CN108828118B - Combined system for nano-flow chromatography separation and plasma mass spectrometry detection - Google Patents
Combined system for nano-flow chromatography separation and plasma mass spectrometry detection Download PDFInfo
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Abstract
A combined system of nano-flow chromatography separation and plasma mass spectrometry detection comprises a connecting part for communicating a nano-flow chromatography separation part and a plasma mass spectrometry detection part; the nano-flow chromatographic column of the connecting part penetrates through the inner cavity of the support body in an airtight manner; an outer pipe is sleeved on a section of the nanoflow chromatographic column close to the second interface, and a gap is formed between the inner wall of the outer pipe and the nanoflow chromatographic column; the orifice at the outer end of the outer tube is flush and aligned with the second interface of the nano-flow chromatographic column; the outer end of the outer tube and the end of the nano-flow chromatographic column where the second interface is located are both sharp heads. The inner end of the outer tube is positioned in the inner cavity of the support body and is communicated with the inner cavity of the support body; the supporting body is provided with an air inlet, one end of the air inlet is communicated with an air source of the atomizing gas, and the other end of the air inlet is communicated with the inner cavity of the supporting body; the second interface is communicated with the plasma mass spectrum detection part through the atomization chamber, and the outer end of the outer tube and the second interface both extend into the inner cavity of the atomization chamber in an airtight manner; the atomizing chamber is also provided with a heating device and a gas transmission pipe.
Description
Technical Field
The invention relates to a combined system for nanoflow chromatography separation and plasma mass spectrometry detection.
Background
Morphological information of elements in environmental and biological samples helps one to understand its toxicity, mobility and bioavailability. The atomic spectrum analysis technology, especially the plasma mass spectrometry technology, is a powerful tool for analyzing the total amount of trace elements at present, but the existing form and the content of the trace elements in complex matrixes such as environment, biology, food and the like are difficult to analyze. The chromatographic analysis mode has various types and wide application range, and is an efficient means for analyzing different morphological species of trace elements in a complex matrix. Both nanoflow liquid chromatography and capillary electrophoresis are chromatographic techniques with high separation efficiency, high speed and small sample consumption, and the nanoflow liquid chromatography has higher separation selectivity. The plasma mass spectrum is used as a detector for capillary electrophoresis and nanoflow liquid chromatography, has high separation efficiency, high sensitivity and high element selectivity, and is a morphological analysis technology with great potential.
However, the combination of nanoflow liquid chromatography and plasma mass spectrometry must design an effective interface, the interface must be compatible with the flow rate of the two, so that the chromatography effluent is efficiently transmitted to the plasma mass spectrometry, and the dead volume of the interface is as small as possible to reduce the chromatography broadening effect. The combination of capillary electrophoresis and plasma mass spectrometry also requires an effective interface to be designed, and the interface needs to solve a problem of reducing the self-priming effect of a pneumatic atomizer used by a plasma mass spectrometer, wherein the self-priming effect of the atomizer can generate laminar flow in a separation capillary tube, interfere with the electrophoretic separation of different species and even cause separation failure. Therefore, the combination of nano-flow liquid chromatography and plasma mass spectrometry is better than the combination of capillary electrophoresis and plasma mass spectrometry in terms of the processing difficulty and separation selectivity of the interface. Nevertheless, the interface for combining nano-flow liquid chromatography with plasma mass spectrometry still needs to solve the problems of flow matching, high-efficiency sample transmission, interface dead volume and the like.
