CN110715972A - Mass spectrum monitoring platform based on double-spray rejection interface and analysis method - Google Patents

Mass spectrum monitoring platform based on double-spray rejection interface and analysis method Download PDF

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CN110715972A
CN110715972A CN201910933874.5A CN201910933874A CN110715972A CN 110715972 A CN110715972 A CN 110715972A CN 201910933874 A CN201910933874 A CN 201910933874A CN 110715972 A CN110715972 A CN 110715972A
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spray
electrospray
double
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熊博
白玉娜
苏醒
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Huazhong Normal University
Central China Normal University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/0027—Methods for using particle spectrometers
    • H01J49/0031—Step by step routines describing the use of the apparatus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/165—Electrospray ionisation

Abstract

The invention belongs to the field of mass spectrometry detection, and particularly relates to a mass spectrometry monitoring platform based on a double-spray rejection interface and an analysis method. The mass spectrum monitoring platform comprises a DRR, a high-voltage direct-current power supply and a high-resolution mass spectrometer, wherein the double-spray rejection reactor is composed of two double-liquid-flow mixed single-spray chips or is an integrated chip composed of two double-liquid-flow mixed single-spray chips, the structure of the double-liquid-flow mixed single-spray comprises a reactant channel, an ESI (electrospray ionization) spray liquid channel and an electrospray tip, the positive and negative electrodes of the high-voltage direct-current power supply are connected to the two electrospray tips, and electrospray formed by the electrospray tip enters the high-resolution mass spectrometer for detection. The invention discloses a double-spray rejection reactor (DRR), which controls the rejection between two Taylor cone beams by adjusting the relative positions of two spray tips, thereby adjusting the reactant mixing area and further achieving the purpose of adjusting and controlling the reaction duration.

Description

Mass spectrum monitoring platform based on double-spray rejection interface and analysis method
Technical Field
The invention belongs to the field of mass spectrometry detection, and particularly relates to a mass spectrometry monitoring platform based on a double-spray rejection interface and an analysis method.
Background
Electrospray ionization (ESI) is a widely used soft ionization technique that converts an analyte into gas-phase ions without destroying the molecular structure of the sample to be detected. In recent years, more and more research teams have developed ESI electrospray instruments with two or more emitters based on conventional ESI ionization sources with only a single nebulizer.
The dual-spray configuration ionization mass spectrometry is usually based on the diffusion of two independent electrospray gases, and the reaction is carried out in the ionization process of a body to be detected, so that the reaction process is monitored in situ and on line. Due to coulomb repulsion of the same charge and the gas and liquid fluid field characteristics tending to diffuse, a balance of mutual repulsion and diffusive mixing exists between the two electrospray species carrying the same charge. If the balance of repulsion and mixing can be controlled, the regulation and control of the double-spray reaction state can be realized, and the representation of the double-spray reaction process can be further realized. In the rejection interface double-spray mass spectrometry, the double-spray reaction state is regulated and controlled based on the rejection phenomenon of double spray, and at least two problems need to be solved: (1) the repulsion and diffusion between the double sprays should be fully understood, thereby obtaining the spatial configuration of the double sprays under different conditions; (2) the stability of the double-spray rejection interface should be improved, and the problem of poor reproducibility of the double-spray mass spectrometry is solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a mass spectrum monitoring platform and an analysis method based on a double-spray rejection interface.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a mass spectrum monitoring platform based on a double-spray rejection interface comprises a double-spray rejection Reactor (DRR), a high-voltage direct-current power supply and a high-resolution mass spectrometer, wherein the double-spray rejection Reactor consists of two double-liquid-flow mixed single-spray chips or is an integrated chip consisting of two double-liquid-flow mixed single-spray chips, the structure of the double-liquid-flow mixed single-spray comprises a reactant channel, an ESI (electronic spray) liquid spray channel and an electrospray tip, the two electrospray tips are respectively connected with the positive electrode and the negative electrode of the high-voltage direct-current power supply, and electrospray formed by the electrospray tip enters the high-resolution mass spectrometer for detection.
In the above scheme, the injector needle is used as the electrospray tip of the double-fluid-flow mixing single-spray chip.
In the scheme, the included angle of the two electrospray tips is 20-90 degrees, and the horizontal distance is 0-15 mm.
In the scheme, the distance between the midpoint of the connecting line of the two electrospray tips and the mass spectrum sample inlet is 5-15 mm.
