荧光光谱与共振瑞利散射技术测定柔红霉素、美洛昔康和镉离子的新方法研究
发布时间：2018-08-01 14:27
【摘要】：本文主要应用荧光光谱与共振瑞利散射技术对柔红霉素、美洛昔康和镉离子进行测定。研究了它们与探针meso-四(4-磺基苯基)卟啉、乙酸双氧铀、邻菲罗啉和赤藓红之间的相互作用。文中还结合吸收光谱和量子化学计算来讨论其相互作用的机理,以此建立了测定柔红霉素、美洛昔康和镉离子的新方法,并将实验方法应用于实际样品的检测。主要研究内容如下： 1.以meso-四(4-磺基苯基)卟啉为探针荧光猝灭法和分光光度法测定柔红霉素 以合成的meso-四(4-磺基苯基)卟啉(TPPS4)为探针,提出了荧光和吸收光谱测定盐酸柔红霉素(DNR)的新方法。在pH4.6的邻苯二甲酸氢钾-NaOH缓冲溶液中,TPPS4与DNR通过静电引力和疏水作用力相互作用,形成1：1的结合产物,导致TPPS4的荧光猝灭和吸收光谱改变。在最大激发波长(λex)和最大发射波长(λem)(λex/λem=435nm/672nm)处检测体系的荧光强度,实验发现TPPS4的荧光猝灭值(AF)与DNR浓度在0.8～6.0mg·L-1呈良好的线性关系,检出限为27.0ng·mL-1。同时,体系的吸光度在433nm处逐渐减弱,而在420nm处出现新吸收峰,两处吸光度变化值(AA)均与DNR浓度在一定范围遵从比耳定律,摩尔吸光系数(ε)分别为ε433=7.75x104L·mol-1·cm-1(褪色法),ε420=5.19×104L·mol-1·cm-1(增色法),当采用双波长叠加法时,摩尔吸光系数可达1.29×105L·mol-1·cm-1。实验研究了荧光猝灭反应的适宜条件和影响因素,考察了共存物质的影响,表明方法具有较好的选择性,适用于血样和尿样中DNR的检测。文中通过吸收光谱、荧光光谱的变化,并结合荧光寿命的测量和量子化学计算,对TPPS4与DNR相互作用的机理、两者之间的作用力、复合物的组成与结构以及荧光猝灭的类型和吸收光谱、荧光光谱变化的原因进行了讨论。 2.荧光光谱法研究美洛昔康与乙酸双氧铀的相互作用及其分析应用 以乙酸双氧铀(UA)为探针,提出了荧光法测定美洛昔康(MLX)的新方法。在pH=7.2的Tris-HCl缓冲溶液中,MLX与UA激发态分子生成瞬时的激发态复合物,导致UA的荧光猝灭,并随着MLX浓度的增大,UA的荧光猝灭值(△F)与MLX浓度在0.02～7.5mg·L-1呈良好的线性关系,检出限为4.49ng-mL-1.实验研究了荧光猝灭反应的适宜条件和影响因素,考察了共存物质的影响,表明方法具有较好的选择性,可用于美洛昔康片剂与胶囊中美洛昔康含量的测定。文中通过对吸收光谱、猝灭常数Kq以及温度对荧光猝灭作用影响的讨论,表明美洛昔康对乙酸双氧铀的荧光猝灭为动态猝灭。 3.邻菲罗啉荧光增强法测定镐 在pH5.5的BR缓冲溶液中,Cd(Ⅱ)与邻菲罗啉(phen)相互作用,导致反应体系的荧光增强,最大激发和最大发射波长分别为328nm和368nm.Cd(Ⅱ)浓度在0.4-21.0μg·mL-1范围内与体系荧光增强值(△F)呈良好的线性关系,检出限为138.9ng-mL-1.实验研究了荧光增强反应的适宜条件和影响因素,考察了共存物质的影响,表明方法具有较好的选择性,可用于环境水样中Cd(Ⅱ)含量的测定。 4.赤藓红-邻菲罗啉-镉(Ⅱ)三元配合物的吸收与共振瑞利散射光谱研究及其分析应用 在pH7.0-8.0的KH2PO4-Na2HPO4缓冲溶液中,Cd(Ⅱ)与邻菲罗啉(phen)形成稳定的阳离子螯合物,再进一步与赤藓红(Ery)阴离子通过静电引力和疏水作用力相互作用生成三元离子缔合物。该缔合反应能引起体系吸收光谱的变化,发生明显的褪色反应,且最大褪色波长位于528nm处。体系吸光度的减小值(△A)在一定范围内与Cd()浓度成正比,据此建立了测定镉离子的高灵敏度的分光光度法,摩尔吸光系数ε528=2.29x105L-mol-1·cm1,检出限为26.5ng-mL-1.此外,其还能引起散射光谱的改变。该反应体系在371nm与590nm波长处均出现共振瑞利散射(RRS)明显增强的现象,在640nm和350nm左右波长处出现二级散射(SOS)和倍频散射(FDS)。在实验最佳条件下,散射增强值(ΔIRRS、ΔISOS和ΔIFDS)均在一定范围内与Cd(Ⅱ)浓度成良好的线性关系。散射方法均具有较高的灵敏度,对Cd(Ⅱ)的检出限分别为1.27ng·mL-1(双波长叠加法)、1.39ng·mL-1(RRS,371nm)、4.03ng·mL-1(RRS,590nm)、5.92ng·mL-1(SOS)和14.7ng·mL-1(FDS),且都可用于环境中痕量Cd(Ⅱ)的测定。本实验研究了反应体系的RRS、SOS、FDS和吸收光谱特征与适宜的反应条件和影响因素,并以RRS法为例考察了方法的选择性。对于环境水样中的Cd(Ⅱ)含量的测定,回收率在93.0%～103.0%范围,相对标准偏差在2.5%～4.3%之间。测定结果与原子吸收分光光度法(AAS)对照,基本一致。
[Abstract]:The determination of daunorubicin, meloxicam and cadmium ions by fluorescence spectroscopy and Resonance Rayleigh scattering technique is mainly used to study their interaction with the probe meso- four (4- sulfonyl phenyl) porphyrin, uranyl acetate, phenanthroline and erythrin. The interaction of their interactions with the absorption spectrum and quantum chemical calculation is also discussed. In this way, a new method for the determination of daunorubicin, meloxicam and cadmium ions was established, and the experimental method was applied to the detection of actual samples. The main contents are as follows:
1. fluorescence quenching and spectrophotometric determination of daunorubicin with meso- four (4- sulfonyl phenyl) porphyrin as probe
