磷酸氯喹的流动注射逆胶束介导化学发光法测定

在酸性条件下,磷酸氯喹分子中氮原子被质子化后与阴离子AuCl4-形成离子缔合物,该缔合物被二氯甲烷带入鲁米诺的氯化十六烷基三甲基铵逆胶束中,离解出来的AuCl4-立即与鲁米诺产生化学发光.在一定的浓度范围内,发光强度与磷酸氯喹的含量呈线性关系,从而间接测定磷酸氯喹的含量.在优化的实验条件下,线性范围为0.001～15 mg/L,检出限(3σ)为0.02 μg/L,对1.0 mg/L的磷酸氯喹进行11次平行测定,RSD为1.6%.该法已成功用于片剂的分析.     

纳米金催化Luminol-AgNO_3化学发光体系测定盐酸阿米替林

碱性条件下,纳米金对Luminol-Ag NO3化学发光体系有增敏作用,盐酸阿米替林对该化学发光体系有显著的增敏作用。基于此,在优化化学发光反应条件的基础上,提出了测定盐酸阿米替林的新方法,并对其化学发光机理进行了探讨。该法测定盐酸阿米替林的线性范围为3.0×10-9~3.0×10-7g/m L,相关系数(r)为0.999 4,检出限(S/N=3)为2.1×10-9g/m L,相对标准偏差(RSD)为2.0%(n=11,ρ盐酸阿米替林=5.0×10-8g/m L)。该法已成功用于药物制剂中盐酸阿米替林含量的测定。     

马来酸噻吗洛尔的CTAC逆胶束介导化学发光法测定

在酸性条件下,马来酸噻吗洛尔分子中氮原子被质子化后与阴离子AuCl4-形成离子缔合物,该缔合物被三氯甲烷带入鲁米诺的氯化十六烷基三甲基铵(cetyltrimethylammonium chlorine,CTAC)逆胶束中(三氯甲烷-环己烷(体积比3∶7)-H2O(0.3 mol.L-1Na2CO3缓冲溶液,pH11.5)),离解出来的AuCl4-立即与鲁米诺产生化学发光。在0.01~20 mg.L-1范围内,发光强度与马来酸噻吗洛尔的含量成线性关系,从而间接测定马来酸噻吗洛尔的含量。检出限(3δ)为0.5μg.L-1,对质量浓度为1.0 mg.L-1的马来酸噻吗洛尔进行11次平行测定,其RSD为1.8%。该法已成功用于片剂和滴眼液中马来酸噻吗洛尔的测定。     

逆胶束介导化学发光法测定甲氧氯普胺

在酸性条件下,甲氧氯普胺分子中氮原子被质子化后与阴离子AuCl4-形成离子缔合物,该缔合物被CH2Cl2带入鲁米诺的氯化十六烷基三甲基铵(Cetyltrimethylammonium Chlorine,CTAC)逆胶束中,离解出来的AuCl4-立即与鲁米诺产生化学发光。在一定浓度范围内,发光强度与甲氧氯普胺的质量浓度成线性关系,从而可间接测定甲氧氯普胺的含量。在优化的试验条件下,甲氧氯普胺的检测线性范围为0.001~10μg/mL,检出限(3σ)为0.05 ng/mL,对1.0μg/mL的甲氧氯普胺进行11次平行测定,其RSD为1.6%。该法已用于片剂、针剂和尿样中甲氧氯普胺的测定。     

逆胶束介导化学发光法测定烟酸占替诺

在酸性条件下,烟酸占替诺分子中氮原子被质子化后与阴离子AuCl-4形成离子缔合物,该缔合物被三氯甲烷带入鲁米诺的氯化十六烷基三甲基铵(CTAC)逆胶束中,离解出来的AuCl-4立即与鲁米诺产生化学发光. 在一定浓度范围内,发光强度与烟酸占替诺的含量呈线性关系. 在优化的试验条件下,烟酸占替诺的检测线性范围为0.01～15×10-6 g/mL,检出限(3σ)为0.4×10-9 g/mL,对浓度为1.0×10-6 g/mL的烟酸占替诺进行11次平行测定,其RSD为1.26%. 方法简单、灵敏,已成功用于针剂中烟酸占替诺的测定.     

