Method for on-site visual detection of Sn < 4 + > by using chlorine (terpyridyl) platinum (II) chloride fluorescent probe

Abstract

The invention provides a method for on-site visual detection of Sn < 4 + > by using a chlorochloride.( terpyridyl) platinum (II) fluorescent probe, which comprises the following steps: generating tin chloride hexane anion ([SnCl6] < 2->) by using self-assembly and charge transfer of a chlorochloride.( terpyridyl) platinum (II) solution and tin ions and a confinement effect of a hydrophobic substrate, and detecting the Sn < 4 + > by using the fluorescent probe after the tin chloride hexane anion ([SnCl6] < 2->). The [SnCl6] < 2-> reacts with the chlorochloride.( terpyridyl) platinum (II) fluorescent probe to generate aggregation-induced self-assembly to generate a yellow-green one-dimensional luminous aggregate to realize detection. The method disclosed by the invention has the characteristics of simplicity in operation, strong specificity, visualization and the like, can provide a good research basis for detection of Sn < 4 + >, and has a wide research background.

Description

Technical Field

[0001] The present invention designs a method for on-site visual detection of Sn using a chlorine chloride·(terpyridine) platinum(II) fluorescent probe 4+ The method specifically involves a detection reagent having the characteristics of simple preparation, mild detection, and easy operation. It has a high specific recognition ability for tin ions (IV) and can be expanded to be applied to the field application of tin ions (IV). Background Art

[0002] Tin (Sn) is one of the earliest metals discovered in ancient times. 4+ and Sn 2+ The two oxidation states are widely present in nature and are used in various industries including food containers, toothpaste, soap, daily chemical products, pharmaceutical industry, tinplate, military industry and light industry.

[0003] Tin (Sn) is also an essential trace mineral for organisms. There is about 17 mg in the human body. An appropriate amount of tin can promote the growth and development of the body, but when its content is too high or too low, it will cause certain harm. When its content is too high, it will cause immune system failure, chromosome damage, liver failure, breathing difficulties, etc., and tin is more toxic to human embryonic kidney cells. Tin deficiency will increase the risk factors associated with poor growth and cancer prevention, and will cause hearing loss, respiratory problems, reduced hemoglobin production and DNA damage.

[0004] At the same time, tin is also involved in many biochemical processes at the cellular level. For example, tin can promote protein synthesis, which is related to the activity of flavonoids, and plays an important role in maintaining the three-dimensional spatial structure of macromolecules such as proteins and nucleic acids. In recent years, some scholars have found that tumor cells absorb significantly more tin than normal cells. In addition, tin can produce one or more compounds containing steroids and peptides (steroidal and peptide tin compounds) in the thymus, which participate in the immune function of the thymus. These steroidal and peptide tin compounds have a direct or indirect effect of inhibiting cancer cells.

[0005] There have been many reports on the detection of tin, such as atomic absorption / X-emission spectroscopy (Mining, Metallurgy & Exploration, 2005, 22, 2), inductively coupled plasma mass spectrometry (ICP-MS) (rchaeometry, 1997, 39, 2), liquid chromatography (Journal of Liquid Chromatography & Related Technologies, 2003, 26, 18), electrochemical analysis (The Analyst, 2021, 146, 20), potentiometric membrane sensing (Analytica Chimica Acta, 2006, 579, 1), inductively coupled plasma optical emission spectroscopy (Food Chemistry, 2012, 134, 1), etc. However, these methods often require expensive and complex large instruments, strict sample preparation, professional technicians and the use of hazardous solvents, which makes them somewhat difficult in practical applications. In the past decade, many people have designed and studied new colorimetric and fluorescent chemical sensors based on these sensing methods due to their low cost, ease of use, responsiveness, reliability, high selectivity and visualization. Therefore, there is an urgent need to develop efficient, rapid, trace and visualized methods to detect tin in organisms. Summary of the invention

[0006] The present invention aims to provide a method for on-site visual detection of Sn using a chlorine chloride·(terpyridine) platinum(II) fluorescent probe. 4+ The method utilizes the self-assembly and charge transfer of chlorine chloride·(terpyridine) platinum (II) solution and tin ions, as well as the confinement effect of the hydrophobic substrate, to generate tin chloride hexacoordinate anion ([SnCl 6 ] 2- ) after [SnCl 6 ] 2- The method described in the present invention has the characteristics of simple operation, strong specificity and visualization, and can be used for Sn 4+ It provides a good research foundation for detection and has a broad research background.