In the scheme, the two electrospray tips are respectively clamped with electrode clamps connected with a high-voltage direct-current power supply.
The method for performing mass spectrometry by adopting the mass spectrometry monitoring platform based on the double-spray rejection interface comprises the following steps:
(1) preparing a reactant A solution, a reactant B solution and an electrolyte solution;
(2) respectively introducing a reactant A solution, a reactant B solution and an electrolyte solution into a reactant channel and an ESI electrospray solution channel, and respectively and uniformly mixing the reactant A and the reactant B with the electrolyte solution in the respective channels to obtain a mixed solution;
(3) the mixed solution forms two strands of electrospray at the electrospray tip loaded with high-voltage direct current, a chemical reaction is carried out on a compound A and a compound B at a Taylor cone beam overlapping interface formed by the two strands of electrospray to generate a product C, and the product C directly enters a sample inlet of a high-resolution mass spectrum electrospray ionization source along with a reactant A and a reactant B, so that high-resolution mass spectrum detection of reactant ions generated by double-spray rejection reaction is realized.
In the scheme, the voltage of the high-voltage direct current is 0.5-2.0 KV.
In the scheme, the flow rate of the reactant A solution and the electrolyte solution in the reactant channel is 0.1-2.0 muL/min, and the flow rate of the reactant B solution and the electrolyte solution is 0.1-2.0 muL/min.
In the scheme, the solution in the reactant channel and the ESI electrospray liquid channel and the flow rate ratio thereof can be controlled on line.
In the invention, COMSOL multi-physical field simulation software is adopted to simulate the mass spectrometry process based on the dual-spray rejection interface mass spectrometry monitoring platform, and the method specifically comprises the following steps:
(1) establishing a two-dimensional model of a double-spray rejection reactor, determining that the fluid in a channel has laminar flow characteristics by calculating the Reynolds number (Re) of the fluid, and solving the liquid flow velocity at the outlet of the electrospray tip under the condition of loading high-voltage direct current, namely the initial velocity v of electrospray particles according to the Navier-Stokes equation of the laminar flow fluid0；
(2) Building a three-dimensional space model of an electrospray tip and a sample inlet of an electrospray ionization source of a high-resolution mass spectrum, calculating the propagation condition of a charged particle beam in a free space, determining the shape of the charged particle beam by solving a group of strong coupling equations describing the potential and the electron trajectory of an electron beam, and finally calculating the reaction time of the charged particle; the specific steps of coupling the transient research step of calculating the particle trajectory with the steady state step of calculating the potential are as follows: calculating particle trajectories by using a transient solver, calculating space charge density according to the trajectories, calculating potential generated by the space charge density of the electron beam by using a steady solver, thereby calculating disturbed particle trajectories, and recalculating the space charge density by using the disturbed trajectories; after multiple iterations, the particle trajectories and the corresponding space charge densities can reach stable self-consistent solutions;
(3) collecting a deposition pattern of double sprays on filter paper under an experimental condition by using the mass spectrum monitoring platform based on the double-spray rejection interface, comparing and analyzing a double-spray distribution pattern under the experimental condition with a double-spray pattern obtained by theoretical simulation, and verifying that the theoretical simulation double-spray pattern obtained by simulation of COMSOL multi-physics field simulation software has high consistency with the theoretical simulation double-spray pattern obtained under the experimental condition;
(4) utilizing COMSOL multi-physics field simulation to simulate a double-spray form to find a double-spray overlapping area which is only the minimum, namely a limit minimum overlapping interface of double sprays; meanwhile, the shortest reaction time and the reaction conversion rate corresponding to the minimum reaction area.
In the above scheme, the expression of the Navier-Stokes equation is
Figure BDA0002221026620000031
ρ is the fluid density (1000 kg/m)3) U is the characteristic velocity of flow (0.025m/s), mu is the viscosity of the fluid (1 mPas), L is the characteristic size of the device (1^10-3m), the concentration of the experimental sample is extremely low (< 5 ng/mu L), the fluid can be regarded as pure water, the density and viscosity values of the fluid in the following calculation process can adopt the characteristic values of the pure water at 20 ℃, therefore, the Reynolds number of the fluid is obviously less than 2000, the flow characteristic of the fluid is laminar flow, and therefore the initial velocity v of the electrospray particles is0Conform to
Figure BDA0002221026620000032
Figure BDA0002221026620000033
Where u is the velocity (m/s) and p represents the pressure (101 KPa).