流动注射微乳液化学发光法测定福尔可定

在酸性条件下,福尔可定分子中氮原子被质子化后与阴离子AuCl4-形成离子缔合物,该缔合物被CH2Cl2带入鲁米诺的氯化十六烷基三甲基铵反胶束微乳液中,离解出来的AuCl4-立即与鲁米诺产生化学发光。在一定浓度范围内,发光强度与福尔可定的质量浓度呈线性关系,从而间接测定福尔可定。线性范围为0.001~15μg/mL,检出限(3σ)为0.04 ng/mL,对1.0μg/mL的福尔可定进行11次平行测定,RSD为2.2%。已成功用于片剂与生物体液中福尔可定的测定。     

流动注射纳米微反应器化学发光法测定盐酸格拉司琼

在酸性条件下,盐酸格拉司琼分子中氮原子被质子化后与阴离子AuC-l4-形成离子缔合物,该缔合物被CH2Cl2带入鲁米诺的氯化十六烷基三甲基铵反胶束纳米微反应器中,离解出来的AuCl4-立即与鲁米诺产生化学发光。在一定浓度范围内,发光强度与盐酸格拉司琼的量成线性关系,从儿间接测定盐酸格拉司琼。在优化的试验条件下,线性范围为0.001~20μg/mL,检出限(3σ)为0.04 ng/mL,对1.0μg/mL的盐酸格拉司琼进行11次平行测定,RSD为1.4%。已用于片剂、针剂和生物体液中盐酸格拉司琼的测定。     

伯胺N1923和三苯基氧化膦萃取金(Ⅲ)的动力学Ⅱ:二元萃取剂体系萃取AuCl4-

用恒界面池法研究了伯胺N1923和三苯基氧化膦(TPPO)二元萃取剂体系从盐酸介质中萃取AuCl4-的动力学,提出了界面化学反应控制机理.认为在界面区域内同时进行着N1923、TPPO以及二者的缔合物萃取AuCl4-的三个平行反应.三者的共同作用使Au(Ⅲ)向有机相的传质较N1923或TPPO的一元萃取剂体系明显加速.文中对这种动力学加速现象和动力学协同效应以及它们与热力学协同萃取的关系进行了讨论.     

流动注射纳米微反应器化学发光法测定盐酸二氧丙嗪

在酸性条件下,盐酸二氧丙嗪分子中氮原子被质子化后与阴离子AuCl-4形成离子缔合物,缔合物又被二氯甲烷带入鲁米诺的氯化十六烷基三甲基铵反胶束纳米微反应器中,离解出的AuCl-4立即与鲁米诺产生化学发光.在一定浓度范围内,发光强度与盐酸二氧丙嗪的含量呈线性关系,可间接测定盐酸二氧丙嗪的含量.在HCI、AuCl-4、鲁米诺、碳酸钠分别为0.05 mol/L、20 mg/L、0.4×10-4mol/L和0/3 mol/L(pH=11.5),R([H2O]/[CTAC])值为11,泵速均为3.6 mL/min(单管),聚四氟乙烯管的内径为0.8 mm,进样体积为120 μL,e至流通池间的距离为8 cm,反应盘管的长度为120 mm,直径为2 mm,负高压为-650 V,二氯甲烷为萃取剂的条件下.线性范围为0.001-20 mg/L,检出限(3σ)为0.06μg/L,对质量浓度为1.0 mg/L的盐酸二氧丙嗪进行11次平行测定,RSD为1.4％.方法可用于片剂和生物体液中盐酸二氧丙嗪的测定.     

流动注射微乳液化学发光法测定溴丙胺太林

在酸性条件下,溴丙胺太林(PB)分子中N原子被质子化后与阴离子AuCl-4形成离子缔合物,该缔合物被二氯甲烷带入鲁米诺的氯化十六烷基三甲基铵微乳液中,离解出来的AuCl-4立即与鲁米诺产生化学发光. 在一定浓度范围内,发光强度与溴丙胺太林的含量呈线性关系,从而间接测定溴丙胺太林的含量. 在优化的试验条件下,线性范围为0.001～10×10 -6 g/mL,检出限(3σ)为0.04×10 -9 g/mL,对浓度为1×10 -6 g/mL的溴丙胺太林进行11次平行测定,RSD为1.32%.     

乙酰胆碱和胆碱化学发光生物传感器的研究

将具有分子识别功能的乙酰胆碱酯酶和胆碱氧化酶及进行换能反应的luminol和Cu^2^+分别固定在多孔玻璃和离子交换剂的柱中,组成流动注射式胆碱和乙酰胆碱化学发光传感器,让传感器分子识别反应和换能反应在各自最佳pH值下进行。这一新型生物传感器优化了发光量子产率,避免了在传感元件上直接发光所产生的散射干扰。测定乙酰胆碱和胆碱的线性范围达到1～1000pmol,检测限为500fmol,每次测定时间为2min,寿命为6个月,已用于鼠脑及人血清中乙酰胆碱和胆碱的测定。     