[0007] The present invention discloses a method for on-site visual detection of Sn using a chlorine chloride·(terpyridine) platinum(II) fluorescent probe 4+ The method is as follows:

[0008] Preparation of detection probe:

[0009] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0010] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at a constant temperature of 40-50° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and obtain a solid of chlorinated chloride·(terpyridine)platinum(II) by rotary evaporation of the filtrate. Wash the solid with 50 ml of ether for 3 times, and dry the solid in air to obtain a chlorinated chloride·(terpyridine)platinum(II) fluorescent probe.

[0011] Base selection:

[0012] c. Substrate: hydrophobic glass or medical grade polystyrene culture dish;

[0013] Prepare probe solution:

[0014] d. Weigh 0.0012 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of pure water, methanol, ethanol, tetrahydrofuran or dichloromethane to obtain a probe solution with a concentration of 2.4056 μM / mL, which is the detection reagent;

[0015] Fluorescence detection of Sn 4+ :

[0016] e. Take 30 μL of the 2.4056 μM / mL detection reagent obtained in step b and drop it onto the hydrophobic glass sheet or medical grade polystyrene culture dish in step c, and add 75 μL of the 27.24 μM / mL sample Sn to the detection reagent. 4+ After complete volatilization, a single crystal with yellow-green fluorescence is formed. When the single crystal is observed under 365nm ultraviolet light, it exhibits yellow-green fluorescence, confirming the presence of Sn 4+ existence.

[0017] The present invention discloses a method for on-site visual detection of Sn using a chlorine chloride·(terpyridine) platinum(II) fluorescent probe 4+ The method uses a chlorinated chlorine·(terpyridine) platinum (II) solution to self-assemble and transfer charges with tin ions, based on a tin (IV) hexachloro anion ([SnCl 6 ] 2-) and terpyridine platinum (II) cations self-assembled and aggregated on the gas-liquid surface of the droplets to form a one-dimensional luminescent aggregate, and effectively suppressed the conventional coffee ring effect during the evaporation of the droplets. This method is simple to prepare, low cost, mild reaction, clear and stable color development, strong specificity and visualization, and is a promising method for Sn 4+ It provides more technical means for detection.

[0018] The present invention discloses a method for on-site visual detection of Sn using a chlorine chloride·(terpyridine) platinum(II) fluorescent probe 4+ The method comprises the following steps: the chemical name of the probe is chlorinated chloride·(terpyridine)platinum(II), and the structural formula (I) is:

[0019] BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The detection reagent of the present invention is Sn 4+ The fluorescence spectrum of the response;

[0021] Figure 2 The detection reagent of the present invention is Sn 4+ Fluorescence images of the series concentration responses;

[0022] Figure 3 The detection reagent of the present invention is Sn 4+ G / R value analysis of fluorescence images in response to a series of concentrations;

[0023] Figure 4 The detection reagent of the present invention is Sn 4+ and selective fluorescence images of other ion responses;

[0024] Figure 5 The detection reagent of the present invention is Sn 4+ and the H value distribution of other ion responses;

[0025] Figure 6 The detection reagent of the present invention is Sn 4+ and interference-resistant fluorescence images of other ion responses;

[0026] Figure 7 The detection reagent of the present invention is Sn 4+ and the △G / √(R 2 +G 2 +B 2 ) value distribution. DETAILED DESCRIPTION

[0027] The present invention is further described below by means of specific examples, but the invention is not limited to these examples.

[0028] Example 1

[0029] Chlorine chloride·(terpyridine) platinum(Ⅱ) fluorescent probe for Sn 4+ Detection:

[0030] Preparation of detection probe:

[0031] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0032] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at 40° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and evaporate the filtrate to obtain a solid, namely, chlorinated chloride·(terpyridine)platinum(II). Wash the solid with 50 ml of ether for three times, and dry the solid in air to obtain a chlorinated chloride·(terpyridine)platinum(II) fluorescent probe.

