Determination Co2+ in vitamin B12 based on enhancement of 2-(4-substituted-phenyl)-4,5-di(2-furyl) imidazole and H2O2 chemiluminescence reaction

In this paper, three kinds of imidazole derivatives, 2-(4-methylphenyl)-4,5-di(2-furyl) imidazole (MDFI), 2-(4-nitrophenyl)-4,5-di(2-furyl) imidazole (NDFI), and 2-(4-tert-butylphenyl)-4,5-di(2-furyl) imidazole (t-BDFI) were synthesized. In an alkaline medium, the chemiluminescence (CL) reaction of imidazole derivatives with H₂O₂ has been investigated. It was also found that MDFI/H₂O₂ and t-BDFI/H₂O₂ systems gave strong CL. When Co²⁺ was added into the two CL systems, the CL intensity was remarkably enhanced. In the optimum conditions, the CL intensity is linearly related to the logarithm of concentration of Co²⁺. The linear ranges are 5 × 10⁻⁹–2.5 × 10⁻⁷ mol/L for MDFI/H₂O₂ system and 5 × 10⁻⁹–2.5 × 10⁻⁷ mol/L for t-BDFI/H₂O₂ system, and the corresponding detection limits are 1.2 × 10⁻⁹ mol/L and 1.1 × 10⁻⁹ mol/L, respectively. The method was applied to the determination of Co²⁺ in vitamin B₁₂ injection. Furthermore, the CL mechanism was also discussed.     

A Chemiluminescence Microarray Based on Catalysis by CeO2 Nanoparticles and Its Application to Determine the Rate of Removal of Hydrogen Peroxide by Human Erythrocytes

In this work, cerium oxide nanoparticles are capable of strongly enhancing the chemiluminescence (CL) of the luminol–hydrogen peroxide (H₂O₂) system. Based on this, a microarray CL method for the determination of the removal rate constant of H₂O₂ by human erythrocytes has been developed. It is providing direct evidence for a H₂O₂-removing enzyme in human erythrocytes that acts as the predominant catalyst. A reaction mechanism is discussed. The proposed microarray CL method is sensitive, selective, simple and time-saving, and has good reproducibility and high throughput. Relative CL intensity is linearly related to the concentration of H₂O₂ in the range from 0.01 to 50 μM. The limit of detection is as low as 6.5?×?10^?11 M (3σ), and the relative standard deviation is 2. 1 % at 1 μM levels of H₂O₂ (for n?=?11).     

Enhancement of peroxyoxalate chemiluminescence intensity by surfactants and its application to detect detergent

Enhancement of peroxyoxalate chemiluminescence (PO-CL) intensity by a surfactant in the H₂O₂/bis(2,4,6-trichlorophenyl)oxalate (TCPO)/rhodamine B system was described. The effects of 15 surfactants were evaluated by comparing the ratio of a relative CL intensity (RCI) with surfactant to that of the blank in each system. In preliminary study, H₂O₂/imidazole-HNO₃ buffer/TCPO/rhodamine B system was used to study the effects of surfactants on PO-CL intensity. Fourteen surfactants reduced the CL intensity at the 2% concentration, where their relative CL intensities ranged from 0.6 to 93.5%. Some of these phenomena may be caused by a notable change of pH that was occurred by adding the surfactant.Additionally, enhancement of PO-CL intensity was studied by using system (1) H₂O₂/TCPO/rhodamine B and (2) H₂O₂/imidazole-HNO₃ buffer/TCPO/systems. In the system 1, the favorable enhancement of CL intensity (ranged from 124 to 472%) was observed with 9 surfactants at the 0.5% concentration. This result suggested that several surfactants might play a role as a catalyst in the PO-CL reaction. There was no tendency to enhance CL intensity among the surfactant types. In the system 2, the enhancement of CL intensity was also observed by adding with 11 surfactants, which might be mainly caused by the fluorescent impurities of surfactants used.Furthermore, detection of detergent commercially available was applied by using the system 1.     

