技术领域technical field
本发明属于荧光探针材料及其制备领域，特别涉及一种检测汞离子的反应型罗丹明类荧光探针及其制备方法与应用。The invention belongs to the field of fluorescent probe materials and preparation thereof, in particular to a reactive rhodamine-based fluorescent probe for detecting mercury ions, a preparation method and application thereof.
背景技术Background technique
汞是典型的有毒的过渡金属离子，可造成生物神经系统的永久性损伤。由于汞高的毒性而被广泛的关注，汞的产生主要来源于自然的和人为的原因，如海洋和火山的喷发，生活垃圾的焚烧和采矿，特别是节能荧光灯的使用造成汞污染的进一步加剧，尤其是环境中的汞在空气中被氧化成水溶性的二价汞离子，随着水流进入江河湖海中，经过水底微生物而变成甲基汞，存在于各种藻类中间，通过食物链在生物组织里高度富集，对自然界和人类具有较大的危害。Mercury is a typical toxic transition metal ion, which can cause permanent damage to the biological nervous system. Due to the high toxicity of mercury, it has been widely concerned. The production of mercury mainly comes from natural and man-made reasons, such as ocean and volcanic eruptions, domestic garbage incineration and mining, especially the use of energy-saving fluorescent lamps, which further aggravates mercury pollution. , especially the mercury in the environment is oxidized into water-soluble divalent mercury ions in the air, enters the rivers, lakes and seas with the water flow, and turns into methylmercury through underwater microorganisms, which exists among various algae and passes through the food chain in the biological Highly enriched in tissues, it has great harm to nature and human beings.
汞原子与生物体有很强的结合性(通常含有N，S，O元素)的能力，与生物分子形成配合物，能够引起酶的巯基、蛋白质结块等，破坏生物体分子结构。同时汞也是一种不可生物降解的重金属元素，汞元素及其化合物通过皮肤呼吸及食物链沉积在肝脏、大脑和其他器官中，在人体中无法正常代谢排出，产生慢性中毒，损害肠道、肾及神经系统，引起各种疾病。1953年在日本熊本县水俣镇发生的“水俣病”即是典型的汞公害病。重金属污染已成为目前环境污染检测中的重大污染源之一，因此发展可在水溶液环境中检测汞离子的快速、简单、灵敏的检测方法，对水体环境中重金属的检测具有重要意义。Mercury atoms have a strong ability to bind to organisms (usually containing N, S, O elements), and form complexes with biomolecules, which can cause sulfhydryl groups of enzymes and protein agglomeration, etc., and destroy the molecular structure of organisms. At the same time, mercury is also a non-biodegradable heavy metal element. Mercury and its compounds are deposited in the liver, brain and other organs through skin respiration and food chain, and cannot be metabolized and excreted normally in the human body, resulting in chronic poisoning and damage to the intestines, kidneys and Nervous system, causing various diseases. The "Minamata disease" that occurred in Minamata Town, Kumamoto Prefecture, Japan in 1953 is a typical mercury pollution disease. Heavy metal pollution has become one of the major pollution sources in the current environmental pollution detection. Therefore, the development of a fast, simple and sensitive detection method that can detect mercury ions in aqueous environment is of great significance to the detection of heavy metals in water environment.
目检测汞元素主要的方法：原子吸收光谱法、中子活化分析法、原子发射光谱法、X射线荧光光谱法、溶出伏安法、双硫腙比色法、涂层压电传感器发和等离子体感应光谱法等。由于上述方法的劣势(专业性强，步骤复杂，耗时，仪器贵重)，荧光化学传感器离子检测拥有众多的优点，它有望取代传统的方法，如测试速度快，设备简单，“裸眼”可视检测，价格低廉，分子结构易于修饰优化，灵敏度高等优点。近年来有许多关于小分子荧光探针法检测汞离子的报道(Sensors and Actuators B：Chemical，2015，210，519-532)，但是由于重金属离子固有的荧光猝灭性质，使得发展高灵敏度的荧光探针具有一定的挑战性。另外用于水体环境的荧光探针，不仅要保证水溶性良好，尤其应用于生物环境的荧光探针，不仅水溶性好，而且还要求在正常的生理环境条件下能够工作，有利于可见光激发而防止紫外光对细胞造成的损失。罗丹明B类荧光染料是一种很好的生物荧光物质，具有良好的光物理性质，其吸收和发射都在长波处(＞550nm)，荧光量子产率高，摩尔消光系数大，背景干扰小等优点，因此在发展荧光探针方面具有重要应用前景。The main methods for visual detection of mercury elements: atomic absorption spectrometry, neutron activation analysis, atomic emission spectrometry, X-ray fluorescence spectrometry, stripping voltammetry, dithizone colorimetry, coating piezoelectric sensor hair and plasma Somatosensory spectroscopy, etc. Due to the disadvantages of the above methods (high professionalism, complicated steps, time-consuming, and expensive instruments), fluorescent chemical sensor ion detection has many advantages, and it is expected to replace traditional methods, such as fast test speed, simple equipment, and "naked-eye" visualization Detection, low price, easy modification and optimization of molecular structure, high sensitivity and other advantages. In recent years, there have been many reports on the detection of mercury ions by small molecule fluorescent probes (Sensors and Actuators B: Chemical, 2015, 210, 519-532), but due to the inherent fluorescence quenching properties of heavy metal ions, the development of highly sensitive fluorescent Probes are somewhat challenging. In addition, the fluorescent probes used in the water environment must not only ensure good water solubility, especially the fluorescent probes used in the biological environment, not only have good water solubility, but also need to be able to work under normal physiological environmental conditions, which is conducive to visible light excitation. Prevents damage to cells caused by ultraviolet light. Rhodamine B fluorescent dye is a kind of good bioluminescent substance with good photophysical properties, its absorption and emission are at long wavelength (>550nm), high fluorescence quantum yield, large molar extinction coefficient, and small background interference etc., so it has important application prospects in the development of fluorescent probes.
