Gold nanoparticle-catalyzed luminol chemiluminescence and its analytical applications

Gold colloids with nanoparticles of different sizes were found to enhance the chemiluminescence (CL) of the luminol-H2O2 system, and the most intensive CL signals were obtained with 38-nm-diameter gold nanoparticles. UV-visible spectra, X-ray photoelectron spectra, and transmission electron microscopy studies were carried out before and after the CL reaction to investigate the CL enhancement mechanism. The CL enhancement by gold nanoparticles of the luminol-H2O2 system was supposed to originate from the catalysis of gold nanoparticles, which facilitated the radical generation and electron-transfer processes taking place on the surface of the gold nanoparticles. The effects of the reactant concentrations, the size of the gold nanoparticles. and some organic compounds were also investigated. Organic compounds containing OH, NH2, and SH groups were observed to inhibit the CL signal of the luminol-H2O2-gold colloids system, which made it applicable for the determination of such compounds.     

Trace analysis of phosphorus in water by sorption preconcentration and luminol chemiluminescence

A new, highly sensitive chemiluminescence method for the determination of sub-ppb quantities of phosphorus in water is described. The method is based on sorption preconcentration of phosphorus as a yellow vanadomolybdophosphoric heteropoly acid (HPA) in the presence or absence of a cationic surfactant on a paper filter, followed by direct chemiluminescence detection of the phosphorus concentrate via reaction with an alkaline luminol solution. The molar ratio of cationic surfactant to HPA in the ion associate sorbed on the filter is 4:1. The detection limits for phosphorus are 0.02 microgram of P L-1 in the presence of surfactant and 0.1 microgram of P L-1 in the absence of surfactant for a sample volume of 150 mL. The calibration plot is linear from 0.06 to 1.7 micrograms of P L-1 in the presence of a surfactant, and the time required for analysis is 25 min. In the absence of surfactant, the selectivities against Si4+ and As5+ are 5 and 40 times greater than those for the standard colorimetric method based on the formation of the blue molybdophosphoric HPA. Applications of the method to the analyses of river water, seawater, and the turbine vapor condensate from a coal-fired power plant are described. It is demonstrated that the sensitivity advantage of the chemiluminescence technique can be combined with the magnesium-induced coprecipitation (MAGIC) method for a more selective measurement of soluble reactive phosphorus.     

安息香-邻菲罗啉-铕三元配合物的合成及光致发光性能

合成了配体安息香(BZ)和新的铕配合物Eu(BZ)_3 phen,并用元素分析(EA)、IR、~1H-NMR和UV对配合物进行了表征;配合物Eu(BZ)_3 phen在波长310nm激发下,发出以铕的特征发射谱线612nm左右为主的强荧光,对应跃迁为~5D_0→~7F_2;安息香对铕离子具有敏化作用,是铕配合物的良好配体.     

Syntheses of photo-active lead(II)-1,10-phenanthroline materials

A facile synthetic technique for the formation of high-purity, stoichiometric 1:1 and 1:2 molecular ratio photo-active materials of lead(II) bromide and lead(II) iodide with 1,10-phenanthroline is described. The method results in the formation of analytically high-purity crystalline materials which are light-sensitive but air-stable. Elemental analyses and X-ray powder diffraction were used to characterize the materials.     

Treatment of 1,10-phenanthroline laboratory wastewater using the solar photo-Fenton process

The red Fe(2+)-phenanthroline complex is the basis of a classical spectrophotometric method for determination of iron. Due to the toxicity of this complexing agent, direct disposal of the wastewaters generated in analytical laboratories is not environmentally safe. This work evaluates the use of the solar photo-Fenton process for the treatment of laboratory wastewaters containing phenanthroline. Firstly, the degradation of phenanthroline in water was evaluated at two concentration levels (0.1 and 0.01%, w/v) and the efficiencies of degradation using ferrioxalate (FeOx) and ferric nitrate were compared. The 0.01% w/v solution presented much higher mineralization, achieving 82% after 30min of solar irradiation with both iron sources. The solar photo-Fenton treatment of laboratory wastewater containing, in addition to phenanthroline, other organic compounds such as herbicides and 4-chlorophenol, equivalent to 4,500mgL(-1) total organic carbon (TOC) resulted in total degradation of phenanthroline and 25% TOC removal after 150min, in the presence of either FeOx or ferric nitrate. A ratio of 1:10 dilution of the residue increased mineralization in the presence of ferrioxalate, achieving 38% TOC removal after 120min, while use of ferric nitrate resulted in only 6% mineralization over the same period.     