In the above scheme, the strong coupling equation of the electron beam potential and the electron trajectory is
Figure BDA0002221026620000034
Figure BDA0002221026620000035
Where e is 1.602176565 × 10-19C is the element charge, V is the voltage 1600V, δ is the dirac δ number (the δ function represents the density distribution of an ideal model of particle, point charge, etc., the function takes a value equal to zero at points other than zero, and its integral over the entire domain is equal to 1), and V is the initial velocity V of particle ejection0。
In the above solution, the charged particle beam morphology may be given by the following formula
Figure BDA0002221026620000036
Where z is the distance from the beam waist, defined here as the initial emission cross-section of the particle beam, i.e. the circular exit of the electrospray, R0Is the girdling radius (instinct)The calculation is the radius of the inner diameter of the electrospray needle tip, 0.1mm), and K is the generalized electron beam conductivity coefficient (the expression of K is:
Figure BDA0002221026620000037
χ is the ratio of beam radius to beam waist radius, and
Figure BDA0002221026620000038
in the above scheme, the contribution of each model particle to the total space charge density of the particle beam can be obtained by the following formula:
Figure BDA0002221026620000041
where e is 1.602176565 × 10-19C is the elementary charge, Z is the number of charges of the particle +1, δ is the dirac δ function, frelThe effective frequency of particle release is the number of particles contained in each model particle per second, 10000 is set in the model, and the self-consistent solution of particle trajectories and beam potentials can be achieved after the formula is subjected to multiple iterative calculations of COMSOL software.
The working principle of the mass spectrum monitoring platform based on the double-spray rejection interface is as follows: the reactant A and the reactant B are respectively and uniformly mixed with electrolyte solution through the square-shaped channel of the chip; two strands of electrospray are formed on the mixed solution at the needle tip of the injector loaded with the high-voltage direct current, chemical reaction occurs at the overlapped interface of the double sprays to generate a product C, the spraying reaction area is regulated and controlled through the double-spraying interface, the reaction duration is further regulated and controlled, and finally the reactant and the product directly enter an ion transmission channel of a mass spectrum to perform mass spectrum characterization.
The invention has the beneficial effects that:
(1) the invention develops a double-spray rejection reactor (DRR), which can control the rejection between two Taylor cone beams by adjusting the relative positions of two spray tips, thereby adjusting the reactant mixing area and further achieving the purpose of regulating and controlling the reaction duration;
(2) the invention utilizes COMSOL software to simulate the repulsion and the spatial distribution of dual-electric spray Taylor cone beams, and obtains the reaction duration with DRRCorresponding repulsion interface is formed, and the initial velocity v of the charged micro-liquid drop at the tip of the electric spray is solved0Fitting is further carried out according to the double-spray distribution configuration under different experimental conditions, and the limit reaction time is obtained through calculation;
(3) according to the method, through evaluating and optimizing various relevant indexes of double sprays, the area of an overlapping area of the double sprays is regulated and controlled on line, the generation of a product is controlled, and a limit minimum reaction area of the double sprays is obtained; on the basis, the integrally formed DRR is constructed, and the on-line detection of the reaction and the determination of the reaction grade can be realized.
Drawings
FIG. 1 is a schematic diagram and a physical diagram of a DRR structure, wherein S1 is a reactant A, S3 is a reactant B, S2 and S4 are ESI solutions, two reaction interfaces are composed of a reactant channel and an electrospray liquid, and a high-voltage power supply is clamped at the tip of the electrospray liquid.
Fig. 2 is a schematic structural diagram and a physical diagram of an integrated 3D printed DRR.
FIG. 318C 6 is the mass spectrum of the coordination reaction and substitution reaction with Na + and K +.
FIG. 4 is an experimental diagram of on-line control of the dual spray reaction zone.
FIG. 5 is a plot of DRR and dual spray configurations.
FIG. 6 is a 2D model diagram of a double spray reactor simulated by COMSOL multi-physics simulation software.
FIG. 7 is a 3D model of the spatial region from the electrospray tip to the mass spectrometry sample inlet.
Fig. 8 is a side view (a), a front view (b), and a cross-sectional view (c) of the propagation fit of the charged particle beam in free space.