The sample injection flow of a conventional atomizer used for plasma mass spectrometry is generally 0.5-2 mL/min, and the sample injection flow of a micro atomizer is generally 5-100 muL/min, which far exceeds the flow rate of nanoflow liquid chromatography (tens of nL/min to muL/min level), so that most interfaces use high-flow sheath flow liquid to balance the flow difference of the two. However, the sheath flow fluid will dilute the analyte concentration in large amounts, significantly reducing the sensitivity of the interface. Another proposal is to use a nano-flow atomizer as a direct connection interfaceExcept for the use of sheath fluid. The nanoflow atomizers used require a high atomization efficiency and stability at the nanoflow level.
nDS-200[ anal. chem.,2006,78,965-]And nDS-200e [ J.anal.at.Spectrum, 2010,25,1963-]And d-NN [ J.anal.At.Spectrum., 2015,30, 1927-]Are nano-flow atomizers with good effect. However, they are complicated to manufacture and expensive, and cannot independently optimize the flow rates of the atomizing gas and the transport gas, the pressure of the atomizing gas is also low, and the sensitivity needs to be further improved. To independently optimize the flow rates of the atomizing and transport gases, the Bings project group developed thermal bubble based drop on demand generators (DOD) [ j.anal.at. spectra., 2011,26,1781-1789 and j.anal.at. spectra., 2012,27, 1234-1244]Groh et al developed DOD [ anal. chem., 2010,82,2568-]And commercialized by GmbH Inc. [ www.microdrop.de ]]. However, these DOD atomizers are very expensive (up to hundreds of thousands), complicated to operate, and have large dead volumes (not less than a few microliters), which limits their use as interfaces for nanofluidic liquid chromatography coupled with plasma mass spectrometry.
Another problem to be considered in the combination of nanoflow liquid chromatography with plasma mass spectrometry is the dead volume of the interface. The larger the dead volume of the interface, the longer the analyte stays there, and the more severe the broadening of the electrophoresis peak, reducing the separation efficiency and detection sensitivity. The existing interface for combining capillary electrophoresis with plasma mass spectrometry generally adopts two-way, three-way or four-way connection to a capillary chromatographic column, a sheath flow liquid pipeline and an atomizer, and the dead volume of the capillary chromatographic column, the sheath flow liquid pipeline and the atomizer is dozens of nanoliters as small as one, and is microliter as large as one, so that the electrophoresis peak is easily widened. The nanofluid atomizers used also have a considerable dead volume (few nanoliters, many hundreds of nanoliters). In addition, the manufacturing difficulty and cost of the coupling interface are both issues that need to be considered.
In addition to the interface, the preparation of capillary chromatography columns is another problem to be considered in the combination of nanoflow liquid chromatography and plasma mass spectrometry. Capillary chromatographic columns can be divided into packed columns, open tubular columns and monolithic columns according to the structure of the bed. Wherein, the packed column has wide application due to large column capacity, good manufacturing reproducibility and rich column materials. However, the packed column requires the production of a plunger, and the plunger is usually produced by a sintering method, a sol-gel method, an integral plunger method, a particle plunger method, a magnetic fixing method, or the like. However, these methods either take time to produce, or lack plunger material, or have poor reproducibility of plunger production, or produce plungers that cause spectral peak broadening.
Disclosure of Invention
In order to solve the problems, the invention provides a combined system of nano-flow chromatography separation and plasma mass spectrometry detection.
In order to achieve the above purpose, one embodiment of the present invention adopts the following technical solutions:
a combined system of nano-flow chromatography separation and plasma mass spectrometry detection comprises a connecting part for communicating a nano-flow chromatography separation part and a plasma mass spectrometry detection part;
the connecting part comprises a support body and a nanoflow chromatographic column, the nanoflow chromatographic column penetrates through the inner cavity of the support body in an airtight manner, and a first interface communicated with the nanoflow chromatographic separation part and a second interface used for communicating with the plasma mass spectrometry detection part are respectively formed at two ends of the nanoflow chromatographic column exposed out of the support body;
an outer pipe is sleeved on a section of the nano-flow chromatographic column close to the second interface, and a gap is formed between the inner wall of the outer pipe and the nano-flow chromatographic column; the outer end of the outer tube is positioned outside the inner cavity of the support body, and the tube opening of the outer end of the outer tube is flush and aligned with the second interface of the nano-flow chromatographic column; the outer end of the outer tube and one end of the nano-flow chromatographic column where the second interface is located are both sharp heads, the outer end of the outer tube forms an atomized gas nozzle, and the second interface forms a sample nozzle;
the inner end of the outer tube is positioned in the inner cavity of the support body and is communicated with the inner cavity of the support body; the supporting body is provided with an air inlet, one end of the air inlet is communicated with an air source of the atomizing gas, and the other end of the air inlet is communicated with the inner cavity of the supporting body;
the second interface is communicated with the plasma mass spectrometry detection part through the atomization chamber, the outer end of the outer tube and the second interface both extend into the inner cavity of the atomization chamber in an airtight manner, and the inner cavity of the atomization chamber is communicated with the plasma mass spectrometry detection part; the atomizing chamber is also provided with a heating device and a transmission gas pipe; the outlet of the transmission pipe is communicated with the inner cavity of the atomization chamber, and the inlet of the transmission gas is communicated with the transmission gas source.
