Online reaction and mass spectrum in-situ sample injection analysis method

Abstract

The invention discloses an on-line reaction and mass spectrum in-situ sample injection analysis method, and belongs to the technical field of chemical analysis. According to the method, the sample is sampled and analyzed in real time under the condition that the reaction environment is not damaged or the reaction is not terminated in advance, the sample is prevented from being damaged by the external environment, the accuracy of an experimental result is improved, and the labor cost is effectively reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical analysis, and in particular relates to a method for online reaction and mass spectrometry in-situ sampling analysis. Background Art

[0002] The iron atom in the sulfinic acid-bridged diiron complex has multiple oxidation states. The sulfinic acid-bridged diiron complex can be mutually converted between different oxidation states. Under certain conditions, it can accept or lose electrons and participate in redox reactions. It can be used as a catalyst in a variety of organic reactions, such as oxidation reactions, reduction reactions, coupling reactions, etc. Its unique structure and electronic properties can activate substrate molecules, reduce the activation energy of the reaction, and improve the selectivity and efficiency of the reaction. In the application of biomedicine, due to its structural similarity with some metal proteins and enzymes in organisms, the sulfinic acid-bridged diiron complex has potential application prospects in the biomedical field, such as as a design template for drug molecules to develop new antibacterial, antiviral or antitumor drugs; or as a bioimaging agent to detect the concentration of metal ions or the distribution of specific biomolecules in organisms.

[0003] Sulfinic acid-bridged diiron complexes are often prepared by oxidation of bionic binuclear iron-sulfur clusters, but bionic binuclear iron-sulfur clusters are sensitive to oxygen and are easily oxidized in the air, which often destroys the reaction environment or terminates the reaction during sampling; therefore, conventional sampling cannot be used for testing and characterization. Summary of the invention

[0004] In order to solve the above-mentioned technical problems, the present invention provides a method for online reaction and mass spectrometry in-situ sampling analysis, which performs real-time sampling and analysis of samples without destroying the reaction environment or terminating the reaction prematurely.

[0005] To achieve the above object, the technical solution of the present invention is as follows: a method for online reaction and mass spectrometry in-situ sampling analysis, comprising the following steps:

[0006]

[0007] S1. First, feed tubes No. 1 and No. 2 in the feeding device inhale nitrogen through a nitrogen protection bottle, then feed tube No. 1 is placed in CH2Cl2, and feed tube No. 2 is placed in a CH2Cl2 solution of compound 1; start the feeding device, and the ratio of feed in feed tube No. 1 to feed tube No. 2 is 9:1;

[0008] S2, the feeding device transports CH2Cl2 and CH2Cl2 solution of compound 1 to the reaction device through the liquid inlet pipe and mixes them evenly; sampling, analysis and testing are performed to obtain a peak m / z 538.0 of compound 1;

[0009] S3, the reaction three-way valve connects the oxygen outlet pipe and the gas inlet pipe; the oxygen in the oxygen source bottle enters the reaction device through the oxygen outlet pipe, the reaction three-way valve, and the gas inlet pipe in sequence, and when the pressure in the pressure sensor monitoring device reaches 1atm, stirring is started and the reaction timing is started;

[0010] S4. Set the sampling volume to 0.1 mL, perform sampling and analysis testing, and obtain the peak m / z 570.0 of compound 2; set sampling and analysis testing at different times to monitor the reaction;

[0011] The sampling process in steps S2 and S4 is as follows: the injection three-way valve is connected to the syringe connecting tube and the six-way valve and three-way valve connecting tube, and the injection six-way valve is connected to the six-way valve and three-way valve connecting tube and the filter and injection connecting tube; the syringe suction is started, and negative pressure is formed in the pipeline, and the sample in the reaction device is extracted, and the sample is filtered through the filter device through the liquid outlet pipe, and then enters the syringe through the filter and injection connecting tube, the injection six-way valve, the six-way valve and three-way valve connecting tube, the injection three-way valve, and the syringe connecting tube in sequence;

[0012] The injection three-way valve is connected to the syringe connecting tube and the six-way valve and three-way valve connecting tube, and the injection six-way valve is connected to the six-way valve and three-way valve connecting tube and the injection and analysis connecting tube; the syringe is pushed, and the sample passes through the syringe connecting tube, the six-way valve and three-way valve connecting tube, and the injection and analysis connecting tube in sequence into the analysis device for analysis.