中国专利201410058568.9“一种检测汞离子的反应型罗丹明荧光探针及其制备方法”，以罗丹明B和水合肼为原料合成罗丹明酰胺，然后和乙醛酸反应得到水溶性良好的产物，对汞离子具有高度的选择性，其它常用离子都无明显的干扰，可在pH＝5-10的环境中应用于生物荧光成像和水样的检测；中国专利201310163699.9“汞离子荧光传感器及其合成方法和应用”，以罗丹明B和水合肼为原料反应生成罗丹明·酰胺，然后加入异氰酸酯反应合成汞离子的荧光荧光传感器；中国专利201410029789.3“一种用于检测水环境中金属离子含量的有机化合物及其应用”，以N-[2-(N’N’-二(烷基巯乙基)氨基苯氧乙基]-N-烷基巯乙基-2-烷氧基苯胺作为离子络合体，适用于各种环境中金属离子浓度的连续检测，尤其对汞离子的检测。Chinese patent 201410058568.9 "A Reactive Rhodamine Fluorescent Probe for Detecting Mercury Ions and Its Preparation Method" uses rhodamine B and hydrazine hydrate as raw materials to synthesize rhodamine amide, and then reacts with glyoxylic acid to obtain a product with good water solubility. It is highly selective to mercury ions, and other common ions have no obvious interference, and can be used in bioluminescent imaging and water sample detection in an environment of pH=5-10; Chinese patent 201310163699.9 "mercury ion fluorescent sensor and its synthesis Method and application", using rhodamine B and hydrazine hydrate as raw materials to generate rhodamine amide, and then adding isocyanate to react to synthesize mercury ion fluorescent fluorescent sensor; Chinese patent 201410029789.3 "An organic Compounds and their applications", using N-[2-(N'N'-bis(alkylmercaptoethyl)aminophenoxyethyl]-N-alkylmercaptoethyl-2-alkoxyaniline as ion complex It is suitable for the continuous detection of metal ion concentration in various environments, especially for the detection of mercury ions.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种检测汞离子的荧光探针及其制备方法与应用，该荧光探针对汞离子有很好的选择性，在环境检测方面具有较好的使用效果。The technical problem to be solved by the present invention is to provide a fluorescent probe for detecting mercury ions and its preparation method and application. The fluorescent probe has good selectivity to mercury ions and has good application effect in environmental detection.
为了解决上述技术问题，本发明提供了一种检测汞离子的反应型罗丹明类荧光探针，其特征在于，其结构式为：In order to solve the above technical problems, the invention provides a reactive rhodamine fluorescent probe for detecting mercury ions, characterized in that its structural formula is:
上述的检测汞离子的反应型罗丹明类荧光探针的制备方法包括：The preparation method of the above-mentioned reactive rhodamine fluorescent probe for detecting mercury ions comprises:
步骤1：将2-溴甲基吡啶氢溴酸盐和叠氮化钠溶于溶剂中，搅拌反应3-4h，萃取，洗涤，干燥，旋蒸，即得产物4-(2-炔基丙氧基)苯甲醛；Step 1: Dissolve 2-bromomethylpyridine hydrobromide and sodium azide in a solvent, stir for 3-4 hours, extract, wash, dry, and rotary evaporate to obtain the product 4-(2-alkynyl propane Oxygen) benzaldehyde;
步骤2：将对羟基苯甲醛和溴丙炔以及催化剂溶于溶剂中，加热回流3-4h，冷却，萃取，干燥，旋蒸，真空干燥，即得2-叠氮甲基吡啶；Step 2: Dissolving p-hydroxybenzaldehyde, propyne bromide and catalyst in a solvent, heating to reflux for 3-4 hours, cooling, extracting, drying, rotary evaporation, and vacuum drying to obtain 2-azidopicoline;
步骤3：将4-(2-炔基丙氧基)苯甲醛和2-叠氮甲基吡啶，在氮气的保护下，溶于混合溶剂中，加入催化剂，搅拌反应20-24h，萃取，干燥，旋蒸，进行柱层析，即得产物R；Step 3: Dissolve 4-(2-alkynylpropoxy)benzaldehyde and 2-azidopicoline in a mixed solvent under the protection of nitrogen, add a catalyst, stir the reaction for 20-24h, extract and dry , rotary evaporation, and column chromatography to obtain the product R;
步骤4：将罗丹明B溶于溶剂中，加入水合肼，加热回流1-3h，冷却到室温，旋蒸，加入盐酸，调节pH，过滤，烘干，即得罗丹明酰胺；Step 4: Dissolve rhodamine B in a solvent, add hydrazine hydrate, heat and reflux for 1-3 hours, cool to room temperature, spin evaporate, add hydrochloric acid, adjust pH, filter, and dry to obtain rhodamine amide;
步骤5：将产物R和罗丹明酰胺溶于溶剂中，加入乙酸，加热回流反应5-6h，反应结束后，旋蒸，即得检测汞离子的反应型罗丹明类荧光探针(RHPT)。Step 5: Dissolve the product R and rhodamine amide in a solvent, add acetic acid, and heat to reflux for 5-6 hours. After the reaction, spin evaporate to obtain a reactive rhodamine-based fluorescent probe (RHPT) for detecting mercury ions.
优选地，所述的步骤1-4中的溶剂分别为N，N-二甲基甲酰胺、丙酮、叔丁醇和水的混合物、乙醇，步骤5中的溶剂为乙醇。Preferably, the solvents in step 1-4 are N,N-dimethylformamide, acetone, a mixture of tert-butanol and water, and ethanol, respectively, and the solvent in step 5 is ethanol.
