毛细管固定过氧化物酶流动注射化学发光法测定过氧化氢的研究

利用固定有辣根过氧化物酶的毛细管柱作为反应器与流通池,建立了一种简单、快速检测过氧化氢的流动注射化学发光分析新方法.当鲁米诺和过氧化氢的混合溶液流经反应器时,辣根过氧化物酶催化过氧化氢氧化鲁米诺产生化学发光.在选定的实验条件下,化学发光信号与过氧化氢的浓度在3.0×10-8～1.0×10-4mol/L范围内分段呈线性关系,检出限为1×10-8mol/L(S/N=3),相对标准偏差1.4%(1.0 μmol/L,n=9).该方法用于雨水中过氧化氢的测定,结果满意.     

鲁米诺化学发光分析法研究进展

从化学发光反应机理和应用进展两个方面对鲁米诺-过氧化氢、鲁米诺-铁氰化钾、鲁米诺-碘化物、鲁米诺-高锰酸钾和鲁米诺-溶解氧等化学发光体系进行了综述;指出鲁米诺化学发光体系是应用最为广泛的一类化学发光体系,同时对鲁米诺化学发光分析法的发展方向进行了展望.     

鲁米诺-H2O2体系化学发光对邻氯代苯亚甲基丙二腈和丙二腈的研究

基于鲁米诺-过氧化氢体系对邻氯代苯亚甲基丙二腈(CS)和丙二腈的化学发光的检测,考察了其反应动力学曲线,详细研究了pH值,鲁米诺浓度,过氧化氢浓度,本底信号的稳定性对化学发光强度的影响.CS的检测线性范围为10-2～10-5mol/L,绝对检测限为1.1ng(S/N=3/1).丙二腈的检测线性范围为10-3～10-6mol/L,绝对检测限为0.5ng(S/N=3/1).建立了鲁米诺-过氧化氢体系对液相化学发光对CS和丙二腈的分析方法,对CS的沙土样品进行测定,结果令人满意.     

流动注射化学发光法测定废水中Mn(Ⅱ)

鲁米诺与K2S2O8在碱性介质中能产生稳定的化学发光信号,Mn2+对鲁米诺过硫酸钾体系的化学发光产生微弱的抑制作用,而Ag+能增强Mn2+对发光体系的抑制作用,据此建立测定了废水中微量Mn2+的流动注射化学发光分析方法。Mn2+的浓度在1.0×10-10～1.0×10-7mol/L范围内与相对发光强度(ΔI)呈良好的线性关系,检出限为1.0×10-12mol/L;对1.0×10-7mol/LMn2+进行11次平行测定,其相对标准偏差RSD为1.3%。方法已用于测定废水中Mn2+的含量。     

Ag(Ⅲ)配合物-鲁米诺流动注射化学发光法测定西维因

在碱性条件下,Ag(Ⅲ)配合物可以氧化鲁米诺产生化学发光,西维因可以增强其发光强度,基于此结合流动注射建立了Ag (Ⅲ)配合物-鲁米诺化学发光体系测定西维因的方法。考察了鲁米诺、Ag(Ⅲ)配合物及NaOH浓度对发光强度的影响,在最佳实验条件下,西维因质量浓度在30～800 ng/L范围内与发光信号增加的强度成良好的线性关系,相关系数R=0.9954,检出限为2.72 ng/L。对质量浓度为50 ng/L的西维因平行测定9次,计算其相对标准偏差(RSD)为3.5%。     

银(Ⅲ)配合物-鲁米诺体系流动注射法测定醋酸泼尼松

在碱性环境下,银(Ⅲ)配合物可与鲁米诺产生化学发光,醋酸泼尼松对该发光体系具有显著的增敏作用,据此提出了流动注射银(Ⅲ)配合物-鲁米诺化学发光体系测定醋酸泼尼松含量的方法。优化的试验条件如下:1鲁米诺溶液中氢氧化钠的浓度为0.6mol·L-1;2鲁米诺溶液的浓度为8.0×10-7 mol·L-1;3银(Ⅲ)配合物溶液中氢氧化钠的浓度为1.7mol·L-1;4银(Ⅲ)配合物溶液的浓度为5.0×10-5 mol·L-1。醋酸泼尼松的线性范围为6.0×10-8~8.0×10-5 mol·L-1,方法的检出限(3s/k)为2.9×10-9 mol·L-1。对1.0×10-6 mol·L-1醋酸泼尼松标准溶液连续测定11次,测定值的相对标准偏差为2.9%。加标回收率在100%~105%之间。     

