was found that SDBS significantly enhanced the fluorescence intensity of the GFLX–Eu³⁺ complex (about 25‐fold). The optimal experimental conditions were determined as follows: excitation and emission wavelengths of 338 and 617 nm, pH 7.5, 3.0 × 10^–6 mol/L europium(III), and 5.0 × 10^–5 mol/L SDBS. The enhanced fluorescence intensity of the system (ΔI_f) showed a good linear relationship with the concentration of GFLX over the range 1.0 × 10^–8–8.0 × 10^–7 mol/L with a correlation coefficient of 0.9990. The detection limit (S:N = 3) was determined as 1.0 × 10^–9 mol/L. This method has been successfully applied for the determination of GFLX in pharmaceuticals and human urine/serum samples. Compared with most other methods reported, the rapid and simple procedure proposed here offered higher sensitivity, wider linear range and good stability. The luminescence mechanism of the system is also discussed in detail. Copyright © 2008 John Wiley & Sons, Ltd.     

The fluorescence enhancement of quercetin–nucleic acid system and the analytical application

Nucleic acid can greatly enhance the fluorescence intensity of quercetin in HMTA‐HCl (pH 5.5) buffer. The enhanced intensity is in proportion to the concentration of nucleic acids in the range 5.0 × 10^?9 to 1.0 × 10^?6 g/mL for fsDNA, 5.0 × 10^?9 to 7.0 × 10^?7 g/mL for ctDNA and 5.0 × 10^?9 to 1.0 × 10^?6 g/mL for yRNA, and their detection limits (S/N = 3) are 3.5 × 10^?9, 7.8 × 10^?10 and 2.6 × 10^?9 g/mL, respectively. In comparison with most reported fluorescent probes for the determination of nucleic acids, the proposed probe has higher sensitivity and lower toxicity. The interaction investigation indicates that quercetin binds with double‐strand DNA in groove binding mode, resulting in fluorescence enhancement of this system. Copyright © 2009 John Wiley & Sons, Ltd.     

Ultrafast liquid chromatographic analysis of erdosteine in human plasma based on fluorimetric detection and precolumn derivatization with 4‐bromomethyl‐7‐methoxycoumarin: Application to pharmacokinetic studies

In this study, a new analytical method for erdosteine (ERD) in plasma based on high‐performance liquid chromatography and a fluorimetric detector, is presented. Precolumn derivatization of ERD with 4‐bromomethyl‐7‐methoxy coumarin (BrMmC) and dibenzo‐18‐crown‐6‐ether as a reaction catalyst led to the production of a fluorescent compound. ERD was monitored by fluorescence with an excitation wavelength λ_ext. = 325 nm and emission wavelength λ_em. = 390 nm. Optimum reaction conditions were carefully studied and optimized. A chromatographic procedure was performed using a C18 column of 150 × 4.6 mm and 3 μm particle size and a mobile phase consisting of methanol:acetonitrile:water (30:30:40, v/v/v) under a flow rate of 0.5 ml min^?1. A calibration plot was established covering analyte concentration range 0.2–3.0 μg ml^?1; the detection limit was 0.015 μg ml^?1 and quantification limit was 0.05 μg ml^?1. Mean recovery was 87.33% and relative standard deviation was calculated to be less than 4.4%. The developed method was successfully used to determine pharmacokinetic preparations of ERD subsequent to administration of a 900 mg dose capsule to a healthy 40‐year‐old woman volunteer.     

Inactivation of Bacillus cereus by Na‐chlorophyllin‐based photosensitization on the surface of packaging

Aims: This study was focused on the possibility to inactivate food‐borne pathogen Bacillus cereus by Na‐chlorophyllin (Na‐Chl)‐based photosensitization in vitro and after attachment to the surface of packaging material. Methods and Results: Bacillus cereus in vitro or attached to the packaging was incubated with Na‐Chl (7·5 × 10^?8 to 7·5 × 10^?5 mol l^?1) for 2–60 min in phosphate buffer saline. Photosensitization was performed by illuminating cells under a light with a λ of 400 nm and an energy density of 20 mW cm^?2. The illumination time varied 0–5 min and subsequently the total energy dose was 0–6 J cm^?2. The results show that B. cereus vegetative cells in vitro or attached to the surface of packaging after incubation with 7·5 × 10^?7 mol l^?1 Na‐Chl and following illumination were inactivated by 7 log. The photoinactivation of B. cereus spores in vitro by 4 log required higher (7·5 × 10^?6 mol l^?1) Na‐Chl concentration. Decontamination of packaging material from attached spores by photosensitization reached 5 log at 7·5 × 10^?5 mol l^?1 Na‐Chl concentration. Comparative analysis of different packaging decontamination treatments indicates that washing with water can diminish pathogen population on the surface by <1 log, 100 ppm Na‐hypochlorite reduces the pathogens about 1·7 log and 200 ppm Na‐hypochlorite by 2·2 log. Meanwhile, Na‐Chl‐based photosensitization reduces bacteria on the surface by 4·2 orders of magnitude. Conclusions: Food‐borne pathogen B. cereus could be effectively inactivated (7 log) by Na‐Chl‐based photosensitization in vitro and on the surface of packaging material. Spores are more resistant than vegetative cells to photosensitization‐based inactivation. Comparison of different surface decontamination treatments indicates that Na‐Chl‐based photosensitization is much more effective antibacterial tool than washing with water or 200 ppm Na‐hypochlorite. Significance and Impact of the Study: Our data support the idea that Na‐Chl‐based photosensitization has great potential for future application as an environment‐friendly, nonthermal surface decontamination technique.     

Chemiluminescence method for the determination of piroxicam by the enhancement of the tris‐(4,7‐diphenyl‐1,10‐phenanthrolinedisulphonic acid) ruthenium(II) (RuBPS)–cerium(IV) system and its application

A simple, rapid chemiluminescence (CL) method was described for the determination of piroxicam, a commonly used analgesic agent drug. A strong CL signal was detected when cerium(IV) sulphate was injected into tris‐(4,7‐diphenyl‐1,10‐phenanthrolinedisulphonic acid) ruthenium(II) (RuBPS)–piroxicam solution. The CL signal was proportional to the concentration of piroxicam in the range 2.8 × 10^–8–1.2 × 10^–5 mol/L. The detection limit was 2 × 10^–8 mol/L and the relative standard deviation (RSD) was 3.7% (c = 7.0 × 10^–7 mol/L piroxicam; n = 11). The proposed method was applied to the determination of piroxicam in pharmaceutical preparations in capsules, spiked serum and urine samples with satisfactory results. Copyright © 2008 John Wiley & Sons, Ltd.