Strong enhancement of the chemiluminescence of the Cu(II)-H<Subscript>2</Subscript>O<Subscript>2</Subscript> system on addition of carbon nitride quantum dots,and its application to the detection of H<Subscript>2</Subscript>O<Subscript>2</Subscript> and glucose

The authors report that carbon nitride quantum dots (CN QDs) exert a strong enhancing effect on the Cu(II)/H₂O₂ chemiluminescent system. Chemiluminescence (CL) intensity is enhanced by CN QDs by a factor of ~75, while other carbon nanomaterials have a much weaker effect. The possible mechanism of the effect was evaluated by recording fluorescence and CL spectra and by examining the effect of various radical scavengers. Emitting species was found to be excited-state CN QDs that produce green CL peaking at 515 nm. The new CL system was applied to the sensitive detection of H₂O₂ and glucose (via glucose oxidase-catalyzed formation of H₂O₂) with detection limits (3σ) of 10 nM for H₂O₂ and 100 nM for glucose. The probe was employed for glucose determination in human plasma samples with satisfactory results.

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Graphical abstract The effect of carbon nitride quantum dots (CN QDs) on Cu(II)-H₂O₂ chemiluminescence reaction was studied and the new CL system was applied for sensitive detection of glucose based on the glucose oxidase (GOx)-catalyzed formation of H₂O₂.

     

Multifunctional gold nanoparticles as signal transducers for fabrication of 1:2 molecular demultiplexer

A label-free and enzyme-free demultiplexer system for the fabrication of 1:2 molecular demultiplexer with luminol functionalized gold nanoparticles (Lum-AuNPs) as signal transducers was developed for the first time. The Lum-AuNPs had both chemiluminescence (CL) activity and surface plasmon resonance property. It was found that organothiols (RSH) could easily induce the aggregation of AuNPs via strong Au–S covalent interactions in the absence of hydrogen peroxide (H₂O₂), generating a red shift in the absorption band of AuNPs. However, the presence of H₂O₂ would readily oxidize RSH to disulfide (RS-SR), and the aggregation of Lum-AuNPs did not occur due to lack of the sulfhydryl group. Meanwhile, H₂O₂ could react with Lum-AuNPs, producing a strong CL emission owing to the enhancement effect of RSH on AuNPs-luminol-H₂O₂ CL system. Thus, RSH, H₂O₂, absorbance ratio, and CL intensity served as the signal input, address input, and two different signal outputs of the 1:2 molecular demultiplexer, respectively.     

Flow injection chemiluminescence determination of isoniazid using luminol and silver nanoparticles

The effect of silver colloidal nanoparticles (AgNPs) on the luminol–isoniazid system was investigated. It was found that AgNPs could act as a nanocatalyst on the luminol–isoniazid system to generate chemiluminescence (CL). The CL emission spectrum of the luminol–isoniazid–AgNPs system showed a peak with a maximum at 425 nm. It was suggested that the luminophor species was the excited state 3-aminophthalate. The reduction of dissolved O₂ to H₂O₂ by isoniazid and decomposition of H₂O₂ to the oxygen-related radicals were attributed to the catalytic effect of AgNPs. Under optimized conditions, the CL signal intensity was linear with the isoniazid concentration in the range of 10–1000 ng mL^{− 1}, with the correlation coefficient of 0.9996. The limit of detection was 2.7 ng mL^{− 1} isoniazid. The relative standard deviations for seven repeated measurements of 60 and 200 ng mL^{− 1} isoniazid were 1.4 and 2.4%, respectively. The effect of potent interfering compounds on the CL signal intensity of the proposed luminol–isoniazid–AgNPs system was investigated. The proposed method was successfully applied to the determination of isoniazid in a pharmaceutical sample.     