[0013] Compared with the prior art, the present invention has the following beneficial effects: the method can perform real-time sampling and analysis of samples without destroying the reaction environment or terminating the reaction in advance, avoiding damage to the samples by the external environment, improving the accuracy of the experimental results, and effectively reducing labor costs. It can effectively reduce the contact of experimental personnel with chemical reagents and reduce the damage to the health of experimental personnel caused by sudden accidents or long-term contact during the experiment. For this reaction, this invention can avoid the uncertainty of the reaction caused by oxidation of raw materials during the sampling process, effectively control the reaction endpoint, improve the accuracy of experimental monitoring, and help study the reaction mechanism. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a structural diagram of the online reaction and analysis system.

[0015] Figure 2 This is a graph of the analysis results obtained by sampling at different times.

[0016] In the figure: 1, auxiliary sampling device, 2, nitrogen protection bottle, 3, feeding device, 4, sampling device, 5, analysis device, 6, cleaning liquid bottle, 7, reaction device, 8, filtering device, 9, nitrogen gas source bottle, 9a, oxygen gas source bottle, 10, auxiliary sampling pipeline, 11, feeding pipeline, 12, syringe connecting pipe, 13, valve and cleaning bottle connecting pipe, 14, six-way valve and three-way valve connecting pipe, 15, liquid inlet pipe, 16, filtration and sampling connecting pipe, 17, sampling and analysis connecting pipe, 18, liquid outlet pipe, 19, gas inlet pipe, 20, nitrogen outlet pipe, 21, oxygen outlet pipe, 22, analysis device outlet pipe, 23, reaction three-way valve, 24, sampling three-way valve, 25, sampling six-way valve, 26, syringe. DETAILED DESCRIPTION

[0017] The technical solution of the present invention will be clearly described below in conjunction with the accompanying drawings. Obviously, the described embodiments are not all embodiments of the present invention, and all other embodiments obtained by ordinary technicians in the field without making creative work are within the protection scope of the present invention.

[0018] It should be noted that, unless otherwise specifically stated, the relative arrangements of components and steps, and numerical expressions set forth in these embodiments should not be construed as limiting the scope of the present invention.

[0019] The following description of the exemplary embodiments is merely illustrative and is not intended to limit the present invention and its application or use in any sense. Techniques, methods and devices known to ordinary technicians in the relevant field may not be discussed in detail here, but where applicable, these techniques, methods and devices should be considered as part of this specification.

[0020] Figure 1 An online reaction and analysis system for the oxidation of a biomimetic binuclear iron-sulfur cluster compound is shown. The oxidation reaction comprises the following steps:

[0021]

[0022] S1, firstly inhale nitrogen through the nitrogen protection bottle 2 into the No. 1 and No. 2 feed tubes in the feed device 3, then put the No. 1 feed tube into CH2Cl2, and put the No. 2 feed tube into the CH2Cl2 solution of compound 1; start the feed device 3, and the feed ratio between the No. 1 feed tube and the No. 2 feed tube is 9:1;

[0023] S2, the feeding device 3 transports CH2Cl2 and the CH2Cl2 solution of compound 1 to the reaction device 7 through the liquid inlet pipe 15, and mixes them evenly; sampling, analysis and testing are performed to obtain a peak m / z 538.0 of compound 1;

[0024] S3, the reaction three-way valve 23 connects the oxygen outlet pipe 21 and the gas inlet pipe 19; the oxygen in the oxygen source bottle 9a passes through the oxygen outlet pipe 21, the reaction three-way valve 23, and the gas inlet pipe 19 in sequence and enters the reaction device 7, and when the pressure in the pressure sensor monitoring device reaches 1 atm, stirring is started and the reaction timing is started;

[0025] S4. Set the sampling volume to 0.1 mL, perform sampling and analysis testing, and obtain the peak m / z 570.0 of compound 2; set sampling and analysis testing at different times to monitor the reaction;

[0026] The sampling process is as follows: the injection three-way valve 24 is connected to the syringe connecting tube 12 and the six-way valve and three-way valve connecting tube 14, and the injection six-way valve 25 is connected to the six-way valve and three-way valve connecting tube 14 and the filtration and injection connecting tube 16; the syringe 26 is started to suck, and a negative pressure is formed in the pipeline, and the sample in the reaction device 7 is extracted. After the sample is filtered by the filter device 8 through the liquid outlet pipe 18, it enters the syringe 26 through the filtration and injection connecting tube 16, the injection six-way valve 25, the six-way valve and three-way valve connecting tube 14, the injection three-way valve 24, and the syringe connecting tube 12 in sequence;

[0027] The injection three-way valve 24 connects the syringe connecting tube 12 and the six-way valve and three-way valve connecting tube 14, and the injection six-way valve 25 connects the six-way valve and three-way valve connecting tube 14 and the injection and analysis connecting tube 17; the syringe 26 pushes, and the sample passes through the syringe connecting tube 12, the six-way valve and three-way valve connecting tube 14, and the injection and analysis connecting tube 17 in sequence into the analysis device 5 for analysis.