基于空间电荷限制电流法研究4,7-diphyenyl-1,10-phenanthroline的电子迁移率

在不同厚度条件下(50～300nm),运用空间电荷限制电流法,对4,7-diphyenyl-1,10-phenanthroline(BPhen)的电子迁移率进行了测量.当厚度处在体性质占有优势的情况下,迁移率的数值与运用飞跃时间法所测得的数值非常吻合.对于有机电致发光器件的典型厚度,Bphen的电子迁移率为2.8×10-4cm2/Vs,在厚度为50nm时小于3.4×10-4cm2/V s.300 nm时,电场强度为0.3mV/cm.较低的迁移率是由界面陷阱状态造成的.     

Positive potential operation of a cathodic electrogenerated chemiluminescence immunosensor based on luminol and graphene for cancer biomarker detection

In this work, we report a cathodic electrogenerated chemiluminescence (ECL) of luminol at a positive potential (ca. 0.05 V vs Ag/AgCl) with a strong light emission on the graphene-modified glass carbon electrode. The resulted graphene-modified electrode offers an excellent platform for high-performance biosensing applications. On the basis of the cathodic ECL signal of luminol on the graphene-modified electrode, an ECL sandwich immunosensor for sensitive detection of cancer biomarkers at low potential was developed with a multiple signal amplification strategy from functionalized graphene and gold nanorods multilabeled with glucose oxidase (GOx) and secondary antibody (Ab(2)). The functionalized graphene improved the electron transfer on the electrode interface and was employed to attach the primary antibody (Ab(1)) due to it large surface area. The gold nanorods were not only used as carriers of secondary antibody (Ab(2)) and GOx but also catalyzed the ECL reaction of luminol, which further amplified the ECL signal of luminol in the presence of glucose and oxygen. The as-proposed low-potential ECL immunosensor exhibited high sensitivity and specificity on the detection of prostate protein antigen (PSA), a biomarker of prostate cancer that was used as a model. A linear relationship between ECL signals and the concentrations of PSA was obtained in the range from 10 pg mL(-1) to 8 ng mL(-1). The detection limit of PSA was 8 pg mL(-1) (signal-to-noise ratio of 3). Moreover, the as-proposed low-potential ECL immunosensor exhibited excellent stability and reproducibility. The graphene-based ECL immunosensor accurately detected PSA concentration in 10 human serum samples from patients demonstrated by excellent correlations with standard chemiluminescence immunoassay. The results suggest that the as-proposed graphene ECL immunosensor will be promising in the point-of-care diagnostics application of clinical screening of cancer biomarkers.     

以对羟基苯甲酸和1,10菲哕啉为配体铜配合物的合成及与DNA的作用

通过元素分析、红外光谱、紫外光谱及差热热重分析,对合成的一种新型铜配合物Cu(phen) (DPA)0.5·3H2O(phen=1,10菲哕啉,DPA=对羟基苯甲酸)进行了结构表征,并以鲱鱼精DNA为靶点,采用光谱法、DNA粘度滴定实验和循环伏安法,研究了该配合物与DNA的键合方式.结果发现:在加入DNA后,配合物的吸收峰出现减色和红移,荧光强度增强;DNA的相对粘度随配合物的加入而增大;配合物在加入DNA后的氧化还原峰电流减小,式量电位发生正移.这些实验结果表明配合物与DNA通过嵌插方式发生作用.     

Initiation of luminol chemiluminescence by two-quantum excitation of U(IV) in aqueous solution

Results of experiments on initiation of luminol chemiluminescence by multiquantum excitation of U(IV) in aqueous solution by dye laser radiation in the visible range are reported.     