Determination of Four Active Oxygen Species Such as H2O2, •OH, •O2 −, and 1O2 by Luminol and CLA-Chemiluminescence Methods and Evaluation of Antioxidative Effects of Hydroxybenzoic Acids

Abstract

Simple and rapid chemiluminescence (CL) assays for H₂O₂, ?OH, ?O₂ ^? and ¹O₂ using 5-amino-2,3-dihydro-1,4-phthalazinedione (luminol) or 2-methyl-6-phenyl-3,7-dihydroimidazo[1,2-α]pyrazin-3-one (CLA) as CL reagents were developed. The means of the intra-assay relative standard deviations of ten replicate measurements of H₂O₂ (25-120 μM), ?OH generated from Fe(II) ion (2.5-10 μM) in the presence of 980 μM H₂O₂, ?O₂ ^? generated from hypoxanthine (HX) (7-50 μM) in the presence of 9 × 10^?3 units xanthine oxidase (XO) and ¹O₂ generated from NaOCl (3-12 mM) in the presence of 97.6 μM H₂O₂ were found to be 4.0%, 2.8%, 2.4% and 8.7%, respectively. To validate the proposed methods, the scavenging abilities of three standard antioxidative compounds, such as L-ascorbic acid, (±)-α-tocopherol and superoxide dismutase (SOD) were examined for four active oxygen species and compared with those by anelectron spin resonance (ESR) spin-trapping method. In addition, the CL methods were also applied to establish the relationships between the decrease of CL intensity and the structures as well as redox characters of syringic acid, 3-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid. From the obtained results, the scavenging effects to H₂O₂, ?OH, ?O₂ ^? and ¹O₂ of other dihydroxybenzoic acids were also evaluated.     

Efficient chemiluminescence by aptamer – reactant platform combination with activated Ag–Au alloy nanoparticles for cobalt detection

This article deals with the detection of Co(II) in real water sample using aptamer – reactant platform combination with activated Ag–Au alloy nanoparticles (NPs) by chemiluminescence (CL) method. CL is attributed to a catalytically enhanced decomposition of H₂O₂ by aptamer conjugated Ag–Au alloy NPs to produce reactive oxygen species. The Ag–Au alloy NPs were prepared by chemical method using double reducing agent (i.e. trisodium citrate and polyethylenimine) and used for detection of Co(II) from water by CL method. CL experiments were carried out with the variation of different parameters such as pH, concentration of luminol, concentration of H₂O₂ and Ag–Au alloy NPs. We found that Ag–Au alloy NPs have very good efficiency towards Co(II) detection. Analytical parameters and kinetics were studied in detail to know the nature and mechanism of CL in presence of aptamer conjugated Ag–Au alloy NPs. The linear range of the CL sensor of Co(II) is covered concentration from 0.01 to 10 µg/L with detection limit of 0.001 µg/L. The relative standard deviation for determination of Co(II) was 6.65 in 10 replicated measurements. CL method is first time applied to detect the Co(II) in real water samples at very low level using aptamer conjugated Ag–Au NPs as a catalyst.     

Platinum nanoparticle-catalyzed lucigenin–hydrazine chemiluminescence

It was found that lucigenin alkaline solution could react with hydrazine in the presence of Pt nanoparticles to generate strong chemiluminescence (CL) centered at 480 nm. In order to explore the CL mechanism, UV–visible spectra, X-ray photoelectron spectra studies before and after the CL reaction were carried out. The effects of O₂ and superoxide dismutase (SOD) on the CL reaction were examined. The catalytic effect of Pt NPs on the hydrazine–O₂ reaction was studied. A possible mechanism is proposed to be due to that Pt NPs catalyzed the reaction between hydrazine and the dissolved oxygen under alkaline conditions to yield hydroperoxide species and superoxide radical anion, which further oxidized lucigenin to produce CL emission. Moreover, the effects of some organic compounds containing hydroxyl (OH), carboxyl (COOH), carbonyl (CO), amino (NH₂), or sulfur groups on the lucigenin–hydrazine–Pt NPs CL system were tested. Thiol-containing compounds such as cysteine (Cys), glutathione (GSH), homocysteine (Hcy), and 6-mercaptopurine (6-MP) were observed to greatly enhance the CL intensity. It is suggested that the CL enhancement might be due to the fact that thiol-containing compounds could facilitate the electron transfer process under the catalysis of Pt nanoparticles and accelerate the generation of OH and O₂^? radicals, leading to the strong CL.     