地塞米松磷酸钠的流动注射-化学发光分析法的研究

实验了地塞米松磷酸钠在K3Fe（CN）6-鲁米诺、KMnO4-鲁米诺、KIO4-鲁米诺、H2O2-鲁米诺体系中的化学发光现象。结果表明,地塞米松磷酸钠能够显著增强K3Fe（CN）6-鲁米诺体系和KMnO4-鲁米诺体系的化学发光强度,而在另外两个体系中没有增强作用。结合流动注射技术,分别在K3Fe（CN）6-鲁米诺体系和KMnO4-鲁米诺体系中建立了测定地塞米松的新方法。方法的线性范围分别为1.0×10^-7-1.0×10^-5g/mL和6.0×10^-8-1.0×10^-5g/mL,检出限分别为3.0×10^-8g/mL和2.0×10^-8g/mL,相对标准偏差分别为1.6%和1.9%（1.0×10^-6g/mL地塞米松,n=11）。此法已用于针剂和片剂样品的测定,结果与药典方法没有显著性差异。     

铜纳米簇催化鲁米诺化学发光体系的研究及应用

合成了牛血清白蛋白修饰的铜纳米簇(BSA-Cu NCs),研究发现在碱性环境中,BSA-Cu NCs对鲁米诺-过氧化氢体系的发光信号有很好的增强作用。对铜纳米簇催化鲁米诺-过氧化氢化学发光的机理进行了研究,并发现色氨酸对鲁米诺-过氧化氢-铜纳米簇化学发光体系信号具有增强作用,基于此,建立了化学发光测定色氨酸的含量的方法。该方法对色氨酸的检测限为6×10-8mol·L-1,线性范围为2.0×10-7~10-4mol·L-1。     

基于氧化石墨烯信号放大的化学发光法联合检测甲胎蛋白和癌胚抗原

提出了一种基于信号放大技术的流动注射化学发光免疫传感器, 用于联合检测人血清中甲胎蛋白(AFP)和癌胚抗原(CEA)的含量. 该传感器首先用表面接枝羧基的氧化石墨烯来吸附固定辣根过氧化物酶(HRP)标记的二抗, 制得信号放大型免疫探针. 然后用合成的磁性介孔材料Fe₃O₄/SiO₂来吸附固定AFP和CEA的单克隆抗体, 用磁铁将其吸附在两个检测池内壁. 当待检样品和信号放大型免疫探针陆续注射进入相应检测池, 发生夹心式免疫反应, 形成的免疫复合物被磁条吸附在检测池内壁. 随后加入鲁米诺和H₂O₂发光底物, 与酶标记物发生酶促增强的化学发光反应, 并通过控制设在两个管路上的开关来控制鲁米诺和H₂O₂的流通, 相继检测两个检测池中的化学发光信号, 从而实现两种待测物的同时检测.     

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.     

基于CoFe(Ⅲ)PBA/GO过氧化物模拟酶化学发光法检测H2O2和抗坏血酸

制备了一种具有过氧化物酶活性的类普鲁士蓝/氧化石墨烯复合纳米材料(CoFe(Ⅲ)PBA/GO)。将具有过氧化物酶活性的CoFe(Ⅲ)PBA/GO和化学发光法相结合,构建了一种用于检测H₂O₂和抗坏血酸(AA)的化学发光分析法。CoFe(Ⅲ)PBA/GO催化H₂O₂产生的O₂·^-,·OH,1O₂自由基氧化Luminol会产生很强的化学发光信号,通过检测化学发光强度可以实现对H₂O₂的检测。该方法检测H₂O₂的线性范围为0~0.8μmol/L,检测限为11 nmol/L。利用AA作为活性氧消除剂可以抑制化学发光反应的特点,实现了AA的检测。该方法测定AA的线性范围为0.02~0.8μmol/L,检测限为20 nmol/L。方法已应用于H₂O₂消毒水中H₂O₂和维生素C片中抗坏血酸的检测。     