FIG. 9 shows the optimization of the linear distance between the midpoint of the line connecting the two spray tips and the mass spectrometer inlet.
Figure 10 optimization of the distance between two spray tips.
FIG. 11 determination of the number of reaction stages of BA with glucose.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
As shown in fig. 1 and 2, the mass spectrometry monitoring platform based on the dual-spray repulsion interface comprises reactant channels S1 and S4, and ESI electrospray fluid channels S2 and S3. The double-spray rejection reactor is composed of 2 double-liquid-flow mixing single-spray chips, an injector needle is used as an electric spray tip of the double-liquid-flow mixing single-spray chip, and two sprays formed by the spray tip can control the flow rate ratio of the solution in each spray on line. The double-spray rejection reactor is characterized in that electrode clamps connected with a controllable direct-current high-voltage power supply are respectively clamped at the tail ends of two needle point metal parts, and high voltage is conducted into a solution to promote the formation of electric spray. As shown in fig. 2, the schematic diagram of the apparatus for performing mass spectrometry detection by using the high-resolution mass spectrometry electrospray ionization source includes a dual-spray rejection reactor, a high-voltage direct-current power supply, a high-resolution mass spectrometry electrospray ionization source, and a mass spectrometry detector. The working principle of mass spectrometry detection is as follows: the reactant A and the reactant B are respectively and uniformly mixed with an electrolyte solution through a square channel of the chip, two strands of electrospray are formed at the needle point of the injector loaded with high-voltage direct current, a chemical reaction is carried out at the overlapped interface of the two sprays to generate a product C, and the product C directly enters a mass spectrum for characterization, so that the high-resolution mass spectrum detection of reactant ions generated by the double-spray rejection reaction is realized.
Example 2
The method for performing mass spectrometry by using the mass spectrometry monitoring platform based on the dual spray rejection interface shown in embodiment 1 comprises the following steps:
(1) respectively preparing an 18C6 solution, a NaCl solution and a KCl solution, wherein the solvents are deionized water;
(2) experiment one, pure 18C6 solution; experiment two, 18C6, NaCl and deionized water are mixed in a volume ratio of 3:1: 2; experiment three, mixing 18C6, KCl and deionized water in a volume ratio of 3:1: 2; experiment four, mixing 18C6, NaCl and deionized water in a volume ratio of 3:1:1, and adding 1 volume of KCl;
(3) the reaction mixture A: 18C6 solution, reactant B: introducing NaCl, KCl solution and electrolyte solution into a double-spray reactor, ionizing by high-voltage current, and then introducing into an ion transmission channel of a mass spectrum for mass spectrum detection, wherein the mass spectrum detection result is shown in figure 3 below.
Wherein the reactant A: the concentration of the 18C6 solution was 3. mu.M; and (3) reaction product B: the concentration of NaCl and KCl solution is 100 mu M, the flow rate of the electric spraying liquid outlet is 1.5 mu L/min, and the voltage is 1.6 KV.
The ion detection results of the reaction products in this example are as follows: in FIG. 3a except for [18C6+ H ]]+Besides the mass spectrum peak of (1), the product also has obvious [18C6+ Na]+、[18C6+K]+And [18C6+ NH4]+Probably because 18C6 is very sensitive to ambient Na+、K+And NH4 +A coordination reaction occurs in which Na bound to 18C6+、K+、NH4 +Possibly from air. FIG. 3b is the mass spectrum of the mixed solution of 18C6 and NaCl in which Na is added to 18C6+Then, [18C6+ H]+The mass spectrum of (1) almost disappears, and [18C6+ Na]+May be 18C6 and Na in solution+A coordination reaction is carried out to generate [18C6+ Na]+. FIG. 3C is the mass spectrum of the mixed solution of 18C6 and KCl, K is added into 18C6 solution+Then, [18C6+ H]+Almost disappears and the mass spectrum of [18C6+ NH ]4]+And [18C6+ Na]+All the signals are relatively reduced in intensity, and [18C6+ K ]]+The signal intensity is relatively high, which may be 18C6 and K in solution+The coordination reaction is carried out, and the coordination ability is stronger. FIG. 3d is [18C6+ Na ]]+Mass spectrum of the mixed solution with KCl at 18C6+ Na]+Adding K into the solution+Then, [18C6+ Na ]]+Will relatively decrease in signal strength, and [18C6+ K]+Then the signal of (2) is relatively high, probably due to K+Can replace Na which is coordinated with 18C6+And laterally demonstrate K+The coordination ability of the compound to 18C6 is stronger than that of Na+. This demonstrated 18C6 and Na+、K+The coordination reaction and the displacement reaction can be smoothly carried out, and reactants and products can be characterized by ESI-TOF type mass spectrum.