A new method for the determination of daunorubicin hydrochloride (DNR) by fluorescence and absorption spectroscopy was proposed with the synthesis of meso- four (4- sulfonphenyl) porphyrin (TPPS4). In pH4.6's Potassium phthalate -NaOH buffer solution, TPPS4 and DNR interact with the electrostatic force and hydrophobic forces to form a binding product of 1:1, resulting in the fluorescence quenching of TPPS4. The fluorescence intensity of the system was detected at the maximum excitation wavelength (lambda Ex) and the maximum emission wavelength (lambda EM) (lambda ex/ lambda em=435nm/672nm). The experimental results showed that the fluorescence quenching value of TPPS4 (AF) had a good linear relationship with the DNR concentration from 0.8 to 6.0mg. L-1, and the detection limit was 27.0ng. ML-1., and the absorbance of the system gradually weakened in the 433nm. A new absorption peak was found at 420nm, and the two absorbance change value (AA) followed the ear law in a certain range with the concentration of DNR. The molar absorption coefficient (epsilon) was epsilon 433=7.75x104L. Mol-1 cm-1 (Discoloration method), epsilon 420=5.19 x 104L. Mol-1 cm-1 (color adding method). When the double wavelength superposition method was used, the molar absorption coefficient could reach 1.29 x 105L. Mol-1. 1. the suitable conditions and influencing factors of fluorescence quenching reaction were studied and the influence of coexistent substances was investigated. The results showed that the method had good selectivity and was suitable for the detection of DNR in blood samples and urine samples. The interaction between TPPS4 and DNR was used by the absorption spectrum, the change of fluorescence spectrum, the measurement of fluorescence lifetime and the quantum chemical calculation. The mechanism, the interaction between the two, the composition and structure of the complex, the types of fluorescence quenching, the absorption spectra and the reasons for the fluorescence spectra changes were discussed.
2. fluorescence spectroscopy study of the interaction between meloxicam and uranyl acetate and Its Analytical Application
A new method for the determination of meloxicam (MLX) by fluorimetric method was proposed with UA as a probe. In the Tris-HCl buffer solution of pH=7.2, the transient excited state complex of MLX and UA excited states was produced, which resulted in the fluorescence quenching of UA. As the concentration of MLX increased, the fluorescence quenching value of UA (delta F) was in good condition with MLX concentration from 0.02 to 7.5mg. The optimum conditions and influencing factors of fluorescence quenching reaction were studied by 4.49ng-mL-1. test, and the effect of coexistent substances was investigated. The results showed that the method had good selectivity and could be used for the determination of meloxicam content in meloxicam tablets and capsules. The absorption spectrum, quenching constant Kq and temperature to fluorescein were used in this paper. The discussion of the effect of photoquenching shows that meloxicam is a dynamic quenching for the fluorescence quenching of uranyl acetate.
