高效液相色谱-化学发光法检测牛奶中磺胺类药物残留

以4种磺胺类药物(Sulfonamides, SAs), 即磺胺脒(Sulfaguanidine, SGD)、磺胺嘧啶(sulfadiazine, SDZ)、磺胺噻唑(sulfathiazole, STZ)和磺胺二甲嘧啶(Sulfamethazine,SMZ)为分析物,基于其在碱性介质中对Ag配合物-鲁米诺(Luminol)与Ni配合物鲁米诺两化学发光体系发光强度均具有抑制作用的性质,建立了高效液相色谱-化学发光法检测牛奶中4种磺胺类药物的方法.将化学发光体系作为高效液相色谱的新型检测器,并对两种化学发光体系的检测器性能进行了比较.4种磺胺药物经高效液相色谱分离后,分别与Ag-Luminol及Ni-Luminol化学发光体系作用.色谱条件为:反相C18分离柱(250 mm × 4.6 mm,5 μm);0.1%甲酸-甲醇为流动相(V/V);梯度洗脱;流速1 mL/min.化学发光条件:Ag、Ni-Luminol两体系中,Ag配合物浓度1.4×10.-4 mol/L(含0.12 mol/L NaOH);Ni配合物浓度1.5×10.-5 mol/L(含0.12 mol/L NaOH);Luminol浓度均为1.2×10.-7 mol/L;试剂流速均为1.0 mL/min.在最佳的分离检测条件下,Ag-Luminol体系检测4种磺胺类药物的检出限分别为0.15、0.96、1.10和1.50 μg/mL,加标回收率为81.0%~101.5%;Ni-Luminol体系检测SGD、SDZ、STZ 3种磺胺类药物的检出限分别为1.5、17.2和16.8 μg/mL,加标回收率为83.9%~110.8%.相比之下,Ag-Luminol体系作为高效液相色谱检测器更佳.应用本方法对牛奶中4种磺胺类药物残留量进行检测,结果令人满意.     

Flow injection determination of cyromazine in natural water samples using diperiodatoargentate(III)–H2SO4–chemiluminescence system

A simple and sensitive chemiluminescence (CL) procedure is proposed for the determination of cyromazine (CYR) using flow injection technique. CYR has strong enhancing effect on the CL reaction of diperiodatoargentate-(III) complex (DPA) in H₂SO₄ medium. The CL intensity with solid phase extraction (SPE) technique and with and without using online ion exchange resin column (IERC; OH-form) was proportional to the concentration of CYR over the range 0.1–200, 10–1000 and 2–2500 µg L^–1 (R² = 0.9974, 0.9980 and 0.9990, n = 7 each), respectively. Under the conditions, the limits of detection (S/N = 3) 0.029, 2.5 and 0.5 µg L^–1, relative standard deviations (n = 3) 1.9–3.6%, 1.4–2.7% and 1.0–3.0% and sample throughputs were 120, 80 and 120 h^–1. The effect of reagents concentration, flow rate, sample loop volume, photomultiplier voltage and IERC length was optimised. The mean results for natural water samples analysed by the proposed method were not significantly different at 95% confidence limit with the previously reported HPLC method. Interference from chloride ions could be eliminated by using SPE procedure or incorporating an in-line IERC. The CL mechanism of DPA–H₂SO₄–CYR system was also discussed briefly.     

A highly sensitive capillary electrophoresis immunoassay strategy based on dual‐labeled gold nanoparticles enhancing chemiluminescence for the detection of prostate‐specific antigen

An enzyme and antibody dual labeled gold nanoparticles enhancing chemiluminescence strategy was developed for highly sensitive CE immunoassay (IA) of prostate‐specific antigen (PSA). In this work, gold nanoparticles were labeled with horseradish peroxidase and antiprostate specific antigen‐antibody, and used as the marker (Ab^*). After PSA (antigen, Ag) was added into the system, a noncompetitive immune reaction was happen between Ab^* and Ag to form an immune complex (Ag–Ab^*). Subsequently, the obtained Ag–Ab^* and unreacted Ab^* were separated by CE, and the chemiluminescence intensity of Ag‐Ab^* was used to estimate PSA concentration. The calibration curve showed a good linearity in the range of 0.25–10 ng/mL. Based on a S/N of 3, the detection limit for PAS was estimated to be 0.092 ng/mL. Proposed CE method was applied for PSA quantification in human serum samples from healthy volunteers and patients with prostate cancer. The obtained results demonstrated that the proposed CE method may serve as an alternative tool for clinical analysis of PSA.     