Improved peroxidase mimetic activity of a mixture of WS<Subscript>2</Subscript> nanosheets and silver nanoclusters for chemiluminescent quantification of H<Subscript>2</Subscript>O<Subscript>2</Subscript> and glucose

It is reported that a mixture of WS₂ nanosheets (WS₂ NS) and silver nanoclusters (AgNCs) displays strongly enhanced peroxidase-mimicking activity. The catalytic effect of the mixture was studied by colorimetry, fluorometry, chemiluminescence (CL) and electrochemistry. The effect is interpreted in terms of a difference between the Fermi energy level of the two nanomaterials. This leads to the formation of charge separation regions which act as active sites for enzyme mimetic interaction with the substrates. The mixture of WS₂ NS and AgNCs was exploited for the non-enzymatic determination of H₂O₂ and glucose. A stopped-flow method was applied as a sensitive CL detection system using the bicarbonate-H₂O₂ reaction. The mixture has a powerful peroxidase mimicking activity on the bicarbonate-H₂O₂ CL reaction, and this effect is much larger than that of any single constituent. In addition, the CL emission is improved several times by using the stopped-flow technique. Under optimum condition, H₂O₂ can be determined in the 2.5–1500 nM concentration range. Moreover, glucose levels in human serum can be quantified via glucose oxidase based oxidation which leads to the generation of H₂O₂. Using this CL assay, a linear relationship was obtained between the intensity of the CL emission and glucose concentration in the range of 0.03–20 μM, with a limit of detection (3S) of 13 nM.

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Graphical abstract An enhanced peroxidase-like catalytic activity for WS₂ nanosheets (WS₂ NS) was revealed in the presence of silver nanoclusters (AgNCs), and was exploited for the non-enzymatic determination of H₂O₂, and of glucose (via glucose oxidase; GOx) using a stopped-flow CL method.

     

Ultrastrong Chemiluminescence Activity of Nanocarbon Materials after Ozonation and Their Effects on Different Chemiluminescent Systems

Ozonized nanocarbon materials with different dimensionalities, structures, and components exhibited significantly different chemiluminescence (CL) activities. The ozonation time and the weight ratio of hydroxyl carbon nanotubes (d≈8 nm, hyCNTs‐8) and graphene oxide (GO) strongly affected the CL activity of ozonized hybrids. Among GO, hyCNTs‐8, and GO/hyCNTs‐8, the GO/hyCNTs‐8 hybrids exhibited the strongest CL‐enhancing properties toward the luminol/H₂O₂ system, in contrast to previous reports. This study provides new understanding of the CL activity and CL‐enhancing properties of nanocarbon materials in signal‐enhanced analytical and biomedical fields.     

Determination of formaldehyde based on the enhancement of the chemiluminescence produced by CdTe quantum dots and hydrogen peroxide

Water-soluble cadmium telluride quantum dots (CdTe QDs) capped with glutathione (GSH) display chemiluminescence (CL) emission on reaction with hydrogen peroxide (H₂O₂) in strongly alkaline medium. It is found that the CL is strongly enhanced on addition of formaldehyde in aqueous solution. A flow injection system was developed, and it is shown that there is good linearity between CL intensity and the concentration of formaldehyde in the 0.06–3.0 μg L^?1 range. The limit of detection is as low as 10 ng L^?1. The method was successfully applied to the determination of formaldehyde in indoor air after adsorption into an aqueous phase. The recoveries for the real samples range from 97 % to 102.5 %, and the relative standard deviation is <3.8 % for intra- and inter-assay precision.

Detection of trace nitrite in waters using a QDs-based chemiluminescence analysis system

In the present work, a novel flow-injection chemiluminescence method based on CdTe quantum dots (QDs) was developed for the determination of nitrite. Weak chemiluminescence (CL) signals were observed from a CdTe QDs–H₂O₂ system under basic conditions. The addition of a trace amount of hemoglobin (Hb) caused the CL from the CdTe QDs–H₂O₂ system to increase substantially. In the presence of nitrite, the ferrous Hb reacted with the nitrate to form ferric Hb and NO. The NO then bound to ferrous Hb to generate iron nitrosyl Hb. As a result, the CL signal from the CdTe QDs–H₂O₂–Hb system was quenched. Thus, a flow-injection CL analytical system for the determination of trace nitrite was established. Under optimum conditions, there was a good linear relationship between CL intensity and the concentration of nitrite in the range 1.0?×?10^?9 to 8.0?×?10^?7 mol L^?1 (R ²?=?0.9957). The limit of detection for nitrite using this system was 3.0?×?10^?10 mol L^?1 (S/N?=?3). This method was successfully applied to detect nitrite in water samples.