[0033] Base selection:

[0034] c. Substrate: hydrophobic glass slide;

[0035] Preparation of detection reagents:

[0036] d. Weigh 0.0012 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of methanol to obtain a probe solution with a concentration of 2.4056 μM / mL, which is the detection reagent;

[0037] Fluorescence detection of Sn 4+ :

[0038] e. Take 30 μL of the 2.4056 μM / mL detection reagent obtained in step d and drop it onto the hydrophobic slide in step c, and then add 75 μL of 27.24 μM / mL of the analyte Sn into the detection reagent. 4+ After complete volatilization, a single crystal with yellow-green fluorescence was observed. When the single crystal was observed under 365nm ultraviolet light, it showed yellow-green fluorescence. The test results showed that the detection system contained Sn 4+ .

[0039] Example 2

[0040] Chlorine chloride·(terpyridine)platinum(II) probe for Sn 4+ Detection:

[0041] Preparation of detection probe:

[0042] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0043] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at 50° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and obtain a solid of chlorinated chloride·(terpyridine)platinum(II) by rotary evaporation of the filtrate. Wash the solid with 50 ml of ether for 3 times, and dry the solid in air to obtain a chlorinated chloride·(terpyridine)platinum(II) fluorescent probe.

[0044] Base selection:

[0045] c. Substrate: Medical grade polystyrene (PS) culture dish;

[0046] Preparation of detection reagents:

[0047] d. Weigh 0.0012 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of ethanol to obtain a probe solution with a concentration of 2.4056 μM / mL, which is the detection reagent;

[0048] Fluorescence detection of Sn 4+ :

[0049] e. Take 30 μL of the 2.4056 μM / mL detection reagent obtained in step d and drop it onto the medical grade polystyrene (PS) culture dish in step c, and add 75 μL of 27.24 μM / mL of the analyte Sn into the detection reagent. 4+ After complete volatilization, a single crystal with yellow-green fluorescence was observed. When the single crystal was observed under 365nm ultraviolet light, it showed yellow-green fluorescence. The test results showed that the detection system contained Sn 4+ .

[0050] Example 3

[0051] Chlorine chloride·(terpyridine)platinum(II) probe for Sn 4+ Detection:

[0052] Preparation of detection probe:

[0053] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0054] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at 45° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and evaporate the filtrate to obtain a solid, namely, chlorine chloride·(terpyridine)platinum(II). Wash the solid with 50 ml of ether for three times, and dry the solid in air to obtain a chlorine chloride·(terpyridine)platinum(II) fluorescent probe.

[0055] Base selection:

[0056] c. Substrate: hydrophobic glass slide;

[0057] Preparation of detection reagents:

[0058] d. Weigh 0.0012 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of tetrahydrofuran to obtain a probe solution with a concentration of 2.4056 μM / mL, which is the detection reagent;

[0059] Fluorescence detection of Sn 4+ :

[0060] e. Take 30 μL of the 2.4056 μM / mL detection reagent obtained in step d and drop it onto the hydrophobic slide in step c, and then add 75 μL of 27.24 μM / mL of the analyte Sn into the detection reagent. 4+ After complete volatilization, a single crystal with yellow-green fluorescence was observed. When the single crystal was observed under 365nm ultraviolet light, it showed yellow-green fluorescence. The test results showed that the detection system contained Sn 4+ .

[0061] Example 4

[0062] Chlorine chloride·(terpyridine)platinum(II) probe for Sn 4+ Detection:

[0063] Preparation of detection probe:

[0064] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0065] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at 42° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and evaporate the filtrate to obtain a solid, namely, chlorinated chloride·(terpyridine)platinum(II). Wash the solid with 50 ml of ether for three times, and dry the solid in air to obtain a chlorinated chloride·(terpyridine)platinum(II) fluorescent probe.

[0066] Base selection:

[0067] c. Substrate: Medical grade polystyrene (PS) culture dish;

[0068] Preparation of detection reagents:

[0069] d. Weigh 0.0012 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of dichloromethane to obtain a probe solution with a concentration of 2.4056 μM / mL, which is the detection reagent;

[0070] Fluorescence detection of Sn 4+ :

[0071] e. Take 30 μL of the 2.4056 μM / mL detection reagent obtained in step d and drop it onto the medical grade polystyrene (PS) culture dish in step c, and add 75 μL of 27.24 μM / mL of the analyte Sn into the detection reagent. 4+ After complete volatilization, a single crystal with yellow-green fluorescence was observed. When the single crystal was observed under 365nm ultraviolet light, it showed yellow-green fluorescence. The test results showed that the detection system contained Sn 4+ .