Further, the device also comprises a nano-flow chromatography separation part and a plasma mass spectrometry detection part.
Further, the nano-flow chromatographic separation part comprises a sample inlet pipe, the inlet end of the sample inlet pipe is sequentially communicated with a sample source and a mobile phase source, and the mobile phase source is communicated with the sample inlet pipe through a high-pressure infusion pump; the exit end of advancing the appearance pipe communicates with first interface, shunt tubes respectively through the tee bend, and receives a class chromatographic column to be located tee bend horizontally one side, the shunt tubes is located tee bend's below, advance the appearance pipe and be located tee bend's top.
Further, the plasma mass spectrometry detection portion is a plasma mass spectrometer.
Further, the nanoflow chromatographic column is coaxially arranged with the outer tube.
Furthermore, the heating device is a heating electric wire wound outside the atomizing chamber, and two ends of the heating electric wire are respectively connected with two voltage output ends of the voltage regulator.
Further, the heating wire is a nickel-chromium wire.
The invention has the beneficial effects that: atomization and transmission efficiency are high, atomization gas and transmission gas are independently optimized, the outer tube and the inner tube used for manufacturing the nanoflow chromatographic column can be quickly replaced, manufacturing cost and reproducibility are good, the dead volume of the interface is extremely low, the chromatogram broadening is less, plunger manufacturing is not needed, the chromatographic column is simply and quickly prepared, and the chromatogram broadening caused by the plunger does not exist. Has the characteristics of high sensitivity, simple structure, convenient operation and low cost.
Drawings
FIG. 1 is a schematic structural diagram of the present invention in one embodiment;
FIG. 2 is a schematic representation of the nano-flow chromatography column and outer tube of FIG. 1;
FIG. 3 is a graph of the sensitivity of the invention described in FIG. 1 as a function of atomizing air back pressure and delivered air flow rate;
FIG. 4 is a graph of sensitivity of the present invention as described in FIG. 1 versus sample flow rate;
FIG. 5 is a chromatogram of a micro-fluidic atomizer, a d-NN nanoflow atomizer, and the separated mercury species of the present invention depicted in FIG. 1; wherein: the chromatogram a represents a chromatogram for collecting the nanoliter liquid chromatogram and the four mercury forms detected by the plasma mass spectrum separation by taking d-NN as a direct connection interface; the chromatogram b represents a chromatogram for collecting the nanoliter liquid chromatogram and separating and detecting four mercury forms by using a micro atomizer as a sheath liquid interface; chromatogram c represents a chromatogram for collecting nano liter liquid chromatogram and separating and detecting four mercury forms by plasma mass spectrum according to the invention shown in FIG. 1;
fig. 6 is a chromatogram of the 6 separated mercury forms of the invention depicted in fig. 1.