Example 3
The method for performing mass spectrometry by using the mass spectrometry monitoring platform based on the dual spray rejection interface shown in embodiment 1 comprises the following steps:
(1) setting the flow rate of the electric spraying liquid outlet at 1.5 mul/min and the voltage at 1.6KV, and introducing [18C6+ Na ] into S1 and S4 respectively]+Introducing electrolyte solution into S2 and S3 sample inlets, and adjusting the initial horizontal distance between the two needle tips to be 5mm, the included angle to be 30 ℃ and the distance to the mass spectrum sample inlet to be 10 mm;
(2) the horizontal distance between the two chips is adjusted to be 1.00, 2.00, 2.50, 3.00, 3.50, 4.00, 4.25, 4.75, 5.00 and 5.25mm from small to large in sequence by reversely and synchronously controlling the two independent three-dimensional adjusting frames, then the horizontal distance is adjusted to be 1.00mm from 5.25mm to small from large to small in sequence, and the midpoint of the connecting line of the two tips is always kept to be aligned with a mass spectrum sample inlet;
(3) collecting [18C6+ K ] in the whole regulation process]+And [18C6+ Na]+The gradient change of the reactant signal was observed, and the horizontal distance of the two spray tips just touching was determined, as shown in fig. 4.
Wherein the reactant [18C6+ Na%]+The concentration of the solution is 1 ng/. mu. L, KCl, and the concentration of the solution is 0.5 ng/. mu.L; the electrolyte solution is methanol V and water V are 4:1, and the initial horizontal distance between the two needle points is 1.00 mm; and in the process of adjusting the horizontal distance between the two spraying reactors, the two adjacent spraying reactors stay for 5 min.
The detection results of the product ion intensities of the different reflection regions in this example are shown in fig. 4, which contains two abscissas, wherein the upper abscissa (5.5 → 1) represents a curve in which the ion intensity gradually decreases from left to right, and the lower abscissa (1 → 5.5) represents a curve in which the ion intensity gradually increases from left to right. From the trend of the two curves, the overlapping area of the double sprays is gradually increased along with the reduction of the horizontal distance between the two tips, and when the horizontal distance is less than a certain critical value (2.00 mm adjusted from small to large and 1.50mm adjusted from large to small), the change of the distance has no obvious influence on the overlapping area of the sprays. From this phenomenon, it is presumed that the overlapping area of the two sprays reaches a minimum value at a distance of 4.75mm between the tips.
The spray overlap area will be at a maximum at a tip distance of between 1.50mm and 2.00 mm. The DRR-MS platform can realize the online regulation and control of the reaction region by adjusting the distance between the two chips.
Example 4
A mass spectrometry process of a mass spectrometry monitoring platform for simulating a double-spray rejection interface by adopting COMSOL-based multi-physical-field simulation software is characterized by comprising the following steps of:
(1) first, the initial velocity v of the electrospray particles was calculated by a two-dimensional model of the DRR (FIG. 6)0Then, a three-dimensional model (figure 7) of a region between the electrospray tip and the mass spectrum injection port is built, a transient solver is used for calculating particle tracks, space charge density is calculated according to the tracks, a steady solver is used for calculating potential generated by the space charge density of the electron beam, so that disturbed particle tracks are calculated, finally the disturbed tracks are used for recalculating the space charge density, and after multiple iterations, the particle tracks and the corresponding space charge density can reach stable self-consistent solution, so that the propagation tracks (figure 5) of the charged particles in the space and the form (figure 8) of the particle beams can be solved, and the reaction time is finally calculated;
(2) additionally setting the distance between two electrospray outlets in the three-dimensional model, respectively setting the vertical distance between the electrospray outlets and the mass spectrum sample inlet to be 6, 7, 8, 9, 10, 12 and 15mm, sequentially calculating, and extracting the calculation result of the charged particle tracking module to obtain a double-electrospray pattern diagram (figure 9a) with different distances between the electrospray outlets and the mass spectrum sample inlet;
(3) setting the distance between two electrospray nozzles in the model and the mass spectrum, sequentially setting the distance between the two spray outlets to be 0, 1, 2, 5, 8, 10 and 15mm, then calculating, and extracting the calculation result of the charged particle tracking module to obtain a double-spray configuration diagram (figure 10a) of the two tips at different distances;
(4) collecting a deposition pattern of double sprays on filter paper under an experimental condition by using the mass spectrum monitoring platform based on the double-spray rejection interface, comparing and analyzing a double-spray distribution pattern under the experimental condition with a double-spray pattern obtained by theoretical simulation, and verifying that the theoretical simulation double-spray pattern obtained by simulation of COMSOL multi-physics field simulation software has high consistency with the theoretical simulation double-spray pattern obtained under the experimental condition; and (3) carrying out comparative analysis on the two groups of spray configurations calculated in the steps (2) and (3) by combining the configuration of the electrospray on the filter paper and the experimental result obtained by the chip-mass spectrometry experiment, and finding out a double-spray overlapping area which is only the minimum, namely the minimum overlapping interface of the double sprays.