Determination of pickaxe by 3. ortho phenanthroline fluorescence enhancement
In the BR buffer solution of pH5.5, the interaction of Cd (II) with adjacent phenanthroline (phen) leads to the enhancement of the fluorescence of the reaction system. The maximum excitation and maximum emission wavelengths are 328nm and 368nm.Cd (II), respectively, in the 0.4-21.0 mu g / mL-1 range, which have a good linear relationship with the fluorescence enhancement value (delta F) of the system. The detection limit is a 138.9ng-mL-1. experimental study. The suitable conditions and influencing factors of the fluorescence enhanced reaction were studied, and the influence of the coexisting substances was investigated. The results showed that the method had good selectivity and could be used for the determination of Cd (II) content in environmental water samples.
Absorption and Resonance Rayleigh scattering spectra of 4. erythrin red phenanthroline cadmium (II) three complexes and their analytical applications
In the KH2PO4-Na2HPO4 buffer solution of pH7.0-8.0, Cd (II) forms a stable cation chelate with adjacent phenanthroline (phen), and further produces a three element ion association with the interaction of Ery anions through electrostatic and hydrophobic forces. The association reaction can cause changes in the absorption spectrum of the system, and a distinct fading reaction occurs. The maximum fading wavelength of the system is located at 528nm. The reduced value of the system absorbance (delta A) is proportional to the concentration of Cd () in a certain range. According to this, a high sensitivity spectrophotometric method for the determination of cadmium ions is established. The molar absorption coefficient is 528=2.29x105L-mol-1. CM1, the detection limit is 26.5ng-mL-1., which can also cause the change of the scattering spectrum. The resonance Rayleigh scattering (RRS) is obviously enhanced at the wavelength of 371nm and 590nm, and two stages of scattering (SOS) and frequency doubling scattering (FDS) appear at the wavelength of 640nm and 350nm. The scattering enhancement (delta IRRS, Delta ISOS and delta IFDS) is in a good linear relationship with Cd (II) concentration in a certain range of experimental conditions. The detection limits for Cd (II) are 1.27ng. ML-1 (double wavelength superposition), 1.39ng. ML-1 (RRS, 371nm), 4.03ng. ML-1 (RRS, 590nm), 5.92ng. The reaction conditions and influencing factors are suitable and the selectivity of the method is examined by the RRS method. The recovery rate of the Cd (II) content in the environmental water samples is from 93% to 103%, the relative standard deviation is between 2.5% and 4.3%. The results are compared with the atomic absorption spectrophotometry (AAS), basically the same.
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：O657.3;R927
本文编号：2157869
[Abstract]:The determination of daunorubicin, meloxicam and cadmium ions by fluorescence spectroscopy and Resonance Rayleigh scattering technique is mainly used to study their interaction with the probe meso- four (4- sulfonyl phenyl) porphyrin, uranyl acetate, phenanthroline and erythrin. The interaction of their interactions with the absorption spectrum and quantum chemical calculation is also discussed. In this way, a new method for the determination of daunorubicin, meloxicam and cadmium ions was established, and the experimental method was applied to the detection of actual samples. The main contents are as follows:
1. fluorescence quenching and spectrophotometric determination of daunorubicin with meso- four (4- sulfonyl phenyl) porphyrin as probe
A new method for the determination of daunorubicin hydrochloride (DNR) by fluorescence and absorption spectroscopy was proposed with the synthesis of meso- four (4- sulfonphenyl) porphyrin (TPPS4). In pH4.6's Potassium phthalate -NaOH buffer solution, TPPS4 and DNR interact with the electrostatic force and hydrophobic forces to form a binding product of 1:1, resulting in the fluorescence quenching of TPPS4. The fluorescence intensity of the system was detected at the maximum excitation wavelength (lambda Ex) and the maximum emission wavelength (lambda EM) (lambda ex/ lambda em=435nm/672nm). The experimental results showed that the fluorescence quenching value of TPPS4 (AF) had a good linear relationship with the DNR concentration from 0.8 to 6.0mg. L-1, and the detection limit was 27.0ng. ML-1., and the absorbance of the system gradually weakened in the 433nm. A new absorption peak was found at 420nm, and the two absorbance change value (AA) followed the ear law in a certain range with the concentration of DNR. The molar absorption coefficient (epsilon) was epsilon 433=7.75x104L. Mol-1 cm-1 (Discoloration method), epsilon 420=5.19 x 104L. Mol-1 cm-1 (color adding method). When the double wavelength superposition method was used, the molar absorption coefficient could reach 1.29 x 105L. Mol-1. 1. the suitable conditions and influencing factors of fluorescence quenching reaction were studied and the influence of coexistent substances was investigated. The results showed that the method had good selectivity and was suitable for the detection of DNR in blood samples and urine samples. The interaction between TPPS4 and DNR was used by the absorption spectrum, the change of fluorescence spectrum, the measurement of fluorescence lifetime and the quantum chemical calculation. The mechanism, the interaction between the two, the composition and structure of the complex, the types of fluorescence quenching, the absorption spectra and the reasons for the fluorescence spectra changes were discussed.