In the figure: the device comprises a 1-nanoflow chromatographic column, a 2-outer tube, a 3-support body, a 4-atomizing gas pipeline, a 5-PEEK joint, 6-atomizing gas, a 7-sealing plug, an 8-atomizing chamber, a 9-heating electric wire, a 10-gas conveying pipe, 11-conveying gas, a 12-voltage regulator, a 13-high-pressure infusion pump, a 14-microliter injection valve, a 15-tee joint, a 16-shunt pipe and a 17-plasma mass spectrometer.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the orientations or positional relationships indicated as the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., appear based on the orientations or positional relationships shown in the drawings only for the convenience of describing the present invention and simplifying the description, but not for indicating or implying that the referred devices or elements must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" as appearing herein are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly stated or limited, the terms "mounted," "connected," and "connected" should be interpreted broadly, e.g., as being fixed or detachable or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Referring to fig. 1 and fig. 2, the invention provides a combined system of nanoflow chromatography separation and plasma mass spectrometry detection, comprising a nanoflow chromatography separation part and a plasma mass spectrometry detection part, and further comprising a connecting part for communicating the nanoflow chromatography separation part and the plasma mass spectrometry detection part;
the connecting part comprises a support body 3 and a nanoflow chromatographic column 1, the nanoflow chromatographic column 1 penetrates through the inner cavity of the support body 3 in an airtight manner, and a first interface communicated with the nanoflow chromatographic separation part and a second interface used for being communicated with the plasma mass spectrometry detection part are respectively formed at two ends of the nanoflow chromatographic column 1 exposed out of the support body;
in some embodiments, the support 3 functions as a tee; the nano flow chromatographic column 1 horizontally penetrates through two opposite pipe orifices of the tee pipe fitting, and the nano flow chromatographic column 1 is hermetically fixed in the two pipe orifices of the tee pipe fitting through a sealing plug, wherein the sealing plug can adopt a PEEK pipe, and the end of the PEEK pipe serving as the sealing plug, which is positioned outside the tee pipe fitting, can be sealed through a PEEK joint 5.
An outer tube 2 is sleeved on a section of the nano-flow chromatographic column 1 close to the second interface, and a gap is formed between the inner wall of the outer tube 2 and the nano-flow chromatographic column 1 so as to allow atomized gas to pass through; the outer end of the outer tube 2 is positioned outside the inner cavity of the support body 3, and the orifice of the outer end of the outer tube 2 is flush and aligned with the second interface of the nano-flow chromatographic column 1 (that is, the cross section where the orifice of the outer end of the outer tube 2 is positioned is coincident with the cross section where the second interface is positioned); the outer end of the outer tube 2 and one end of the nano-flow chromatographic column 1 where the second interface is located are pointed ends, the outer end of the outer tube forms an atomized gas nozzle, and the second interface forms a sample nozzle;
in some embodiments, the outer tube 2 and the nano-flow chromatography column 1 are both quartz capillary tubes, and the tips of the outer tube 2 and the nano-flow chromatography column 1 can be made by self-manufacturing, for example, by a flame heating two-step stretching method, which comprises the following specific steps:
(1) a commercial quartz capillary tube with the length of 8cm and the specification of 0.53mm i.d. × 0.69mm o.d. is cut out to be used for manufacturing the outer tube 2, and a commercial quartz capillary tube with the length of 20cm and the specification of 0.1mm i.d. × 0.365mm o.d. (wherein, i.d. represents the inner diameter, and o.d. represents the outer diameter) is cut out to be used for manufacturing the inner tube (the nano-flow chromatographic column 1 comprises the inner tube and a chromatographic column bed which is fixedly filled in the inner tube and is formed by chromatographic packing materials);
(2) firstly, burning off a polyimide outer coating at one end (a part which is about 3cm away from a port) of a quartz capillary, then heating and softening in butane flame, simultaneously manually and slowly pulling two ends of the capillary in a horizontal reverse direction to thin a heating part into a thinning section, wherein the external diameter of the thinnest part of the thinning section of the outer tube 2 is about 150 mu m, and the external diameter of the thinnest part of the thinning section of the inner tube is about 75 mu m;
(3) then the thinning section is placed on alcohol flame for heating, and simultaneously, the two ends of the capillary tube are manually and rapidly pulled in the horizontal direction and the reverse direction, so that the thinning section is broken into two sections to form a sharp head; the size of the tip port of the outer tube 2 (namely, the orifice at the outer end of the outer tube) is 52.4 +/-0.9 mu mi.d. multiplied by 61.5 +/-1.4 mu m o.d., and the size of the tip port of the inner tube (namely, the second interface) is 13.8 +/-0.5 mu m i.d. multiplied by 16.5 +/-0.6 mu m o.d.