[0028] The feeding device 3 is a quaternary low-pressure pump, which can set the flow rate range to 0~10 mL / min. There are four feeding pipelines 11 on it, which can absorb the chemical reagents required for 4 chemical reactions at the same time. The material of the feeding pipeline 11 is tetrafluoroethylene, which has good corrosion resistance to acids, alkalis and organic reagents. The other end of the feeding pipeline 11 is placed in a nitrogen protection bottle 2. The feeding device 3 has an outlet pipeline-liquid inlet pipe 15, which is made of the same material as the feeding pipeline 11 and is connected to the liquid inlet of the reaction device 7, so that automatic feeding can be achieved according to the reaction requirements.

[0029] The reaction device 7 is explosion-proof. The reaction device is divided into an inner frame and an outer frame. A Peltier element is placed between the inner and outer frames, and its function can provide heating and cooling functions for the reactor body. Insulation cotton is placed between the inner and outer frames to avoid the position of the Peltier element to prevent heat loss inside the device. A control panel and a temperature display are set on the outer surface of the outer frame of the reactor body. The control panel can set the functional parameters of the feeding device, the reaction device, the sampling device and the cleaning device to realize automatic control of the reaction. The temperature display can display the temperature of the current reaction.

[0030] A 2-position 3-way electromagnetic switching valve - a reaction three-way valve 23 is placed on the outer surface of the outer frame of the reaction device 7. One hole on the electromagnetic switching valve is connected to the Yangqi outlet pipe 21, another hole is connected to the nitrogen outlet pipe 20, and the remaining hole is connected to the reaction device cover as the electromagnetic switching valve gas outlet through the gas inlet pipe 19, which can realize automatic switching of different gases. The reaction device cover is arc-shaped, and there is a sensor on it to monitor the liquid level change and the pressure and temperature in the reactor.

[0031] The inner tank inside the reaction device is made of quartz material and is placed in the inner frame of the reaction device. After the reaction, it can be taken out, cleaned and reused. A magnetic particle is placed at the bottom for stirring during the reaction.

[0032] The inlet of the filtering device 8 is connected to the liquid outlet pipe 18 on the reaction device 7, and the outlet is connected to the injection device 4 through the filtering and injection connecting pipe 16. The function is to filter the sample solution absorbed by the injection device as needed to avoid contamination of the injection device and the detection device.

[0033] The inlet of the sample injection device 4 is connected to the outlet of the filtering device 8, and is composed of a 2-position 6-way electromagnetic switching valve-sample injection six-way valve 25, a 2-position 3-way electromagnetic valve-three-way valve 24 and a syringe 26. The 2-position 6-way electromagnetic switching valve-sample injection six-way valve 25 has two holes connected to the quantitative loop, one hole connected to the analysis device 5 through the sample injection and analysis connecting pipe, one hole connected to the filtration and sample injection connecting pipe 16, one hole connected to the auxiliary sample injection device 1 through the auxiliary sample injection pipeline 10, and one hole connected to the 2-position 3-way electromagnetic valve-sample injection three-way valve 24 through the six-way valve and three-way valve connecting pipe 14. The remaining two holes of the 2-position 3-way electromagnetic valve-sample injection three-way valve 24, one hole is connected to the cleaning liquid bottle 6 through the valve and the cleaning liquid bottle connecting pipe 13, to provide cleaning liquid for the syringe 26 when cleaning; the other hole is connected to the syringe 26 through the syringe connecting pipe 12. During injection, the injection three-way valve 24 switches to the syringe connection channel to draw the sample for injection; during cleaning, the injection three-way valve 24 switches to the cleaning liquid channel to draw the cleaning liquid to clean the injection device pipeline.

[0034] The analysis device 5 is generally a gas chromatograph GC, a mass spectrometer MS or a gas chromatography-mass spectrometry detector GC-MS. The instrument function parameters are set according to the properties of the sample, and the sample can be automatically analyzed.