2. fluorescence spectroscopy study of the interaction between meloxicam and uranyl acetate and Its Analytical Application
A new method for the determination of meloxicam (MLX) by fluorimetric method was proposed with UA as a probe. In the Tris-HCl buffer solution of pH=7.2, the transient excited state complex of MLX and UA excited states was produced, which resulted in the fluorescence quenching of UA. As the concentration of MLX increased, the fluorescence quenching value of UA (delta F) was in good condition with MLX concentration from 0.02 to 7.5mg. The optimum conditions and influencing factors of fluorescence quenching reaction were studied by 4.49ng-mL-1. test, and the effect of coexistent substances was investigated. The results showed that the method had good selectivity and could be used for the determination of meloxicam content in meloxicam tablets and capsules. The absorption spectrum, quenching constant Kq and temperature to fluorescein were used in this paper. The discussion of the effect of photoquenching shows that meloxicam is a dynamic quenching for the fluorescence quenching of uranyl acetate.
Determination of pickaxe by 3. ortho phenanthroline fluorescence enhancement
In the BR buffer solution of pH5.5, the interaction of Cd (II) with adjacent phenanthroline (phen) leads to the enhancement of the fluorescence of the reaction system. The maximum excitation and maximum emission wavelengths are 328nm and 368nm.Cd (II), respectively, in the 0.4-21.0 mu g / mL-1 range, which have a good linear relationship with the fluorescence enhancement value (delta F) of the system. The detection limit is a 138.9ng-mL-1. experimental study. The suitable conditions and influencing factors of the fluorescence enhanced reaction were studied, and the influence of the coexisting substances was investigated. The results showed that the method had good selectivity and could be used for the determination of Cd (II) content in environmental water samples.
Absorption and Resonance Rayleigh scattering spectra of 4. erythrin red phenanthroline cadmium (II) three complexes and their analytical applications
In the KH2PO4-Na2HPO4 buffer solution of pH7.0-8.0, Cd (II) forms a stable cation chelate with adjacent phenanthroline (phen), and further produces a three element ion association with the interaction of Ery anions through electrostatic and hydrophobic forces. The association reaction can cause changes in the absorption spectrum of the system, and a distinct fading reaction occurs. The maximum fading wavelength of the system is located at 528nm. The reduced value of the system absorbance (delta A) is proportional to the concentration of Cd () in a certain range. According to this, a high sensitivity spectrophotometric method for the determination of cadmium ions is established. The molar absorption coefficient is 528=2.29x105L-mol-1. CM1, the detection limit is 26.5ng-mL-1., which can also cause the change of the scattering spectrum. The resonance Rayleigh scattering (RRS) is obviously enhanced at the wavelength of 371nm and 590nm, and two stages of scattering (SOS) and frequency doubling scattering (FDS) appear at the wavelength of 640nm and 350nm. The scattering enhancement (delta IRRS, Delta ISOS and delta IFDS) is in a good linear relationship with Cd (II) concentration in a certain range of experimental conditions. The detection limits for Cd (II) are 1.27ng. ML-1 (double wavelength superposition), 1.39ng. ML-1 (RRS, 371nm), 4.03ng. ML-1 (RRS, 590nm), 5.92ng. The reaction conditions and influencing factors are suitable and the selectivity of the method is examined by the RRS method. The recovery rate of the Cd (II) content in the environmental water samples is from 93% to 103%, the relative standard deviation is between 2.5% and 4.3%. The results are compared with the atomic absorption spectrophotometry (AAS), basically the same.
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：O657.3;R927
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