(4) Processing a capillary tube with the length of 8cm according to the steps (2) and (3) to obtain an outer tube 2;
(5) processing a capillary tube with the length of 20cm according to the steps (2) and (3) to obtain an inner tube; then, a homogenate pressure filling method is adopted to prepare the nano-flow chromatographic column 1, and the process is as follows: the chromatographic packing (the chromatographic packing in the embodiment can adopt C with the diameter of 3 μm18Spherical silica gel, and optionally C from Zhejiang Yue Xue science and technology Limited18Spherical silica gel) was uniformly dispersed in a vessel containing methanol (mass concentration of 20mg/mL), and the vessel was then brought into contact with a standard of 4.6mm i.d.. times.5 cm (wherein 5cm means a long one)Degree), and the other end of the sampling tube is communicated with the non-tapered end of the inner tube through a high-pressure infusion pump 13; under ultrasonic oscillation, a high-pressure infusion pump (constant pressure mode, 40MPa) conveys chromatographic packing into the inner tube, and the chromatographic packing is fixed in a pointed end of the inner tube due to a wedge effect to gradually form a chromatographic column bed; when the column bed reaches a predetermined length, for example, 15cm, the filling is stopped, and after the back pressure is reduced to 0, the inner tube and the high-pressure liquid delivery pump are separated, and the inner tube is washed with 1. mu.L/min of methanol for 4 hours, and the inner tube and the packed column filled in the inner tube form the nano-flow column 1.
The inner end of the outer tube 2 is positioned in the inner cavity of the support body 3 and is communicated with the inner cavity of the support body 3; an air inlet is formed in the support body 3, one end of the air inlet is communicated with an air source of the atomizing gas 6, and the other end of the air inlet is communicated with an inner cavity of the support body 3; atomized gas is sprayed out through the air inlet, the inner cavity of the support body, a gap between the inner wall of the outer tube and the nano-flow chromatographic column and the atomized gas nozzle in sequence;
in some embodiments, the air inlet is communicated with the air source of the atomizing gas 6 through an atomizing gas pipeline 4, the atomizing gas pipeline 4 is hermetically inserted in the air inlet, one end of the atomizing gas pipeline 4 is communicated with the outer pipe 2 through the inner cavity of the support body 3, and the other end is communicated with the air source of the atomizing gas 6. Atomizing gas pipeline 4 can adopt the preparation of multiple material, for example atomizing gas pipeline 4 can be the PEEK pipe, and in this embodiment atomizing gas 6 is high pressure argon gas, atomizing gas 6's air supply is the high pressure argon gas steel bottle, and the high pressure argon gas steel bottle has pressure regulating valve, pressure regulating valve's output pressure is 0.0 ~ 1.5 MPa.
The second interface is communicated with the plasma mass spectrometry detection part through an atomization chamber 8, the outer end of the outer tube 2 and the second interface both extend into the inner cavity of the atomization chamber in an airtight manner, the inner cavity of the atomization chamber 8 is communicated with the plasma mass spectrometry detection part, and the atomization chamber 8 is further provided with a heating device and a transmission gas tube 10; the outlet of the air delivery pipe 10 is communicated with the inner cavity of the atomizing chamber 8, and the inlet of the air delivery pipe 10 is communicated with the air source of the transmission air 11.
In some embodiments, the transmission air pipe 10 is vertically disposed at one side of the atomizing chamber 8, and the central axis of the transmission air pipe 10 is perpendicular to the central axis of the atomizing chamber 8; the atomizing chamber and the transmission air pipe 10 can be made of glass materials, and the specification of the transmission air pipe 10 can be 4mm i.d. multiplied by 6mm o.d.