Properties of Water-Soluble Porphyrin as a Sensitizer in Peroxyoxalate-Hydrogen Peroxide Chemiluminescence System and Its Application to the Quenching FluorometriC Determination of Copper(II)

ABSTRACT

Six kinds of water-soluble porphyrin were examined as a sensitizer (fluorophore) in the bis(2,4,6-trichlorophenyl)oxalate(TCPO)-hydrogen peroxide (H₂O₂) chemiluminescence(CL) system. Among them, coproporphyrin III showed the highest CL intensity. Moreover, the TCPO-H₂O₂-coproporphyrin III CL system was separately examined in each micelle solution using a non-ionic surfactant such as Briji 35 and Triton X-100, and an ionic surfactant such as cetyltrimethylammonium chloride(CTAC) and sodium dodecylsulfate. As a result, the CL intensity along with the coexistence of the CTAC micelle increased approximately 36 times compared to that in the absence of surfactant. Based on these findings, the quenching CL determination of copper(II) was established using the complex formation of coproporphyrin III and copper(II) ion. The calibration graph for the concentration of copper(II) was linear in the range of 2×10^?8M to 1×10^?6M, and the detection limit(3σ) was 1.26×10^?8M. Moreover, the relative standard deviation was 2.9%(10 determinations). The proposed method was applied to the determination of copper(II) ion in waste water and satisfactory results were obtained.     

Diimine ligand as a novel chemiluminescence enhancer of luminol-containing compounds

A series of diimine ligands (DLs) have been synthesized and evaluated for their non-enzymatic chemiluminescence (CL) enhancement of isoluminol or luminol-containing compounds. Of the DLs, N,N’-bis(m-hydroxylbenzylidene)propylenediamine (DL 10) was found to greatly enhance their CLs approximately 40 folds for isoluminol, 10 folds for luminol and 6 folds for a luminol-containing polymer. The CL enhancement of the compounds was observed in the presence of CH₃CN, H₂O₂, tetra-n-propylammonium hydroxide (TPA), and Fe (III) ion. The possible mechanism of this CL enhancement was discussed on the basis of the chelate formation of the ligand and the metal ions.     

Stopped-flow study of the enhanced chemiluminescence for the oxidation of luminol with hydrogen peroxide catalyzed by microperoxidase 8

The presence of carbonate or Tris causes a dramatic enhancement in the cheminluminescence (CL) for the oxidation of luminol with hydrogen peroxide catalyzed by microperoxidase 8 (MP8). A nearly constant enhancement in CL was observed over a wide range of H₂O₂ and luminol concentrations. The enhancement in CL is strongly pH-dependent, varying from 1.3 to 22.2 for carbonate and 1.6 to 10.2 for Tris. The CL enhancement is much more prominent at pH 9-10 than at high pH (>10.5) because of the extremely weak CL emission at pH below 10 when no enhancer is present. The CL enhancement is attributed to an accelerated CL cycle and the existence of alternative routes for luminol CL, possibly involving the carbonate, or Tris radicals. The dramatic enhancement in CL of the MP8-luminol-H₂O₂ system by the readily available reagents, sodium carbonate or Tris, will have general applications for sensitive CL assays. As an example, the presence of antioxidant results in a diminished and delayed CL emission, allowing the determination of its concentration at sub-micromolar level.     

A novel method for measuring initial-burst chemiluminescence in a liquid scintillation counter using the myeloperoxidase-H20Cl− reaction

These studies show that there is an initial quantifiable burst of luminol-enhanced CL associated with the interaction of MPO with H₂O₂ and Cl^?. They also confirm that the reaction is H₂O₂-concentration dependent (2). The novel method for quantifying initial-burst CL in a liquid scintillation counter introduced in this study provides many advantages over previous CL studies using the same counter, as noted above. This method provides for more efficient representation of CL associated with the MPO reaction, and allows for valid conclusions concerning the drug effects on this reaction. The ability to “see” the initial part of the reaction may also allow kinetic analysis of this (and other) enzyme CL reactions.     