Wherein, the voltage of the needle point used for simulating the distance between the two electrospray nozzles and the mass spectrum is 1.6kV, the distance between the two needle points is 5mm, and the included angle is 30 degrees; the used needle point voltage when the distance between the two electrospray outlets of the model is 1.6kV, the midpoint of the connecting line of the two spray tips is 10mm away from the mass spectrum sample inlet, and the included angle is 30 degrees.
The results obtained in this example by simulation are as follows: as can be seen from fig. 9 and 10, in order to ensure that the double sprays have the smallest possible overlapping area in the subsequent experiment, 0mm to 15mm should be selected as the optimal linear distance between the midpoint of the connection line of the two spray tips and the mass spectrum injection port, and 5mm to 15mm should be selected as the distance between the two spray tips, taking the overlapping area, the ionization efficiency, and the stability of the double sprays into comprehensive consideration. The fitting result of the COMSOL software under the condition has good consistency with the effect achieved by the deposition pattern of the double spray on the filter paper.
Example 5
An analysis method for continuously monitoring the generation condition of a product by adopting a mass spectrometry monitoring platform based on an integrated DRR is characterized by comprising the following steps:
(1) and (3) constructing an experimental device shown in the figure 2b, opening high-voltage direct current, setting voltage and flow rate, introducing a BA solution into an injection port S1, sealing an injection port S2 by using a solid screw, introducing pure acetonitrile into the injection port S3, and introducing a glucose (Glu) solution into the injection port S4. Keeping the total flow rate of the glucose and the acetonitrile constant in a certain time period, and sequentially changing the ratio of the flow rate of the glucose to the total flow rate to 1/6, 1/3, 1/2, 2/3, 5/6 and 1;
(2) in the whole collection process [18C6+ K]+Signal and product of [ BA + Glu ]]+And performing optimized calculation and analysis of internal standard substanceChange in glucose concentration vs product [ BA + Glu]+Influence of production amount;
(3) keeping various parameters unchanged, sealing an S3 sample inlet by using a solid screw, introducing acetonitrile into an S2 sample inlet, keeping the initial flow rate of glucose and acetonitrile at 1.5 mu L/min and the initial flow rate of BA at 0, keeping the total flow rate of BA and acetonitrile unchanged in a certain time period, and simultaneously sequentially changing the ratio of the flow rate of BA in the total flow rate to 1/32, 1/16, 1/8, 1/4, 1/2 and 1;
(4) in the whole collection process [18C6+ K]+Signal and product of [ BA + Glu ]]+Was optimized and analyzed for changes in glucose concentration versus product [ BA + Glu]+The results of the influence of the amount of production are shown in FIG. 11.
Wherein 1 percent of [18C6+ K ] is added into the solution]+And 5% formic acid [18C6+ K ]]+The method is characterized in that the method is an internal standard substance, the voltage is 1.6kV, the time periods are 2-5 min, 12-15 min, 22-25 min, 32-35 min, 42-45 min and 52-55 min, and the flow rate ratio of the rest time periods is returned to the initial setting.
The results of the reaction of the reactants BA and Glu in this example were as follows: as can be seen from fig. 11, when the glucose concentration is linearly increased, the ionic strength of the product is linearly increased in the first order, and the reaction rate is in the first order index with respect to glucose, but the amount of the product is not changed according to the change of the BA concentration, and thus the reaction rate is in the zero order index with respect to BA. Since there are only two reactants, the reaction is overall a first order reaction.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Thus, obvious variations or modifications can be made without departing from the scope of the invention.