Use of The Luminol Reaction for Metal Ion Detection in Liquid Chromatography

Abstract

The use of high performance liquid chromatography (HPLC) for the separation and quantitation of trace metals in solution has been hampered by the lack of A suitable detection system. The method generally used with classical metal ion separations - fraction collection and subsequent colorimetric detection - cannot easily be used in HPLC. To overcome this problem, A novel metal ion detection system based on the luminol reaction has been developed. Column effluent is successively mixed with luminol and then hydrogen peroxide before entering A chamber where chemiluminescence from the oxidation of the luminol is detected. The reaction is catalyzed by at least 20 different metal ions, and over A wide range the luminescence is proportional to metal ion concentration. The design of the system and some of its performance characteristics are described.     

A new chemiluminescence method for the determination of nickel ion

A new chemiluminescence (CL) phenomenon described as the second-chemiluminescence (SCL) was observed and a strong CL signal was detected, when Ni(II) ion was injected into the mixture after the end of the reaction of potassium permanganate with alkaline luminol. The possible CL mechanism is proposed based on the kinetic curve of the CL reaction, CL spectra, UV-vis spectra and some other experiments. A flow-injection analysis for the determination of nickle(II) ion has been developed, based on the catalysis of nickel(II) ion on the CL reaction between potassium manganate produced on-line and luminol under alkaline condition. Under the optimum conditions, the SCL intensity is linear with the concentration of nickel(II) ion in the range of 8.0-200.0 microg l-1 and 0.2-2.0 mg l-1. The R.S.D. was 4.5% for 11 determinations of 250 microg l-1 nickel(II) ion and the detection limit (3sigma) for nickel(II) ion was 0.33 microg l-1. The method was applied to determine nickel(II) ion in synthetic samples with satisfactory results.     

The Upper Limit of Luminol's Amphiprotism: The Crystal Structure of 5-Ammonium-2-hydro-1,4-phthalzinediol Sulfate(IV)

Luminol is chemically sufficiently stable to be diprotonated at high proton concentrations as provided by concentrated sulfuric acid. The luminol dication (5-ammonium-2-hydro-1,4-phthalzinediol) sulfate was isolated as macroscopic single crystals and its structure was determined and refined from single-crystal X-ray data collected at 173 K [cell parameters: a = 8.3994(17) Å, b = 6.9985(14) Å, c = 17.486(4) Å, β = 90.85(3)°, V = 1027.8(4) ų, space group P2₁/c]. The structure is comprised of layers stacked along the b axis. Intralayer interactions are accomplished by strong hydrogen bonds of three luminol dications to one central [SO₄]^2– ion. Interlayer interactions are formed by weak hydrogen bonds of one luminol dication to two [SO₄]^2– ions in the adjacent layers, respectively, and alternating sandwich and parallel-displaced π-π-stacking of the 1-hydropyridazine-3,6-diol moieties of luminol dications in adjacent layers, respectively.     

Catalytic behavior of tris(2,2'-bipyridine)iron(II) complex in chemiluminescence reaction of luminol in reversed micellar medium of cetyltrimethylammonium chloride

Tris(2,2'-bipyridine) complex of iron(II) was found to cause an increase in the chemiluminescence (CL) emission of luminol dispersed in the reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1:1 (v/v) dichloromethane-cyclohexane/water, when the iron(II) complex in dichloromethane was mixed directly with the reversed micellar solution containing luminol. Visible absorption measurements showed that, when dispersed in the CTAC reversed micellar medium, the iron(II) complex dissociates easily. In the reverse micelle, subsequently the free iron(II) ion produced may catalyze the CL oxidation of luminol even in the absence of hydrogen peroxide. The CL emission produced under the optimized experimental conditions was detectable at a minimum iron(II) concentration of 1.0 x 10(-9) M using a flow injection system.     

Luminol Chemiluminescence with Heteropoly Acids and its Application to the Determination of Arsenate,Germanate, Phosphate and Silicate by Ion Chromatography