优选地，所述的步骤1中的2-溴甲基吡啶氢溴酸盐和叠氮化钠的摩尔比为1∶2.5～3。Preferably, the molar ratio of 2-bromomethylpyridine hydrobromide to sodium azide in step 1 is 1:2.5-3.
优选地，所述的步骤1中的萃取为：在反应体系中加入水，用二氯甲烷萃取，步骤1中的溶剂、水和二氯甲烷的体积比为1∶0.2～0.5∶5～10。Preferably, the extraction in step 1 is: add water to the reaction system, extract with dichloromethane, the volume ratio of solvent, water and dichloromethane in step 1 is 1:0.2～0.5:5～10 .
优选地，所述的步骤2中催化剂为碳酸钾，对羟基苯甲醛、溴丙炔以及催化剂的摩尔比为1∶0.4～0.45∶0.4～0.45。Preferably, the catalyst in step 2 is potassium carbonate, and the molar ratio of p-hydroxybenzaldehyde, propyne bromide and the catalyst is 1:0.4-0.45:0.4-0.45.
优选地，所述的步骤2中的萃取为：在反应体系中加入水，用二氯甲烷萃取，步骤2中的溶剂、水和二氯甲烷的体积比为1∶0.2～0.3∶0.5～1。Preferably, the extraction in step 2 is: add water to the reaction system, extract with dichloromethane, the volume ratio of solvent, water and dichloromethane in step 2 is 1:0.2～0.3:0.5～1 .
优选地，所述的步骤3中的催化剂为CuSO4·5H2O和抗坏血酸钠，所述的4-(2-炔基丙氧基)苯甲醛、2-叠氮甲基吡啶、CuSO4·5H2O和抗坏血酸钠的摩尔比为1∶0.5～1∶0.5～0.8∶0.8～1。Preferably, the catalyst in step 3 is CuSO4 .5H2 O and sodium ascorbate, and the 4-(2-alkynylpropoxy)benzaldehyde, 2-azidomethylpyridine, CuSO4 . The molar ratio of 5H2 O and sodium ascorbate is 1:0.5-1:0.5-0.8:0.8-1.
优选地，所述的罗丹明B、水合肼和盐酸的摩尔比为1∶0.02～0.05∶0.03～0.05。Preferably, the molar ratio of rhodamine B, hydrazine hydrate and hydrochloric acid is 1:0.02-0.05:0.03-0.05.
优选地，所述的步骤4中的调节pH为使用氢氧化钠调节pH＝9.0-10.0。Preferably, the pH adjustment in step 4 is using sodium hydroxide to adjust pH=9.0-10.0.
优选地，所述的步骤5中产物R、罗丹明酰胺和乙酸的摩尔比为1∶0.8～1∶0.02～0.03。Preferably, the molar ratio of product R, rhodamine amide and acetic acid in step 5 is 1:0.8-1:0.02-0.03.
本发明还提供了上述的检测汞离子的反应型罗丹明类荧光探针的应用方法，其特征在于，包括：将不同浓度的汞离子的水溶液分别加入含有上述的检测汞离子的反应型罗丹明类荧光探针的pH＝4.0-12.0的H3PO4/H2PO4-的缓冲体系中，测定荧光强度，激发波长为560nm，发射波长为577-580nm，以汞离子的浓度为横坐标，荧光强度的变化为纵坐标作图，得到线性工作曲线；将含有汞离子的污水加入含有上述的检测汞离子的反应型罗丹明类荧光探针的pH＝4.0-12.0的H3PO4/H2PO4-的缓冲体系中，通过测定污水中的汞离子的荧光强度即可得到溶液中汞离子的含量。The present invention also provides the application method of the above-mentioned reactive rhodamine-based fluorescent probe for detecting mercury ions, which is characterized in that it includes: respectively adding aqueous solutions of different concentrations of mercury ions into the above-mentioned reactive rhodamine for detecting mercury ions In the buffer system of H3 PO4 /H2 PO4- with a pH=4.0-12.0 of the fluorescent probe, measure the fluorescence intensity, the excitation wavelength is 560nm, the emission wavelength is 577-580nm, and the concentration of mercury ions is taken as the abscissa , the change of the fluorescence intensity is plotted on the ordinate to obtain a linear working curve; the sewage containing mercury ions is added to the H 3 PO 4 /H3 PO4 / In the buffer system of H2 PO4- , the content of mercury ions in the solution can be obtained by measuring the fluorescence intensity of mercury ions in the sewage.
优选地，所述的H3PO4/H2PO4-的缓冲体系的pH＝7.0。Preferably, the pH of the H3 PO4 /H2 PO4- buffer system is 7.0.
本发明含有罗丹明B基的酰胺基团，中间含有碳氮双键和三唑吡啶的引入，其中的一些基团对汞离子具有识别作用。其机理在于：由于C＝N双键的异构化，加入离子后，分子的刚性改变和共轭性改变对于汞在荧光增强的同时颜色红移，颜色改变有利于提高探针的灵敏性。其制备路线如图7所示。本发明所述的新型荧光探针RHPT自身荧光很弱，在汞离子的条件下，经过560nm可见光激发，580nm处的荧光信号显著增强，通过记录荧光强度即可检测汞离子的浓度。荧光探针RHPT在pH＝7.0的缓冲溶液中对汞离子可进行高选择性检测。The invention contains the amide group of rhodamine B group, the middle contains carbon-nitrogen double bond and the introduction of triazolpyridine, and some of the groups have a recognition effect on mercury ions. The mechanism is: due to the isomerization of the C=N double bond, after the addition of ions, the rigidity and conjugation of the molecule change to red-shift the color of mercury while the fluorescence is enhanced, and the color change is conducive to improving the sensitivity of the probe. Its preparation route is shown in Figure 7. The autofluorescence of the novel fluorescent probe RHPT described in the present invention is very weak. Under the condition of mercury ions, the fluorescence signal at 580nm is significantly enhanced after being excited by 560nm visible light, and the concentration of mercury ions can be detected by recording the fluorescence intensity. The fluorescent probe RHPT can detect mercury ions with high selectivity in the buffer solution of pH=7.0.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
(1)本发明的荧光探针对汞离子有很好的选择性和灵敏度，在环境检测方面具有较好的使用效果。(1) The fluorescent probe of the present invention has good selectivity and sensitivity to mercury ions, and has good application effect in environmental detection.