Claims (9)

1. A mass spectrum monitoring platform based on a double-spray rejection interface is characterized by comprising a double-spray rejection Reactor (DRR), a high-voltage direct-current power supply and a high-resolution mass spectrometer, wherein the double-spray rejection Reactor is composed of two double-liquid-flow mixed single-spray chips or is an integrated chip composed of two double-liquid-flow mixed single-spray chips, the structure of the double-liquid-flow mixed single-spray comprises a reactant channel, an ESI (electrospray ionization) liquid channel and an electrospray tip, the anode and the cathode of the high-voltage direct-current power supply are respectively connected to the two electrospray tips, and the electrospray formed by the electrospray tip enters the high-resolution mass spectrometer for detection.
2. The dual spray exclusion interface-based mass spectrometry monitoring platform of claim 1, wherein a syringe needle is used as an electrospray tip for the dual stream mixing single spray chip.
3. The dual-electrospray repulsion interface-based mass spectrometry monitoring platform of claim 1, wherein the angle between the two electrospray tips is 20 ° -90 ° and the horizontal distance is 0 mm-15 mm.
4. The dual-electrospray repulsion interface-based mass spectrometry monitoring platform according to claim 1, wherein the distance between the midpoint of the connection line of the two electrospray tips and the mass spectrometry sample inlet is 5-15 mm.
5. The dual-electrospray repulsion interface-based mass spectrometry monitoring platform of claim 1, wherein electrode clamps connected to a high voltage direct current power supply are clamped on each of said two electrospray tips.
6. The method for performing mass spectrometry by using the mass spectrometry monitoring platform based on the dual-spray rejection interface as claimed in any one of claims 1 to 5, is characterized by comprising the following steps:
(1) preparing a reactant A solution, a reactant B solution and an electrolyte solution;
(2) respectively introducing a reactant A solution, a reactant B solution and an electrolyte solution into a reactant channel and an ESI electrospray solution channel, and respectively and uniformly mixing the reactant A and the reactant B with the electrolyte solution in the respective channels to obtain a mixed solution;
(3) the mixed solution forms two strands of electrospray at the electrospray tip loaded with high-voltage direct current, a chemical reaction is carried out on a compound A and a compound B at a Taylor cone beam overlapping interface formed by the two strands of electrospray to generate a product C, and the product C directly enters a sample inlet of a high-resolution mass spectrum electrospray ionization source along with a reactant A and a reactant B, so that high-resolution mass spectrum detection of reactant ions generated by double-spray rejection reaction is realized.
7. The method of mass spectrometry of claim 6, wherein the high voltage direct current has a voltage of 0.5-2.0 KV.
8. The method of mass spectrometry of claim 6, wherein the flow rates of the reactant A solution and the electrolyte solution in the reactant channel are 0.1-2.0 μ L/min, and the flow rates of the reactant B solution and the electrolyte solution are 0.1-2.0 μ L/min.
9. The method of mass spectrometry of claim 6, wherein the solution and flow ratio in the reactant and ESI electrospray fluid channels are controlled on-line.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105753890A (en) * 2016-02-05 2016-07-13 东华理工大学 Method for synthesizing metal organic framework material by adopting electrostatic spraying method
CN205628359U (en) * 2016-02-05 2016-10-12 东华理工大学 Two electrostatic spray devices

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105753890A (en) * 2016-02-05 2016-07-13 东华理工大学 Method for synthesizing metal organic framework material by adopting electrostatic spraying method
CN205628359U (en) * 2016-02-05 2016-10-12 东华理工大学 Two electrostatic spray devices

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
熊博: "基于微流控技术的高精度氮气辅助NANO电喷雾电离源及其应用", 《中国化学会第二届全国质谱分析学术报告会会议摘要集》 *
熊博: "基于聚焦型双喷雾芯片-质谱方法的反应在线调控和状态仿真", 《第三届全国质谱分析学术报告会摘要集》 *
白玉娜: "基于双参比微流控芯片_质谱的精确质荷比测定", 《中国化学会第十二届全国微全分析系统学术会议、第七届全国微纳尺度生物分离分析学术会议、第七届国际微流控学学术论坛》 *

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