[0072] Example 5

[0073] Chlorine chloride·(terpyridine)platinum(II) probe for Sn 4+ Detection:

[0074] Preparation of detection probe:

[0075] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0076] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at a constant temperature of 46°C for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and obtain a solid of chlorinated chloride·(terpyridine)platinum(II) by rotary evaporation of the filtrate. Wash the solid with 50 ml of ether for three times, and dry the solid in air to obtain a chlorinated chloride·(terpyridine)platinum(II) fluorescent probe.

[0077] Base selection:

[0078] c. Substrate: hydrophobic glass slide;

[0079] Preparation of detection reagents:

[0080] d. Weigh 0.0024 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of methanol to obtain a probe solution with a concentration of 4.8112 μM / mL, which is the detection reagent;

[0081] Fluorescence detection of Sn 4+ :

[0082] e. Take 30 μL of the 4.8112 μM / mL detection reagent obtained in step d and drop it onto the hydrophobic slide in step c, and then add 75 μL of 27.24 μM / mL of the analyte Sn into the detection reagent. 4+ After complete volatilization, a single crystal with yellow-green fluorescence was observed. When the single crystal was observed under 365nm ultraviolet light, it showed yellow-green fluorescence. The test results showed that the detection system contained Sn 4+ .

[0083] Example 6

[0084] Chlorine chloride·(terpyridine)platinum(II) probe for Sn 4+ Detection:

[0085] Preparation of detection probe:

[0086] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0087] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at a constant temperature of 40-50° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and obtain a solid of chlorine chloride·(terpyridine)platinum(II) by rotary evaporation of the filtrate. Wash the solid with 50 ml of ether for 3 times, and dry the solid in air to obtain chlorine chloride·(terpyridine)platinum(II) fluorescent probe [Pt(tpy)Cl]·Cl;

[0088] Base selection:

[0089] c. Substrate: hydrophobic glass slide;

[0090] Preparation of detection reagents:

[0091] d. Weigh 0.0024 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of ethanol to obtain a probe solution with a concentration of 4.8112 μM / mL, which is the detection reagent;

[0092] Fluorescence detection of Sn 4+ :

[0093] e. Take 30 μL of the 4.8112 μM / mL detection reagent obtained in step d and drop it onto the hydrophobic slide in step c, and then add 75 μL of 27.24 μM / mL of the analyte Sn into the detection reagent. 4+ After complete volatilization, a single crystal with yellow-green fluorescence was observed. When the single crystal was observed under 365nm ultraviolet light, it showed yellow-green fluorescence. The test results showed that the detection system contained Sn 4+ .

[0094] Example 7

[0095] Chlorine chloride·(terpyridine)platinum(II) probe for a series of concentrations of Sn 4+ Detection:

[0096] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0097] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at 48° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and evaporate the filtrate to obtain a solid, namely, chlorine chloride·(terpyridine)platinum(II). Wash the solid with 50 ml of ether for three times, and dry the solid in air to obtain chlorine chloride·(terpyridine)platinum(II) fluorescent probe [Pt(tpy)Cl]·Cl;

[0098] Base selection:

[0099] c. Substrate: hydrophobic glass sheet;

[0100] Preparation of detection reagents:

[0101] d. Weigh 0.0012 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of pure water to obtain a probe solution with a concentration of 2.4056 μM / mL, which is the detection reagent;

[0102] Fluorescence detection of Sn 4+ :

[0103] e. Prepare a series of concentration solutions of the substance to be tested:

[0104] 27.24 μM / mL Sn 4+ The aqueous solution was diluted to obtain a series of standard solutions with concentrations of 6.81, 5.45, 4.09, 3.40, 2.72, 2.04, 1.36 and 0.16 μM / mL;