A flow-injection chemiluminescence (CL) method has been proposed for sensitive determination of arsenate, germanate, phosphate and silicate, after separation by ion chromatography (IC). The post-column detection system involved formation of heteropoly acid in a H₂SO₄ medium before the CL reaction with luminol in an NaOH medium. For separation, heteropoly acid formation and the CL detection reaction, pH requirements were not compatible. When present as a heteropoly acid complex with molybdenum(VI), ger- manium(IV) and silicon(IV) caused CL emission from oxidation of luminol, and such a CL oxidation of luminol was observed analogously for arsenic(V) and phosphorus(V) but with the addition of metavanadate ion to the acid solution of molybdate. Good sensitivity for the three analytes arsenic(V), ger- manium(IV) and phosphorus(V) could be given by a single set of reagent conditions, chosen carefully. Another set was suitable for determining phosphorus(V) and silicon(IV). The minimum detectable concentrations of arsenic(V), germanium(IV), phosphorus(V) and silicon(IV) were 10, 50, 1 and 10 μg l⁻¹, respectively. Linear calibrations for arsenic(V), germanium(IV), phosphorus(V) and silicon(IV) were established over the respective concentration ranges of 10–1000, 50–25000, 1–1000 and 50–1 μg l⁻¹. The proposed IC–CL method was successfully applied to analyses of a seaweed reference material, rice wine and water samples.     

Effect of gold nanoparticle as a novel nanocatalyst on luminol-hydrazine chemiluminescence system and its analytical application

In this work the catalytic role of unsupported gold nanoparticles on the luminol–hydrazine reaction is investigated. Gold nanoparticles catalyze the reaction of hydrazine and dissolved oxygen to generate hydrogen peroxide and also catalyze the oxidation of luminol by the produced hydrogen peroxide. The result is an intense chemiluminescence (CL) due to the excited 3-aminophthalate anion. In the absence of gold nanoparticles no detectable CL was observed by the reaction of luminol and hydrazine unless an external oxidant is present in the system. The size effect of gold nanoparticles on the CL intensity was investigated. The most intensive CL signals were obtained with 15-nm gold nanoparticles. UV–vis spectra and transmission electron microscopy studies were used to investigate the CL mechanism. The luminol and hydroxide ion concentration, gold nanoparticles size and flow rate were optimized. The proposed method was successfully applied to the determination of hydrazine in boiler feed water samples. Between 0.1 and 30 μM of hydrazine could be determined with a detection limit of 30 nM.     

Inhibition of superoxide dismutase, Vitamin C and glutathione on chemiluminescence produced by luminol and the mixture of sulfite and bisulfite

In a system which consisted of luminol (3-aminophthalhydrazide), cobalt sulfate (CoSO4), alkaline buffer and the mixture of NaSO3 and sodium bisulfite (NaHSO3) (sulfite and bisulfite=3:1, m/m), a strong chemiluminescence (CL) was observed using a BPCL ultra-weak luminometer. The CL signals resulted from 3-aminophthalate (the product of oxidized luminol), and were affected by the buffer pH, buffer medium and the concentrations of luminol, CoSO4 and the NaSO3-NaHSO3 mixture. The observation that the CL intensities were inhibited by superoxide dismutase (SOD), Vitamin C (Vc) and glutathione (GSH) in a dose-dependent manner suggested that superoxide radical (O2*-) was involved in the CL reaction and responsible for oxidation of luminol.     

铂电极在碱性含氧溶液中的预还原处理对鲁米诺电 致化学发光的影响

研究了铂电极的不同预极化处理过程对碱性鲁米诺阳极电致化学发光(ECL)和阳极极化曲线的影响,发现在碱性含氧溶液中预还原处理的铂电极可增强0.22V(vs.SCE)处发光峰强度,且催化产生1.07V(vs.SCE)附近氧气析出过程并伴随产生明显的ECL发光峰;在酸性溶液中预处理电极可抑制这些活性。给出了催化氧气析出的可能作用机理：在碱性溶液中溶解氧还原生成了吸附在铂电极表面的(OH^-)~a~d~s,从而回忆了氧气的析出过程。同时给出了在碱性含氧溶液中预还原的铂电极上两个可能的ECL反应通道：(1)在0.22V鲁米诺阴离子氧化为鲁米诺自由基,然后与溶解氧反应而发光;(2)1.07V处析出的新鲜氧与鲁米诺阴离子反应而发光。     

Determination of chloride ion by electrochemiluminescence and investigation of the mechanism

The electrochemiluminescence (ECL) of luminol in aqueous alkaline solution was studied.Trace amounts of chloride showed significant effect on the efficiency of light emission of luminol as a posi-tive trigonometrical wave pulse was exerted on the solution. The detection limit for the chloride is5.0 ×10~(-6) mol/L and the linear calibration range extends up to 1.0 ×10~(-2) mol/L; the relative standarddeviation for 1.0 ×10~(-5) mol / L chloride is 5%. The influencing factors for chloride determination arealso discussed. The possible mechanism for the electrochemiluminescence reaction may be due to theoxidation of chloride ion in the solution to ClO~-, and the latter acts on luminol and then gives outluminescence. The method has been applied to determine the total chloride in tap water with satisfactoryresults.