The outer end of the outer tube 2 and one end of the second interface of the nanoflow chromatographic column 1 need to hermetically penetrate through the inlet end of the atomization chamber 8, for example, a sealing plug 7 is arranged at the inlet of the atomization chamber 8, the sealing plug 7 is a teflon sealing plug, and a through hole through which the outer tube 2 can hermetically penetrate is formed in the sealing plug 7; the outlet of the atomization chamber 8 is communicated with the plasma mass spectrometry detection part.
In some embodiments, the nanofluidic separation section comprises a sample inlet tube, the inlet end of which is in communication with a sample source and a mobile phase source in sequence, and the mobile phase source is in communication with the sample inlet tube via a high pressure infusion pump 13; the exit end of advancing the appearance pipe passes through tee bend 15 and communicates respectively with first interface, shunt tubes 16, and receives a class chromatographic column to be located 15 horizontally one side of tee bend, shunt tubes 16 are located the below of tee bend 15 advances the appearance pipe to be located the top of tee bend 15.
The mobile phase delivered by the high-pressure infusion pump 13 is divided into a nano-flow mobile phase in the chromatographic column 1 and a micro-flow mobile phase in the shunt tube 16 by the tee 15, and a microliter sample zone of the microliter injection valve 14 is also divided into a nano-liter sample zone flowing into the chromatographic column 1 and microliter sample waste liquid flowing into the shunt tube 16 by the tee 15. The nanoliter sample band is separated into different analytes in the nanoflow chromatographic column 1, the different analytes flow out and are atomized into fine aerosol through high-pressure argon 6 introduced into the outer tube 2, and the fine aerosol is loaded into a plasma mass spectrum 17 through a heated atomization chamber 8 under the combined conveying of the high-pressure argon 6 and transmission gas 11 for detection.
In some embodiments, the plasma mass spectrometer 17 is used as the plasma mass spectrometer, and the tee 15 can be made of various materials with certain strength requirements, such as stainless steel.
In some embodiments, the nanoflow chromatography column 1 is disposed coaxially with the outer tube 2.
In some embodiments, the heating device is a heating wire wound outside the atomization chamber 8, and two ends of the heating wire are respectively connected with two voltage output ends of a voltage regulator 12 serving as a power supply so as to regulate heating power.
In some embodiments, the heating wire is a nichrome wire having a resistance of 100 to 200 Ω. The two ends of the nichrome wire are connected with the voltage output end of the voltage regulator 12, the voltage output range of the voltage regulator 12 is 0-100V, for example, the output voltage of the voltage regulator 12 can be controlled to enable the heating power of the nichrome wire to be 10W.
In some embodiments, the gas inlet end of the transport gas tube 10 is in communication with the nebulizing gas tube of the plasma mass spectrometer 17, the transport gas 11 being provided by the plasma mass spectrometer 17.
The cross section area of an air gap (atomizing air nozzle) and the cross section area of liquid (sample nozzle) at the nozzle of the two sharp-pointed nano-flow chromatographic columns 1 and the outer tube used in the invention are both greatly reduced, the wall thickness of the inner tube is less than 5 mu m, and high atomization efficiency can be provided at a nano-flow level by combining argon gas with high back pressure (up to 1.0MPa), so that the use of sheath flow liquid is avoided. Meanwhile, the original atomization gas of the plasma mass spectrometer 17 is changed into the transmission gas 11, so that the atomization gas 6 and the transmission gas 11 are independently optimized, and better sensitivity is obtained.
The invention combines the sample inlet pipe of the atomizer and the nano-flow chromatographic column into a whole, thereby not only reducing the dead volume of the interface to zero and improving the chromatographic broadening, but also avoiding the preparation of a plunger for filling the chromatographic column and simplifying the preparation of the chromatographic column.