利用H2O2-KI-鲁米诺体系化学发光法测定痕量钼

钼(Ⅵ)可以催化H₂O₂氧化I^-的反应,生成的I₂在碱性水溶液中能氧化鲁米诺而产生化学发光^[1],本文将这两个反应结合起来,建立了铝的化学发光分析法,方法有较高的灵敏度,检出限为6×10^-10g/cm³Mo,测定的相对标准偏差小于6%,工作曲线的线性范围是1×10^-9～1×10^-7g/cm³Mo,用EDTA作掩蔽剂,排除了大多数金属离子的干扰,方法有较好的选择性,应用此法对一些粮食样品中的痕量钼进行了测定,结果比较满意。     

Effect of pH on the characteristics of potassium permanganate–luminol CL reaction in the presence of trace aluminum(III) and its analytical application

At pHs ≥ 11.45, trace Al was found to enhance the CL from luminol–KMnO₄ system. However, at pHs ≤ 10.42, it was found to inhibit strongly the CL from luminol–KMnO₄ system. The effect of pH, luminol and potassium permanganate concentrations on the kinetic characteristics of CL system was investigated in the presence of trace Al. On this basis, a flow injection inhibition chemiluminescence method was established for the determination of trace Al in this study. Under optimized conditions, the CL decreased linearly with Al(III) concentration in the range of 8–500 μg L⁻¹ and the detection limit (3σ) of 2 μg L⁻¹. The relative standard deviation (R.S.D.) is 3.6% for 100 μg L⁻¹ Al(III) (n = 11). The method has been applied to the determination of trace Al in real water samples with satisfactory results without the pretreatment of samples. The results given by the proposed method are in good agreement with those given by ICP-AES detection method.     

Effect of complexones and tensides on selectivity of nitrogen dioxide determination in air with a chemiluminescence aerosol detector

Modification of the luminol solution by means of addition of various complexones and surfactants has been investigated to eliminate interferences from gaseous co-pollutants in the determination of ambient nitrogen dioxide using a chemiluminescence aerosol detector. The simultaneous presence of EDTA and triton X-100 or X-405 together with sulphite and iodide in the luminol solution suppressed interferences from ozone and peroxyacetyl nitrate to a negligible level and no scrubbers or corrections of the NO₂ measurements were needed.

In general, the best composition of the reagent solution included luminol, KOH, Na₂SO₃, KI, Na₂EDTA and triton X-100. From the point of view of selectivity of NO₂ determination, an optimum reagent solution consisted of luminol (0.002 M), KOH (0.5 M), Na₂SO₃ (0.2 M), KI (0.1 M), Na₂EDTA (0.05 M) and triton X-100 (0.5 vol.%). Interferences from ozone (170 ppb (v/v)) and peroxyacetyl nitrate (81 ppb (v/v)) were 0.2 and 1.2%, respectively, for nitrogen dioxide at a concentration of 50 ppb (v/v) and 0.25 and 1.7%, respectively, for 0.5 ppb (v/v) NO₂. The calibration graph was linear for NO₂ concentrations ranging from 3 to 665 ppb (v/v). Below 3 ppb (v/v) NO₂ the detector response to nitrogen dioxide can be fitted with a linear equation of the third order.     

A system consisted of flame ionization detector and sulfur chemiluminescence detector for interference free determination of total sulfur in natural gas

A new detection system consisted of a flame ionization detector (FID) and a sulfur chemiluminescence detector (SCD) was developed for sensitive and interference free determination of total sulfur in natural gas by non-separation gas chromatography. In this system, sulfur containing compounds and hydrocarbons were firstly burned in the FID using oxygen rich flame and converted to SO₂, CO₂ and H₂O, respectively. The products from FID were transported into the SCD with hydrogen rich atmosphere wherein only SO₂ could be reduced to SO and reacted with O₃ to produce characteristic chemiluminescence. Therefore, the chemiluminescence of CO found in conventional SCD were eliminated because CO₂ could not be reduced to CO under these conditions. The experimental parameters were systematically investigated. Limit of detection obtained by the proposed system is better than 0.5 μmol/mol for total sulfur and superior to those previously reported. The proposed method not only retains the advantages of the conventional SCD but also provides several unique advantages including no hydrocarbon interference, better stability, and easier calculation. The utility of this technique was demonstrated by the determination of total sulfur in real samples and two certified reference materials (GBW 06332 and GBW (E) 061320).     