Quenching effect of deferoxamine on free radical-mediated photon production in luminol and ortho-phenanthroline-dependent chemiluminescence

Removing excessive free radicals （FRs） by a synthetic chemical might give a clue for treatment of many iron-mediated diseases. Deferoxamine （DFO） can be one of the chemicals of choice for the clue. To investigate photoredox properties of DFO, its quenching effect on superoxide radical （O2°）, hydrogen peroxide （H202） and hydroxyl radical （OH~） was examined using luminol and ortho-phenanthroline （o- phen） chemiluminescence （CL） systems and UV-vis spectrophotometry. Stern-Volmer equation was also used for the CL kinetics. The observed quenching effect of DFO on CL]photon production in luminol and o-phen CL systems strongly confirmed the static arm of quenching properties of DFO on OH° and H2O2, but much less pronounced on O2^-°; the quenching property was maximal when iron was involved in the reaction systems. The Stern-Volmer plots in the designed photochemical reaction systems also confirmed a potent quenching effect of DFO on FR-mediated CL. Our study highlights strong photoreducing and antioxidant properties of DFO with huge quenching capacity on excessive FRs, and thus implies its promising prospects for therapeutic applications.     

A Simple,Selective and Sensitive Immunoassay for Determination of Human Chorionic Gonadotrophin Based on Chemiluminescence Resonance Energy Transfer

A simple, selective and sensitive immunoassay was developed for the determination of human chorionic gonadotrophin (HCG) based on the chemiluminescence resonance energy transfer (CRET). Two kinds of antibodies were used to form a sandwich‐type immunocomplex to ensure the selectivity of immunoassay. Based on the simple magnetic separation, amplification feature of gold nanoparticles and CRET phenomenon, this method could be used for highly sensitive determination of HCG without tedious washing steps. Under the optimized conditions, a linear range was obtained when the concentrations of HCG were changed from 0.15 to 5 mIU mL^?1 (R = 0.992). This immunoassay could be used for the determination of HCG in serum samples, which provided a promising potential in clinical diagnosis.     

Gold Nanoparticles‐enhanced Chemiluminescence Determination of Fenfluramine

A simple and sensitive chemiluminescence method was developed for the determination of fenfluramine. The chemiluminescence signal arising from the reaction between alkaline luminol and N‐bromosuccinimide was found to be greatly enhanced by fenfluramine in the presence of gold nanoparticles. But fenfluramine alone slightly inhibited the CL signal of N‐bromosuccinimide‐luminol in the absence of gold nanoparticles. The experimental parameters that affected the chemiluminescence signal were thoroughly investigated. Under the optimum experimental conditions, the enhanced chemiluminescence intensity was proportional to the concentration of fenfluramine in the range of 0.005‐1.0 mg/L. The detection limit was 0.9 μg/L fenfluramine with a relative standard deviation of 2.5% for 0.1 mg/L fenfluramine solution (n = 11). The method was applied to the determination of fenfluramine in some weight‐reducing tonics and in spiked human urine. A possible CL reaction mechanism was proposed.     