[0105] Take 30 μL of the 2.4056 μM / mL detection reagent obtained in step d and drop it onto the hydrophobic slide in step c, and add 75 μL of the analyte Sn with concentrations of 6.81, 5.45, 4.09, 3.40, 2.72, 2.04, 1.36 and 0.16 μM / mL to the detection reagent, respectively. 4+ After complete volatilization, a single crystal with yellow-green fluorescence is formed. When the single crystal is observed under 365nm ultraviolet light, it exhibits yellow-green fluorescence. The test results show that the detection system contains Sn 4+ ,like Figure 2, the detected image is used to extract the RGB value of the image using Photoshop, Sn 4+ There is an obvious linear relationship between the concentration and the G / R value of the image, such as Figure 3 shown.

[0106] Example 8

[0107] Chlorine chloride·(terpyridine)platinum(II) probe for Sn 4+ Selective detection of:

[0108] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0109] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at 50° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and obtain a solid of chlorinated chloride·(terpyridine)platinum(II) by rotary evaporation of the filtrate. Wash the solid with 50 ml of ether for 3 times, and dry the solid in air to obtain a chlorinated chloride·(terpyridine)platinum(II) fluorescent probe.

[0110] Base selection:

[0111] c. Substrate: hydrophobic glass sheet;

[0112] Preparation of detection reagents:

[0113] d. Weigh 0.0012 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of pure water to obtain a probe solution with a concentration of 2.4056 μM / mL, which is the detection reagent;

[0114] Fluorescence detection of Sn 4+ :

[0115] Prepare the selective solution:

[0116] e. Selective substances include: Sn 2+ 、Na + , Li + , K + , Cs + , Ca 2+ Mg 2+ 、Zn 2+ 、Ni 2+、Co 2+ , Mn 2+ 、Cd 2+ , Ba 2 + , Cu 2+ , Sr 2+ , Fe 2+ , Pb 2+ , Fe 3+ ,La 3+ 、Al 3+ , CH 3 COO - 、NO 3 - 、SO 4 2- 、 HCO 3 - , HPO 4 2- , all prepared as 27.24 μM / mL aqueous solutions;

[0117] Take 30 μL of 2.4056 μM / mL detection reagent obtained in step d and drop it onto the hydrophobic slide in step c, and 2+ 、Na + , Li + , K + , Cs + , Ca 2+ Mg 2+ 、Zn 2+ 、Ni 2+ 、Co 2+ , Mn 2+ 、Cd 2+ , Ba 2+ , Cu 2+ , Sr 2+ , Fe 2+ , Pb 2 + , Fe 3+ ,La 3+ 、Al 3+ , CH 3 COO - 、NO 3 - 、SO 4 2- 、 HCO 3 - , HPO 4 2- Add 75 μL of the analyte Sn into the interference solution. 4+After complete volatilization, a single crystal with yellow-green fluorescence is formed. When the single crystal is observed under 365nm ultraviolet light, it exhibits yellow-green fluorescence. The test results show that the detection system contains Sn 4+ ; During the test process, it was shown that only Sn 4+ Yellow-green, such as Figure 4 , the detected image is extracted with Photoshop, and the image hue H value and saturation S value are used to make a polar coordinate diagram. The polar angle is within the range of 60-120, only Sn 4+ Existence, such as Figure 5 shown.

[0118] The results showed that this method can detect Sn 4+ Has good selectivity.

[0119] Example 9

[0120] Chlorine chloride·(terpyridine)platinum(II) probe for Sn 4+ Anti-interference detection:

[0121] a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is obtained. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in sequence to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II);

[0122] b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at 50° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and obtain a solid of chlorinated chloride·(terpyridine)platinum(II) by rotary evaporation of the filtrate. Wash the solid with 50 ml of ether for 3 times, and dry the solid in air to obtain a chlorinated chloride·(terpyridine)platinum(II) fluorescent probe.