Effect of model ligands on iron redox speciation in natural waters using flow injection with luminol chemiluminescence detection

The effects of dissolved organic compounds on the determination of nanomolar concentrations of Fe(II) have been compared using two luminol-based flow injection chemiluminescence (FI-CL) methods. One used the direct injection of sample into the luminol reagent stream, and the other incorporated on-line solid-phase extraction of the analyte on an 8-hydroxyquinoline microcolumn. The CL signals from analyses of dissolved iron species (Fe(II) and Fe(III)) with model ligands and organic compounds were examined in high-purity water and seawater. The organic compounds included natural reducing agents (e.g., ascorbic acid), nitrogen sigma-donor/pi-acceptor compounds (e.g., 1,4-dipyridine, protoporphyrin IX), aromatic compounds (e.g., 1,4-dihydroxybenzene), synthetic iron chelators (e.g., EDTA), and natural iron binding compounds (e.g., desferrioxamine B, ferrichrome A). Fe(II) determinations for both luminol FI-CL methods were affected by submicromolar concentrations of redox-active compounds, strong iron binding ligands (i.e., log K(FeL) > 6), and compounds with electron-donating functional groups in both high-purity water and seawater. This was due to reactions between organic molecules and iron species before and during analysis, rather than chemiluminescence caused by the individual organic compounds. In addition, the effects of strong ligands and size speciation on Fe(II) recoveries from seawater following acidification (pH 2) and reduction (100 microM sodium sulfite) were investigated.     

Carbon dioxide capture and geological storage

Carbon dioxide capture and geological storage is a technology that could be used to reduce carbon dioxide emissions to the atmosphere from large industrial installations such as fossil fuel-fired power stations by 80-90%. It involves the capture of carbon dioxide at a large industrial plant, its transport to a geological storage site and its long-term isolation in a geological storage reservoir. The technology has aroused considerable interest because it can help reduce emissions from fossil fuels which are likely to remain the dominant source of primary energy for decades to come. The main issues for the technology are cost and its implications for financing new or retrofitted plants, and the security of underground storage.     

Development of a gas sensor utilizing chemiluminescence on nanosized titanium dioxide.

A gas-sensing mode based on chemiluminescence generated on the surface of nanosized materials is proposed in the present work. Seven nanosized materials were tested, and chemiluminescence was detected from six of them during the catalytic oxidation of organic vapors in air. The luminescence characteristics of ethanol and acetone vapors passing through the surface of TiO2 chosen were studied with a chemiluminescence-based detection system. The linear range of chemiluminescence intensity versus concentration of organic compounds is 40-400 microg/mL for ethanol and 20-200 microg/mL for acetone dissolved in water, respectively. X-ray powder diffraction and Raman spectrometry were used to investigate the changes in catalytic activity of TiO2 after a 60-h reaction at 380 degrees C. The results showed that the carbon deposited on the surface of TiO2, decreasing the catalytic activity, but can be removed in air by controlling the temperature at 500 degrees C for 3 h. Regenerability and no consumption of sensor substrate signify the long lifetime of the gas sensor.     

Carbon dioxide gas sensor based on ionic liquid-induced electrochemiluminescence

Electrochemiluminescence of the luminol-O(2) system in an electrolyte-free N,N-dimethylformamide (DMF)-dipropylamine (DPA) cosolution is induced by the formation of a carbamate ionic liquid (IL) from the reaction between CO(2) and DPA, on the basis of which a facile ECL sensor for measuring atmospheric CO(2) has been developed. This ECL sensing method shows several advantages in the detection of CO(2), such as high safety, high selectivity, wide linear response range, and good sensitivity. The gas sensor was found to have a linear response range from 100 ppm to 100 v/v% and a detection limit of 80 ppm (at signal-to-noise ratio of 3). This is the first reported IL-induced ECL sensor for a gas, thus the principle of this type of sensor and the IL-induced ECL mechanism have been demonstrated in detail.