Mechanistic Investigation of H2O2-dependent Chemiluminescence from Tetrabromo-1,4-Benzoquinone

As a H₂O₂-dependent bioluminescent substrate, tetrabromo-1,4-benzoquinone (TBBQ) was first isolated from acorn worm. The mechanism of chemiluminescence (CL) corresponding to the bioluminescence (BL) of acorn worm is largely unknown, let alone the mechanism of BL. In this article, we firstly studied the chemical and physical processes, and mechanism of H₂O₂-dependent CL from TBBQ by theoretical and experimental methods. The research results indicate: the CL process is initiated by a nucleophilic substitution reaction, which leads to the formation of an anionic dioxetane through five consecutive reactions; the anionic dioxetane decomposes to the first singlet excited state (S₁) via a conical interaction of the potential energy surfaces (PESs) between the ground (S₀) and S₁ state; the anionic S₁-state changes to its neutral form by a proton transfer from the solvent and this neutral product is assigned as the actual luminophore. Moreover, the experimental detection of CL, ^.OH and the identifications of 2,3-dibromo maleic acid and 2-bromo malonic acid as the major final products provide direct evidence of the theoretically suggested mechanism. Finally, this study proves that the activity of the H₂O₂-dependent CL from TBBQ is significantly lower than the one from tetrachloro-1,4-benzoquinone (TCBQ), which is caused by the weaker electron withdrawing effect and the stronger heavy atomic effect of bromine.     

Chemiluminescence behavior of sodium hydrogen carbonate in the potassium permanganate-hydrogen peroxide reaction

Chemiluminescence (CL) phenomenon of hydrogen peroxide with potassium permanganate in the presence of sodium hydrogen carbonate was reported. Effects of the surfactant on the CL system were investigated. Nonionic surfactants could effectively increase the CL signal. Radical scavengers and organic reagents such as nitro blue tetrazolium chloride (NBT), cytochrome c, sodium azide, ascorbic acid, thiourea, tert-butanol and dimethyl sulphoxide were used to study the emitting species. CL emission spectrum was recorded and the results showed that the maximal emission wavelengths of NaHCO₃-H₂O₂-KMnO₄ system were 440 and 634 nm. The mechanism was discussed based on electron spin resonance (ESR) spectra, fluorescence spectra and UV-vis absorption spectra. The addition of rhodamine B or uranine into this CL system enhanced the CL signal. It was due to part of the energy transfer from singlet oxygen and excited triplet dimers of two CO₂ molecules to rhodamine B or uranine. The CL could be induced by excited rhodamine B or uranine.     

Label‐Free,Non‐Derivatization CRET Detection Platform for 6‐Mercaptopurine Based on the Distance‐Dependent Optical Properties of Gold Nanoparticles

A label‐free, non‐derivatization chemiluminescence resonance energy transfer (CRET) detection platform has been developed for the detection of the non‐fluorescent small molecule 6‐mercaptopurine. This CRET process arose from a chemiluminescent (CL) donor–acceptor system in which the reaction of bis(2,4,6‐trichlorophenyl)oxalate (TCPO)–H₂O₂–fluorescein (maximum emission at 521.6 nm) served as the donor and gold nanoparticles (AuNPs, maximum absorption at 520.0 nm) served as the acceptor. This process caused a significant decrease in the CL signal of the TCPO–H₂O₂–fluorescein reaction. The presence of 6‐mercaptopurine induced an aggregation of AuNPs with the assistance of Cu²⁺ ions through cooperative metal–ligand interactions that was accompanied by a distinct change in color and optical properties. The maximum absorption band of the AuNPs was red‐shifted to 721.0 nm and no longer overlapped with the CL spectrum of the reaction; as a result, the CL signal was restored. This CRET system exhibited a wide linear range, from 9.0 nmol L^?1 to 18.0 μmol L^?1, and a low detection limit (0.62 nmol L^?1) for 6‐mercaptopurine. The applicability of the proposed CRET system was evaluated by analysis of 6‐mercaptopurine in spiked human plasma samples.