[0035] The auxiliary sample injection device 1 is a single pump, which is connected to the sample injection device through a pipeline 10, and absorbs specific reagents, such as acetonitrile, dichloromethane, etc., and transports the sample to the analysis device.

[0036] Example 1

[0037] According to the reaction conditions, an automated multifunctional online reaction and mass spectrometry in-situ sampling system provided by the present invention is used to perform reaction and product analysis.

[0038] 1) Firstly, feed pipelines No. 1 and No. 2 of the feed device inhale nitrogen through a nitrogen protection bottle, then put pipeline No. 1 into CH2Cl2, and pipeline No. 2 into a CH2Cl2 solution of bionic sulfur-bridged diiron amide 1, connect position 1 of the solenoid valve on the reaction device to the O2 gas bottle, position 2 to the nitrogen gas bottle, and connect the gas outlet pipe to the gas inlet pipe on the reactor cover.

[0039] 2) Through the control panel, set the flow rate of the feeding device to 5 mL / min, the time to 2.5 min, the channel selections to 1 and 2, the ratio to 9:1, the gas channel of the reaction device to 1 (O2), the pressure to 1 atm, the temperature to room temperature, the reaction time to 24 h, and run the system after setting.

[0040] 3) The feeding device transports CH2Cl2 and CH2Cl2 solutions of compound 1 into the inner tank of the reaction device through pipelines in proportion, stirs them evenly, takes samples, and tests them to obtain a raw material peak m / z 538.0.

[0041] 4) Switch the solenoid valve on the reaction device to position 1 through the control panel, inject O2 into the reaction device through the pipeline, wait until the pressure in the device monitored by the pressure sensor reaches 1 atm, and when the reaction device parameters are ready, turn on the stirring function, start the reaction timing, set the sampling volume to 0.1 mL, and inject samples into the MS at different times (see Figure 2 ), the reaction generates a product peak m / z 570.0, and the endpoint of the reaction is monitored.

[0042] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for online reaction and mass spectrometry in-situ sampling analysis, characterized in that: The following steps are involved: ； S1. First, the No. 1 and No. 2 feed tubes in the feed device (3) are allowed to inhale nitrogen through the nitrogen protection bottle (2), and then the No. 1 feed tube is placed in CH2Cl2, and the No. 2 feed tube is placed in the CH2Cl2 solution of compound 1; the feed device (3) is started, and the feed ratio between the No. 1 feed tube and the No. 2 feed tube is 9:1; S2, the feeding device (3) transports CH2Cl2 and the CH2Cl2 solution of compound 1 to the reaction device (7) through the liquid inlet pipe (15), and mixes them evenly; performs sampling, analysis and testing, and obtains a peak m / z 538.0 of compound 1; S3, the reaction three-way valve (23) is connected to the oxygen outlet pipe (21) and the gas inlet pipe (19); the oxygen in the oxygen source bottle (9a) passes through the oxygen outlet pipe (21), the reaction three-way valve (23), and the gas inlet pipe (19) in sequence and enters the reaction device (7); when the pressure in the pressure sensor monitoring device reaches 1 atm, stirring is started and the reaction timing is started; S4. Set the sampling volume to 0.1 mL, perform sampling and analysis testing, and obtain the peak m / z 570.0 of compound 2; set sampling and analysis testing at different times to monitor the reaction; The sampling process in steps S2 and S4 is as follows: the injection three-way valve (24) is connected to the syringe connecting tube (12) and the six-way valve and three-way valve connecting tube (14), and the injection six-way valve (25) is connected to the six-way valve and three-way valve connecting tube (14) and the filtration and injection connecting tube (16); the syringe (26) is started to suck, a negative pressure is formed in the pipeline, and the sample in the reaction device (7) is extracted. After the sample is filtered through the filter device (8) through the liquid outlet tube (18), it enters the syringe (26) in sequence through the filtration and injection connecting tube (16), the injection six-way valve (25), the six-way valve and three-way valve connecting tube (14), the injection three-way valve (24), and the syringe connecting tube (12); The injection three-way valve (24) is connected to the syringe connecting tube (12) and the six-way valve and three-way valve connecting tube (14), and the injection six-way valve (25) is connected to the six-way valve and three-way valve connecting tube (14) and the injection and analysis connecting tube (17); the syringe (26) pushes the sample, and the sample passes through the syringe connecting tube (12), the six-way valve and three-way valve connecting tube (14), and the injection and analysis connecting tube (17) in sequence and enters the analysis device (5) for analysis.

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