(2)本发明虽然合成步骤比较多，但反应条件比较简单，设备要求简单易于操作，合成的荧光探针对汞离子具有较好的选择性和灵敏度。在溶液中加入汞离子前后颜色区别大，可进行现场实时定性及半定量的目视比色法检测。(2) Although the present invention has many synthesis steps, the reaction conditions are relatively simple, the equipment requirements are simple and easy to operate, and the synthesized fluorescent probe has good selectivity and sensitivity to mercury ions. The color difference between before and after adding mercury ions in the solution is large, and real-time qualitative and semi-quantitative visual colorimetric detection can be carried out on site.
附图说明Description of drawings
图1为荧光探针加入汞离子前后的紫外变化图谱；在图1中，横坐标为紫外吸收波长(nm)，纵坐标为吸光度。Fig. 1 is the ultraviolet change spectrum of fluorescent probe before and after adding mercury ion; In Fig. 1, the abscissa is the ultraviolet absorption wavelength (nm), and the ordinate is the absorbance.
图2a和2b分别为荧光探针加入汞离子前后的荧光变化图谱；在图2中，横坐标为荧光发射波长(nm)，纵坐标为荧光强度。Figures 2a and 2b are the fluorescence change spectra of the fluorescent probe before and after adding mercury ions; in Figure 2, the abscissa is the fluorescence emission wavelength (nm), and the ordinate is the fluorescence intensity.
图3为(浓度为10μM)在乙腈溶液中对汞离子的荧光光谱响应图。在图3中，横坐标为荧光发射波长(nm)，纵坐标为荧光强度；图中插图为Hg2+浓度增加与荧光强度的趋势图(激发波长在560nm)。Fig. 3 is a graph of the fluorescence spectrum response to mercury ions in acetonitrile solution (with a concentration of 10 μM). In Fig. 3, the abscissa is the fluorescence emission wavelength (nm), and the ordinate is the fluorescence intensity; the inset in the figure is the trend diagram of Hg2+ concentration increase and fluorescence intensity (excitation wavelength is at 560nm).
图4为(浓度为10μM)在乙腈溶液中对不同的金属离子(Cu、Co、Mn、Mg、Fe、Ba、Ca、K、Na、Ni、Pb、Cd)选择干扰性检测的荧光响应图；在图4中，横坐标为不同的金属离子，纵坐标为荧光强度。Figure 4 is a graph of the fluorescence response to selective interference detection of different metal ions (Cu, Co, Mn, Mg, Fe, Ba, Ca, K, Na, Ni, Pb, Cd) in acetonitrile solution (concentration is 10 μM) ; In Figure 4, the abscissa is the different metal ions, and the ordinate is the fluorescence intensity.
图5为(浓度为50μM)与汞离子络合比的Job-Plot曲线；横坐标为c[Hg2+]/c[Hg2++探针]，纵坐标为荧光F-F0，其中F、F0是在560nm的荧光发射强度。Figure 5 is the Job-Plot curve of the complexation ratio with mercury ions (with a concentration of 50 μM); the abscissa is c[Hg2+ ]/c[Hg2+ +probe], and the ordinate is fluorescence FF0 , where F, F0 is the fluorescence emission intensity at 560 nm.
图6为(浓度为50μM)的探针溶液使用磷酸二氢盐/磷酸盐缓冲溶液配置了一系列不同pH的缓冲溶液，然后向探针溶液中加入一定量的汞离子，检测荧光强度横坐标为荧光发射波长(nm)，纵坐标为荧光强度。Figure 6 is a probe solution (with a concentration of 50 μM) using a dihydrogen phosphate/phosphate buffer solution to configure a series of buffer solutions with different pHs, and then adding a certain amount of mercury ions to the probe solution to detect the fluorescence intensity on the abscissa is the fluorescence emission wavelength (nm), and the ordinate is the fluorescence intensity.
图7为本发明的检测汞离子的反应型罗丹明类荧光探针的制备路线图。Fig. 7 is a preparation route diagram of the reactive rhodamine-based fluorescent probe for detecting mercury ions of the present invention.
图8为实施例2得到的线性工作曲线。Fig. 8 is the linear working curve that embodiment 2 obtains.