[0123] Base selection:

[0124] c. Substrate: hydrophobic glass sheet;

[0125] Preparation of detection reagents:

[0126] d. Weigh 0.0012 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of pure water to obtain a probe solution with a concentration of 2.4056 μM / mL, which is the detection reagent;

[0127] Fluorescence detection of Sn 4+ :

[0128] Prepare interferor solution:

[0129] e. Potential interfering substances include: Sn 2+ 、Na + , Li + , K + , Cs + , Ca 2+ Mg 2+ 、Zn 2+ 、Ni 2+ 、Co 2+ , Mn 2+ 、Cd 2+ , Ba 2+ , Cu 2+ , Sr 2+ , Fe 2+ , Pb 2+ , Fe 3+ ,La 3+ 、Al 3+ , CH 3 COO - 、NO 3 - 、SO 4 2- 、 HCO 3 - , HPO 4 2- , were prepared as 27.24 μM / mL aqueous solutions;

[0130] Take 30 μL of 2.4056 μM / mL detection reagent obtained in step d and drop it onto the hydrophobic slide in step c, and 2+ 、Na + , Li + , K + , Cs + , Ca 2+ Mg 2+ 、Zn 2+ 、Ni 2+ 、Co 2+ , Mn 2+ 、Cd 2+ , Ba 2+ , Cu 2+ , Sr 2+ , Fe 2+ , Pb 2 + , Fe 3+ ,La 3+ 、Al 3+ , CH 3 COO- 、NO 3 - 、SO 4 2- 、 HCO 3 - , HPO 4 2- Add 75 μL of the analyte Sn into the interfering solution. 4+ After complete volatilization, a single crystal with yellow-green fluorescence is formed. When observed under 365nm ultraviolet light, the single crystal exhibits yellow-green fluorescence. The test results show that this method has good anti-interference ability. The anti-interference fluorescence image is as follows Figure 6 As shown in the figure, the detected image is extracted with Photoshop to obtain the RGB value of the image and the △G / √(R 2 +G 2 +B 2 ) value is around 0.8, except Cu 2+ , Fe 3+ , Pb 2+ Sn 2+ 、Zn 2+ Other ions will not react with Sn 4+ The detection of Figure 7 shown.

[0131] The results show that: 2+ , Fe 3+ , Pb 2+ Sn 2+ 、Zn 2+ In addition, this detection method is effective for Sn 4+ Has good anti-interference ability.

Claims

1. A method for on-site visualization detection of Sn using a chlorine chloride·(terpyridine) platinum(II) fluorescent probe 4+ The method is characterized in that Follow these steps: Preparation of detection probe: a. Weigh 1 g of potassium chloroplatinite and dissolve it in 20 ml of water, add 24 ml of acetic acid and 1 ml of 1,5-cyclooctadiene, heat to 80°C, react for 30 minutes, and a light yellow single crystal precipitate is produced. The precipitate is washed with 50 ml of water, 50 ml of ethanol and 50 ml of ether in turn to remove unreacted raw materials, and then dried at 60°C for 1 hour to obtain dichloro(1,5-cyclooctadiene)platinum(II); b. Place 0.15 g of dichloro(1,5-cyclooctadiene)platinum(II) obtained in step a in 10 ml of water, add 0.094 g of terpyridine, and heat at a constant temperature of 40-50° C. for 15 minutes to dissolve the solid. Filter the unreacted dichloro(1,5-cyclooctadiene)platinum(II), and evaporate the filtrate to obtain a solid, namely, chlorinated chloride·(terpyridine)platinum(II). Wash the solid with 50 ml of ether for three times, and dry the solid in air to obtain a chlorinated chloride·(terpyridine)platinum(II) fluorescent probe. Base selection: c. Substrate: hydrophobic glass or medical grade polystyrene culture dish; Prepare probe solution: d. Weigh 0.0012 g of chloro(III)·(terpyridine)platinum(II) obtained in step b and dissolve it in 10 ml of pure water, methanol, ethanol, tetrahydrofuran or dichloromethane to obtain a probe solution with a concentration of 2.4056 μM / mL, which is the detection reagent; Fluorescence detection of Sn 4+ : e. Take 30 μL of the 2.4056 μM / mL detection reagent obtained in step b and drop it onto the hydrophobic glass slide or medical grade polystyrene culture dish in step c, and add 75 μL of the 27.24 μM / mL sample Sn to the detection reagent. 4+ After complete volatilization, a single crystal with yellow-green fluorescence is formed. When the single crystal is observed under 365 nm ultraviolet light, it exhibits yellow-green fluorescence, confirming the presence of Sn 4+ existence.

Images