Chemiluminescent determination of pyridoxine hydrochloride in pharmaceutical samples using flow injection

A chemiluminescent method using flow injection is described for the determination of pyridoxine hydrochloride. Its detection limit, linearity and reproducibility were examined. The method is based on the enhancing effect of pyridoxine hydrochloride on the chemiluminescence generated by the oxidation of luminol with hydrogen peroxide in aqueous potassium hydroxide and sodium oxalate. The proposed method is simple and inexpensive. The chemiluminescence intensity is a linear function of pyridoxine hydrochloride concentration over the range 10–250 μg ml⁻¹ with a detection limit of 6 μg ml⁻¹. The applicability of the method was demonstrated by the determination of pyridoxine hydrochloride in different tablet formulations and some dietary sources.     

Development of a luminol-based chemiluminescence flow-injection method for the determination of dichlorvos pesticide

A simple, fast chemiluminescence (CL) flow-injection method based on the reaction of luminol with H₂O₂ in the presence of a cationic surfactant (cyltrimethylammonium bromide, CTMAB) has been described for the direct determination of dichlorvos pesticide (DDVP). Under the optimal conditions, the CL intensity was linear to the DDVP concentration in the range of 0.02–3.1 μg ml⁻¹ (r=0.9998, n=10). The relative standard deviation was 3.4% at 0.35 μg ml⁻¹ (n=10), with a detection limit (3σ) of 0.008 μg ml⁻¹ DDVP. The possible reaction mechanism was also discussed. This method has been successfully applied to the determination of trace DDVP residue in vegetable sample and results have been compared with that of the UV method.     

纳米银增敏化学发光体系测定间苯二酚

采用柠檬酸钠包覆化学还原法制备纳米银粒子,将该纳米银粒子加入到碱性鲁米诺-铁氰化钾化学发光体系,体系的化学发光强度明显增强,而间苯二酚的加入能抑制该体系的化学发光,据此建立了流动注射化学发光法定量分析痕量间苯二酚的新方法.考察了鲁米诺、铁氰化钾、氢氧化钠以及纳米银浓度对化学发光体系的影响.在优化的实验条件下,该方法测定...     

Flow injection chemiluminescence detection and solvent extraction for human skin ointment dexamethasone acetate absorption analysis and the reaction mechanism study

A flow-injection chemiluminescence (CL) method coupled with solvent extraction for the determination of dexamethasone acetate (DA) in ointment was presented in this paper. It was based on the enhancing effect of the studied drug on CL emission of luminol–K₃Fe(CN)₆ system. This method has the advantages of simple sample treatment, cheap instrumentation and rapid detection. Under the optimum conditions, relative CL intensities were proportional to DA concentrations in the 0.044–4.4 μg ml⁻¹ range. The limit of detection was 0.01 μg ml⁻¹ (3σ) for DA. The method was applied to DA quantification in commercial DA ointment pharmaceutical and to human skin DA absorption analysis. Experiments were performed to evaluate the nature of DA enhanced luminol–K₃Fe(CN)₆ CL reaction. Based on the experimental results, it was suggested that in this CL system, DA was oxidized by K₃Fe(CN)₆ to form a medium product (DAox), DAox oxidized luminol with a faster kinetic step comparing with K₃Fe(CN)₆ oxidized luminol to an active form. As a result, DA speed the luminol CL reaction, and finally intensified the CL signal.     

A novel electrogenerated chemiluminescence sensor for pyrogallol with core-shell luminol-doped silica nanoparticles modified electrode by the self-assembled technique

The core-shell luminol-doped SiO₂ nanoparticles were synthesized and immobilized on the surface of chitosan film coating graphite electrode by the self-assembled technique. Then, a novel electrogenerated chemiluminescence (ECL) sensor for pyrogallol was developed based on its ECL enhancing effect for the core-shell luminol-doped silica nanoparticles. The ECL analytical performances and the sensing mechanism of this ECL sensor for pyrogallol were investigated in detail. The corresponding results showed that: compared with the conventional ECL reaction procedures by luminol ECL reaction system, the electrochemical (EC) reaction of pyrogallol and its subsequent chemiluminescence (CL) reaction occurred in the different spatial region whilst offering a high efficiency to couple the EC with the CL reaction to form the ECL procedures. In this case, this new sensing scheme offered more potential to improve the analytical performances of the ECL reaction. Under the optimum experimental conditions, this ECL sensor showed less than 5% decrease in continuums over 100 times ECL measurements, the detection limit was 1.0 × 1.0⁻⁹ mol/L for pyrogallol. The linear range extended from 3.0 × 10⁻⁹ mol/L to 2.0 × 10⁻⁵ mol/L for pyrogallol.