具体实施方式detailed description
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例中所用的2-溴甲基吡啶氢溴酸盐的纯度为95～99％。叠氮化钠的纯度为95～99％。溶剂N，N-二甲基甲酰胺的纯度为95～98％。萃取剂二氯甲烷的纯度为95～98％。干燥剂无水硫酸镁的纯度为95～99％。对羟基苯甲醛的纯度为95～99％。2-叠氮甲基吡啶的纯度为95～99％。萃取剂二氯甲烷的纯度为95～98％。催化剂碳酸钾的纯度为95～99％。溶剂丙酮的纯度为95～98％。干燥剂无水硫酸镁的纯度为95～99％。叔丁醇的纯度为95～98％。萃取剂乙酸乙酯纯度为95～98％。催化剂五水硫酸铜的纯度为95～99％。催化剂抗坏血酸钠的纯度为95～99％。干燥剂无水碳酸氢钠的纯度为95～99％。罗丹明B的纯度为95～99％。水合肼的纯度为95～98％。溶剂乙醇的纯度为95～98％。氢氧化钠的纯度为95～99％。溶剂乙醇的纯度为95～98％，溶剂乙酸的纯度为95～98％。以上百分数为质量百分数。The purity of the 2-bromomethylpyridine hydrobromide used in the examples is 95-99%. The purity of sodium azide is 95-99%. The purity of the solvent N,N-dimethylformamide is 95-98%. The purity of the extractant dichloromethane is 95-98%. The purity of the desiccant anhydrous magnesium sulfate is 95-99%. The purity of p-hydroxybenzaldehyde is 95-99%. The purity of 2-azidomethylpyridine is 95-99%. The purity of the extractant dichloromethane is 95-98%. The purity of the catalyst potassium carbonate is 95-99%. The purity of the solvent acetone is 95-98%. The purity of the desiccant anhydrous magnesium sulfate is 95-99%. The purity of tert-butanol is 95-98%. The purity of the extractant ethyl acetate is 95-98%. The purity of the catalyst copper sulfate pentahydrate is 95-99%. The purity of the catalyst sodium ascorbate is 95-99%. The purity of the desiccant anhydrous sodium bicarbonate is 95-99%. The purity of Rhodamine B is 95-99%. The purity of hydrazine hydrate is 95-98%. The purity of the solvent ethanol is 95-98%. The purity of sodium hydroxide is 95-99%. The purity of the solvent ethanol is 95-98%, and the purity of the solvent acetic acid is 95-98%. The above percentages are percentages by mass.
实施例1Example 1
一种检测汞离子的反应型罗丹明类荧光探针，其结构式为：A reactive rhodamine-based fluorescent probe for detecting mercury ions, the structural formula of which is:
上述的检测汞离子的反应型罗丹明类荧光探针的制备方法为：The preparation method of the above-mentioned reactive rhodamine fluorescent probe for detecting mercury ions is:
(1)中间体1的合成：(1) Synthesis of Intermediate 1:
在50mL三颈瓶中将0.50g(1.9mmol)的2-溴甲基吡啶氢溴酸盐和0.39g(5.9mmol)的叠氮化钠溶于10mL的DMF溶剂中，室温下搅拌反应4h，反应结束后，加入5.0mL的水后，再用50.0mL的CH2Cl2萃取，上层为黄色澄清溶液，下层为淡粉红色混浊状液体，下层为有机层，收集并合并有机层，用大量水洗(洗去过量的NaN3)，用无水MgSO4干燥半小时，有机溶剂用旋转蒸发仪蒸去，得到黄色的油状物(4-(2-炔基丙氧基)苯甲醛)。产率：60-80％。1H NMR(300MHz，CDCl3)：8.61(d，J＝4.2Hz，1H)，7.73(td，J＝1.8，7.8Hz，1H)，7.35(d，J＝7.8Hz，1H)，7.26(m，1H)，4.50(s，2H)。In a 50mL three-necked flask, 0.50g (1.9mmol) of 2-bromomethylpyridine hydrobromide and 0.39g (5.9mmol) of sodium azide were dissolved in 10mL of DMF solvent, stirred at room temperature for 4h, After the reaction, add 5.0mL of water, then extract with 50.0mL of CH2 Cl2 , the upper layer is a yellow clear solution, the lower layer is a pale pink turbid liquid, and the lower layer is an organic layer, collect and combine the organic layers, and use a large amount of Wash with water (to remove excess NaN3 ), dry with anhydrous MgSO4 for half an hour, and evaporate the organic solvent with a rotary evaporator to obtain a yellow oil (4-(2-alkynylpropoxy)benzaldehyde). Yield: 60-80%.1 H NMR (300MHz, CDCl3 ): 8.61 (d, J = 4.2Hz, 1H), 7.73 (td, J = 1.8, 7.8Hz, 1H), 7.35 (d, J = 7.8Hz, 1H), 7.26 ( m, 1H), 4.50 (s, 2H).
(2)中间体2的合成：(2) Synthesis of Intermediate 2:
在500mL三颈瓶中将0.30g(0.25mol)对羟基苯甲醛和7.7mL(0.98mol)溴丙炔以及14.00g(0.98mol)的K2CO3做催化剂溶于150mL的丙酮溶剂中，80℃下加热回流(用TCL点板跟踪)大约需要4h。冷却到室温，加入37.0mL水后，用100.0mL CH2Cl2萃取，合并有机层，用无水MgSO4干燥半小时，用旋转蒸发仪蒸去溶剂，放入20℃真空干燥箱内烘干至恒重，得到淡黄色产物(2-叠氮甲基吡啶)。mp：85-86℃，产率96％。FTIR(KBr)：v＝3210cm-1(C≡CH)，2122cm-1(C≡C)，1668cm-1(C＝O)，1603cm-1，1577cm-1，1508cm-1，1453cm-1(C＝C)，3070cm-1(Ar-H)，2836cm-1(CH)，1250cm-1(C-O).1HNMR(400MHz，CDCl3)：9.87(s，1H，-CHO)，7.70(d，J＝8.8Hz，2H，Ar-H)，6.96(d，J＝9.0Hz，2H，Ar-H)，4.68(s，2H，O-CH2)，2.51(s，1H，C≡CH)。In a 500mL three-necked flask, 0.30g (0.25mol) of p-hydroxybenzaldehyde, 7.7mL (0.98mol) of propyne bromide and 14.00g (0.98mol) of K2CO3were dissolved in 150mLof acetone solvent as a catalyst, and 80 It takes about 4 hours to heat to reflux at ℃ (track with TCL spot plate). Cool to room temperature, add 37.0mL of water, extract with 100.0mL CH2 Cl2 , combine the organic layers, dry with anhydrous MgSO4 for half an hour, evaporate the solvent with a rotary evaporator, and dry in a vacuum oven at 20°C To constant weight, a pale yellow product (2-azidomethylpyridine) was obtained. mp: 85-86°C, 96% yield. FTIR (KBr): v=3210cm-1 (C≡CH), 2122cm-1 (C≡C), 1668cm-1 (C=O), 1603cm-1 , 1577cm-1 , 1508cm-1 , 1453cm-1 ( C=C), 3070cm-1 (Ar-H), 2836cm-1 (CH), 1250cm-1 (CO).1 HNMR (400MHz, CDCl3 ): 9.87(s, 1H, -CHO), 7.70(d , J=8.8Hz, 2H, Ar-H), 6.96(d, J=9.0Hz, 2H, Ar-H), 4.68(s, 2H, O-CH2 ), 2.51(s, 1H, C≡CH ).