Chemiexcitation efficiency for the charge-transfer-induced chemiluminescent decomposition of 3-hydroxyphenyl-substituted dioxetanes in an aqueous system

The decomposition of 3-oxyphenyl-3-methoxy-4-(2′-spiroadamantane)-1,2-dioxetane (A) and 5-tert-butyl-4,4-dimethyl-1-(3-oxyphenyl)bicyclo[3.2.0]heptane (B) in NaOH/H₂O gives light in poor yield, which is several orders of magnitude lower than that in aprotic solvents. To understand the poor chemiluminescence efficiency in NaOH/H₂O, we investigated the behaviors of the authentic emitters, methyl 3-oxidobenzoate (C) and 2,2,4,4-tetramethyl-3-oxopentyl 3-oxidobenzoate (D). We found that D was weakly fluorescent though hydrolyzed in NaOH/H₂O, and estimated that the singlet-chemiexcitation efficiency Φ_S was 6.1 × 10⁻³ for the decomposition of B in NaOH/H₂O. On the other hand, Φ_S for A could not be estimated, since C was hydrolyzed too rapidly to observe its fluorescence.     

Sonoluminescence

Abstract

Sonoluminescence is the light emission phenomenon from collapsing bubbles in liquid irradiated by an ultrasonic wave. In the present review, theoretical and experimental studies of the two types of sonoluminescence [single‐bubble sonoluminescence (SBSL) and multibubble sonoluminescence (MBSL)] are described. SBSL is a sonoluminescence from a single stably pulsating bubble trapped at the pressure antinode of a standing ultrasonic wave. MBSL is a sonoluminescence occurring from many bubbles in liquid irradiated by an ultrasonic wave. The theoretical and experimental studies suggest that SBSL originates in emissions from plasma inside the heated bubble at the bubble collapse, whereas MBSL originates both in emissions from plasma and in chemiluminescence inside heated bubbles at the bubble collapse. Unsolved problems of sonoluminescence have also been explained in detail.     

化学发光抑制法测定抗坏血酸

利用抗坏血酸对DTMC H2 O2 化学发光体系的抑制作用 ,研究了对抗坏血酸进行间接测定的可能性。试验发现 ,化学发光猝灭率 (R)与抗坏血酸浓度在 1 0× 10 - 7～ 8 0× 10 - 6 mol·L- 1 范围内呈线性关系 ,检出限达到 8 0× 10 - 8mol·L- 1 (S N =3)。对 1 0× 10 - 6 mol·L- 1 抗坏血酸进行 10次平行测定 ,其化学发光强度猝灭率相对标准偏差为 4 6 %。该猝灭体系不需要额外的掩蔽剂 ,方法简单、选择性好 ,可直接应用于一些食品中微量抗坏血酸的测定。     

Development of a sampling and flow injection analysis technique for iron determination in the sea ice environment

A trace metal clean method for sampling and analysis of iron is set up and applied to sea ice and its associated snow, brine, and underlying seawater sampled during the Antarctic expedition “ARISE in the East” (Antarctic Remote Ice Sensing Experiment, AA03-V1, September-October 2003, 64-65°S/112-119°E, RV Aurora Australis). For clean sampling, a non-contaminating electropolished stainless steel ice corer is designed in conjunction with a polyethylene lathe equipped with Ti chisels to remove possibly contaminated outer layers of ice cores. A portable peristaltic pump with clean tubing is used on the ice to sample the underlying seawater (interface ice-water = 0, 1 and 30 m) and sea ice brine from access holes. Considering the extreme range of salinities (1-100) and Fe concentrations (0.1-100 nM) previously observed in similar environments, it is of paramount importance to set up a simple and sensitive Fe analyser adapted to such gradients. We use a flow injection analysis (FIA) technique and successfully demonstrate its capability to measure Fe concentrations directly in the sample without an on-line preconcentration/matrix separation step. We test the sensitivity, accuracy, precision and long-term stability of the analytical procedure. Also we explore and remediate interferences from a suite of other trace elements, such as Ni, Cd, Cr, Mn, Cu, Zn and Co. Analysis of reference materials NASS-5 and CASS-3 gives a good agreement with the certified values. Repeated measurements over a period of 5 months of an “in-house” Antarctic seawater standard yields a concentration of 1.02 ± 0.07 nM (n = 17, 1σ). The detection limit (3σ of the blank) is on average 0.12 nM. We report here results of the Fe distribution in sea ice that are in good agreement with previously published data. To our knowledge, this work provides the first complete profiles of total dissolvable and dissolved Fe in sea ice.