(3)中间体3的合成：(3) Synthesis of Intermediate 3:
在250mL三颈瓶中加入0.32g(2.0mmol)的4-(2炔基丙氧基)苯甲醛和0.26g(2.0mmol)的2-叠氮甲基吡啶，在N2的保护下，溶于体积比为1∶1的叔丁醇和水的混合溶液30.0mL中，加入5mol％的CuSO4·5H2O和10mol％的抗坏血酸钠作为催化剂，在室温下搅拌反应24h。应后得到黄色的产物，用30.0mL乙酸乙酯进行萃取，合并有机层，用无水Na2SO4干燥半小时，旋干得到棕色的油状物。在进行柱层析得到白色固体(产物R)。产率70％。mp：106-107℃。FTIR：v＝3139cm-1(C＝CH)，3075cm-1(Ar-H)，2847cm-1，2864cm-1(C-H)，1681cm-1(C＝O)，1603cm-1，1577cm-1，1508cm-1，1476cm-1(C＝C)，1577cm-1，1422cm-1(Py-H)，1392cm-1(C-H的面内弯曲)，1254cm-1(C-O)，870cm-1，835cm-1(Ar中C＝H的倍频峰)。1HNMR(400MHz，CDCl3)：9.88(s，1H，-CHO)，8.55(d，J＝3.2Hz，1H)，8.3(s，1H)，7.90(d，J＝6.0Hz，2H)，7.26(d，J＝8.6Hz，2H)，7.84(t，J＝8.60Hz，1H)，7.37(t，J＝5.8Hz，1H)，7.32(d，J＝8.0Hz，1H)，5.76(s，2H)，5.30(s，2H)。In a 250mL three-necked flask, add 0.32g (2.0mmol) of 4-(2 alkynylpropoxyl) benzaldehyde and 0.26g (2.0mmol) of 2-azidopicoline, under the protection ofN2 , dissolve 5 mol% CuSO4 ·5H2 O and 10 mol% sodium ascorbate were added as catalysts to 30.0 mL of a mixed solution of tert-butanol and water at a volume ratio of 1:1, and the reaction was stirred at room temperature for 24 hours. After the reaction, a yellow product was obtained, which was extracted with 30.0 mL ethyl acetate, and the organic layers were combined, dried with anhydrous Na2 SO4 for half an hour, and spin-dried to obtain a brown oil. Column chromatography gave a white solid (product R). Yield 70%. mp: 106-107°C. FTIR: v=3139cm-1 (C=CH), 3075cm-1 (Ar-H), 2847cm-1 , 2864cm-1 (CH), 1681cm-1 (C=O), 1603cm-1 , 1577cm-1 , 1508cm-1 , 1476cm-1 (C=C), 1577cm-1 , 1422cm-1 (Py-H), 1392cm-1 (in-plane curvature of CH), 1254cm-1 (CO), 870cm-1 , 835cm- 1 (octave peak of C=H in Ar).1 HNMR (400MHz, CDCl3 ): 9.88(s, 1H, -CHO), 8.55(d, J=3.2Hz, 1H), 8.3(s, 1H), 7.90(d, J=6.0Hz, 2H), 7.26(d, J=8.6Hz, 2H), 7.84(t, J=8.60Hz, 1H), 7.37(t, J=5.8Hz, 1H), 7.32(d, J=8.0Hz, 1H), 5.76( s, 2H), 5.30 (s, 2H).
(4)中间体4的合成：(4) Synthesis of Intermediate 4:
在250mL三颈瓶中，称取1.2g的罗丹明B，溶于30mL乙醇中，在室温下逐滴加入3.0mL质量浓度为85％的水合肼溶液，滴加完了后，80℃加热回流2h，溶液从紫色慢慢变为黄色澄清溶液，反应结束后，冷却到室温，溶剂旋干后加入1M HCl 50.0mL，在慢慢滴加1MNaOH大约70.0mL，pH约为9.0-10.0，溶液由红色变为粉红色，沉淀减压过滤并用15.0mL的水洗三次，得到产物烘干，得到粉红色粉末(罗丹明酰胺)。产率：90％。mp：171-172℃。FTIR：v＝3424cm-1(-OH)，3415cm-1(-NH2)2969cm-1，2928cm-1(C-H)，1696cm-1(C＝O，1615cm-1，1547cm-1，1514cm-1，1374cm-1(C＝C)，1357cm-1(CH的面内弯曲振动)，1219cm-1，1118cm-1(C-C)，819cm-1，787cm-1，699cm-1(苯环上CH伸缩振动的倍频峰)。1HNMR(400MHz，CDCl3)：1.16(t，12H，NCH2CH3)，3.34(q，8H，NCH2CH3)，3.61(bs，2H，NH2)，6.29(dd，2H，xanthene-H)，6.42(d，2H，xanthene-H)，6.48(d，2H，xanthene-H)，7.11(m，1H，Ar-H)，7.45(m，2H，Ar-H)，7.94(m，1H，Ar-H)。In a 250mL three-necked bottle, weigh 1.2g of Rhodamine B, dissolve it in 30mL of ethanol, add 3.0mL of hydrazine hydrate solution with a mass concentration of 85% dropwise at room temperature, and heat to reflux at 80°C for 2h after the dropwise addition , the solution slowly changed from purple to yellow clear solution, after the reaction, cooled to room temperature, after the solvent was spin-dried, 50.0mL of 1M HCl was added, and about 70.0mL of 1M NaOH was slowly added dropwise, the pH was about 9.0-10.0, and the solution changed from red to It turned pink, and the precipitate was filtered under reduced pressure and washed three times with 15.0 mL of water, and the product was dried to obtain a pink powder (rhodamine amide). Yield: 90%. mp: 171-172°C. FTIR: v=3424cm-1 (-OH), 3415cm-1 (-NH2 ) 2969cm-1 , 2928cm-1 (CH), 1696cm-1 (C=O, 1615cm-1 , 1547cm-1 , 1514cm-1 , 1374cm-1 (C=C), 1357cm-1 (in-plane bending vibration of CH), 1219cm-1 , 1118cm-1 (CC), 819cm-1 , 787cm-1 , 699cm-1 (CH stretching on the benzene ring double frequency peak of vibration).1 HNMR (400MHz, CDCl3 ): 1.16 (t, 12H, NCH2 CH3 ), 3.34 (q, 8H, NCH2CH3 ), 3.61 (bs, 2H, NH2 ), 6.29 ( dd, 2H, xanthene-H), 6.42 (d, 2H, xanthene-H), 6.48 (d, 2H, xanthene-H), 7.11 (m, 1H, Ar-H), 7.45 (m, 2H, Ar- H), 7.94 (m, 1H, Ar-H).
(5)荧光探针的制备(5) Preparation of fluorescent probes
在250mL三颈瓶中，称取0.15g(0.50mmol)的BPT(产物R)加入10.0mL乙醇加热溶解，再称取0.23g(0.50mmol)罗丹明酰胺(RHD)，把其溶于5.0mL乙醇(呈淡粉色)，慢慢滴加到三颈瓶中，加入3～4滴乙酸，加热至80℃，回流反应5-6h，用TCL点板跟踪，反应结束后，用旋转蒸发仪蒸干，得到紫红色的固体(检测汞离子的反应型罗丹明类荧光探针)。产率：89％。Mp：199-200℃。FTIR：v＝2970cm-1(C-H)，1716cm-1(C＝O)，1613cm-1，1547cm-1，1514cm-1，1466cm-1(C＝C)，1264cm-1(C-O)，1235cm-1，1219cm-1(C-C)1118cm-1，1005cm-1，758cm-1(苯环上H的CH伸缩振动的倍频峰)。1HNMR(400MHz，CDCl3)：1.20(t，12H，NCH2CH3)，3.75(q，8H，NCH2CH3)，5.20(s，2H，OCH2)，5.76(s2H，CH2)，5.65(s，1H)，5.71(s，1H)，6.88(s，1H，CH＝N)，6.90(s，1H，Ar-H)，7.12(s，1H，triazole-H)，7.15(s，2H，xanthene-H)，7.19(d，2H，xanthene-H)，7.28(d，1H，Pyridine-H)，7.45(d，2H，Ar-H)，7.50(t，1H，Ar-H)，7.69(t，1H，Ar-H)，7.77(d，2H，xanthene-H)，7.87(t，1H，Pyridine-H)，8.01(d，1H，Ar-H)，8.60(d，1H，xanthene-H)，8.63(d，1H，Pyridine-H)。In a 250mL three-necked bottle, weigh 0.15g (0.50mmol) of BPT (product R) and add 10.0mL of ethanol to dissolve it, then weigh 0.23g (0.50mmol) rhodamine amide (RHD), and dissolve it in 5.0mL Slowly add ethanol (in light pink color) to the three-necked bottle, add 3-4 drops of acetic acid, heat to 80°C, reflux for 5-6h, track with TCL spot plate, after the reaction, evaporate with a rotary evaporator Dry to obtain a purple-red solid (a reactive rhodamine-based fluorescent probe for detecting mercury ions). Yield: 89%. Mp: 199-200°C. FTIR: v=2970cm-1 (CH), 1716cm-1 (C=O), 1613cm-1 , 1547cm-1 , 1514cm-1 , 1466cm-1 (C=C), 1264cm-1 (CO),1235cm -11 , 1219cm-1 (CC) 1118cm-1 , 1005cm-1 , 758cm-1 (the double peak of the CH stretching vibration of H on the benzene ring).1 HNMR (400MHz, CDCl3 ): 1.20 (t, 12H, NCH2 CH3 ), 3.75 (q, 8H, NCH2 CH3 ), 5.20 (s, 2H, OCH2), 5.76 (s2H, CH2), 5.65 (s, 1H), 5.71(s, 1H), 6.88(s, 1H, CH=N), 6.90(s, 1H, Ar-H), 7.12(s, 1H, triazole-H), 7.15(s, 2H, xanthene-H), 7.19 (d, 2H, xanthene-H), 7.28 (d, 1H, Pyridine-H), 7.45 (d, 2H, Ar-H), 7.50 (t, 1H, Ar-H) , 7.69(t, 1H, Ar-H), 7.77(d, 2H, xanthene-H), 7.87(t, 1H, Pyridine-H), 8.01(d, 1H, Ar-H), 8.60(d, 1H , xanthene-H), 8.63 (d, 1H, Pyridine-H).
配制探针溶液浓度为10μM，以及探针浓度和离子浓度分别为10μM和100μM的溶液，在紫外吸收光谱下检测，结果如图1所示。The probe solution concentration was 10 μM, and the probe concentration and ion concentration were 10 μM and 100 μM, respectively, and detected under ultraviolet absorption spectrum. The results are shown in FIG. 1 .
配制探针溶液浓度为10μM，以及探针浓度和离子浓度分别为10μM的溶液，激发峰为560nm处激发，测得激发峰和发射峰，结果如图2a和2b所示。The probe solution concentration was 10 μM, and the probe concentration and ion concentration were 10 μM respectively. The excitation peak was excited at 560 nm, and the excitation peak and emission peak were measured. The results are shown in Figures 2a and 2b.
固定探针溶液的浓度为10μM，再加入不同的汞离子浓度，汞离子分别从0到1000μM，分别检测其荧光强度，结构如图3所示。The concentration of the fixed probe solution was 10 μM, and then different concentrations of mercury ions were added. The mercury ions ranged from 0 to 1000 μM, and the fluorescence intensity was detected respectively. The structure is shown in FIG. 3 .
配制探针溶液浓度为10μM，各种离子的浓度也为10μM。分别用荧光检测探针加入不同离子的荧光强度，以及荧光探针加入汞离子后再加入不同离子总溶液的荧光强度，结果如图4所示。The concentration of the probe solution was prepared to be 10 μM, and the concentration of various ions was also 10 μM. The fluorescence intensity of different ions was added to the fluorescent probe, and the fluorescence intensity of the total solution of different ions was added to the fluorescent probe after adding mercury ions. The results are shown in Figure 4.
固定RHPT和Sn2+的浓度和为50μM。然后分别让RHPT和Sn2+的浓度比按照0∶10；1∶9；2∶8；3∶7；4∶6；5∶5；6∶4；7∶3；8∶2；9∶1；10∶0.分别在同一狭缝下，检测其荧光强度。然后配制溶液的一系列的浓度分别为0，5，10，15，20，25，30，35，40，45，50μM的溶液用荧光检测其荧光强度，进行数据处理，结果如图5所示。The concentration sum of RHPT and Sn2+ was fixed at 50 μM. Then let the concentration ratio of RHPT and Sn2+ be 0:10; 1:9; 2:8; 3:7; 4:6; 5:5; 6:4; 7:3; 8:2; 9: 1;10:0. Under the same slit, detect the fluorescence intensity. Then prepare a series of solutions with concentrations of 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 μM, and use fluorescence to detect the fluorescence intensity and perform data processing. The results are shown in Figure 5 .
将所得的检测汞离子的反应型罗丹明类荧光探针溶于乙腈溶剂中配成10μM的探针溶液，加入磷酸二氢盐/磷酸盐缓冲溶液配置了一系列不同(pH＝1.0、2.0、3.0、4.0、5.0、6.0、7.0、8.0、9.0、10.0、11.0、12.0)pH的缓冲溶液，然后向探针溶液中加入1.0x10-4M的汞离子，检测不同pH条件下探针溶液荧光强度的变化(图6)。发现在pH＝1.0-3.0的时候荧光强度明显下降，pH＝4.0-12.0荧光强度变化不明显，探针溶液比较稳定，因此该荧光探针在乙腈溶剂中pH＝1.0-3.0以下受到酸性条件影响比较大，在pH＝4.0-12.0下探针溶液稳定有利于检测。The obtained reactive rhodamine-based fluorescent probe for detecting mercury ions was dissolved in acetonitrile solvent to form a 10 μM probe solution, and a series of different (pH=1.0, 2.0, pH=1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0) pH buffer solution, then add 1.0x10-4 M mercury ions to the probe solution, and detect the fluorescence of the probe solution under different pH conditions Changes in intensity (Figure 6). It was found that the fluorescence intensity decreased significantly at pH=1.0-3.0, the fluorescence intensity did not change significantly at pH=4.0-12.0, and the probe solution was relatively stable, so the fluorescent probe was affected by acidic conditions below pH=1.0-3.0 in acetonitrile solvent Relatively large, the stability of the probe solution at pH=4.0-12.0 is favorable for detection.
实施例2Example 2
应用实施例1中的检测汞离子的反应型罗丹明类荧光探针检测污水中汞离子的含量的具体步骤为：The specific steps of detecting the content of mercury ions in sewage by the reactive rhodamine fluorescent probe detecting mercury ions in Example 1 are as follows:
将1.0mL浓度为1.5x10-4M、3.0x10-4M、6.0x10-4M的汞离子的水溶液分别加入1.0mL含有重量浓度为1.0x10-5M的上述的检测汞离子的反应型罗丹明类荧光探针的pH＝7.0的H3PO4/H2PO4-的缓冲体系中，测定荧光强度，激发波长为560nm，发射波长为580nm，以汞离子的浓度为横坐标，荧光强度的变化为纵坐标作图，得到线性工作曲线图8所示；Add 1.0mL of aqueous solutions of mercury ions with a concentration of 1.5x10-4 M, 3.0x10-4 M, and 6.0x10-4 M to 1.0mL of the above-mentioned reactive rhodan for detecting mercury ions with a weight concentration of 1.0x10-5 M In the buffer system of H3 PO4 /H2 PO4- with pH=7.0 of the bright fluorescent probe, measure the fluorescence intensity, the excitation wavelength is 560nm, and the emission wavelength is 580nm. The change of is plotted on the ordinate, and the linear working curve is obtained as shown in Fig. 8;
将1.0mL含有汞离子的污水加入1.0mL含有重量浓度为1.0x10-5M的上述的检测汞离子的反应型罗丹明类荧光探针的pH＝7.0的H3PO4/H2PO4-的缓冲体系中，通过测定污水中的汞离子的荧光强度即可得到溶液中汞离子的含量为1.0x10-6M。Add 1.0 mL of sewage containing mercury ions to 1.0 mL of H3 PO4 /H2 PO4- containing the above-mentioned reactive rhodamine-based fluorescent probe for detecting mercury ions with a weight concentration of 1.0x10-5 M at pH = 7.0 In the buffer system, the content of mercury ions in the solution can be obtained as 1.0x10-6 M by measuring the fluorescence intensity of mercury ions in the sewage.
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