The invention uses the atomizing chamber 8 with a single channel to transmit the sample aerosol, the atomizing chamber 8 has small dead volume, the broadening of the chromatographic peak can be reduced, the heating of the atomizing chamber 8 accelerates the desolventizing of the aerosol, the transmission efficiency is improved, and simultaneously, the atomization process of the aerosol in the plasma is facilitated, thereby improving the sensitivity.
The aerosol particle size distribution of the nano-flow chromatography column 1 of the present invention was examined as follows:
the nebulization chamber 8 of the invention is removed such that the sample tap of the nano-flow chromatography column 1 is exposed. Using 1% nitric acid solution as a mobile phase, and using a quartz capillary tube with the length of 60cm and the specification of 0.05mm i.d. multiplied by 0.365mm o.d. as a shunt tube 16; the high-pressure infusion pump 13 delivers the mobile phase at a flow rate of 0.175mL/min, at which time the flow rate of the mobile phase in the nano-flow chromatographic column 1 is 510 nL/min; the high pressure argon cylinder was opened. The output pressure of the pressure regulating valve is sequentially regulated to be 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa and 0.8MPa, meanwhile, 4cm multiplied by 4cm pH test paper (the pH color change range of the pH test paper is 1.4-3.0) is placed at a concentric position 2cm away from the nozzle of the atomizer to collect the generated aerosol, and the generated aerosol is collected for 10min under each backpressure. Meanwhile, aerosol generated by d-NN under the same conditions (namely, the sampling flow rate is 510nL/min, the back pressure is 0.2MPa, and the collection time is 10min) is collected by using the same pH test paper, the aerosol particle size distribution is detected by observing the area size and the chroma depth of a shadow formed by the aerosol on the collected pH test paper, the area size of the shadow can reflect the distribution range of the aerosol, the larger the shadow area is, the wider the aerosol distribution is, and otherwise, the narrower the aerosol distribution is; the shade of the shade can reflect the distribution density of aerosol particles, the darker the shade of the shade, the more concentrated the distribution of the aerosol, and the more sparse the distribution of the aerosol. The particle size of the aerosol generated by the invention is obviously smaller than that of the aerosol generated by a d-NN nano-flow atomizer.
The analysis process of the invention comprises four stages of balance, sample introduction, separation and detection:
a. in the balancing stage, the high-pressure infusion pump 13 conveys a nano-flow mobile phase (containing internal standard elements) to the nano-flow chromatographic column 1, the output piezoelectric of the voltage regulator 12 is set to be 50-70V, the back pressure of the atomized gas is gradually increased (the output pressure of a pressure regulating valve of an argon steel cylinder is regulated), and the flow of the transmission gas 11 is changed under each back pressure of the atomized gas, so that the signals of the internal standard elements are strongest and stable;
b. in the sample injection stage, the microliter injection valve 14 is placed in the Load state, a certain volume of sample to be analyzed is manually sucked by an injector and injected into a quantitative ring of the microliter injection valve 14, and then the microliter injection valve 14 is immediately rotated to switch the valve position to the Inject state;
c. in the separation detection stage, when the microliter injection valve 14 is switched to the Inject state, a data acquisition program of the plasma mass spectrometer 17 is started immediately to start signal acquisition; the sample zone is driven by pressure flow of a mobile phase, and enters the nano-flow chromatographic column 1 after being shunted by the tee 15, and each component in the sample is separated due to the difference of the interaction between the components and a stationary phase.
d. In the detection stage, after separated sample molecules flow out of the nano-flow chromatographic column 1, the separated sample molecules are immediately atomized by the high-pressure atomizing gas 6 to form aerosol, and part of the aerosol is dissolved by the heating atomizing chamber 8 and finally enters the plasma mass spectrometer 17 for analysis and detection.
An analysis experiment is performed by using the combined system of the nano-flow chromatography separation and the plasma mass spectrometry detection in the embodiment according to the analysis process:
A 500 μ g/L multi-element mixed standard solution was used as the mobile phase, and a 60cm long quartz capillary tube with a specification of 0.05mm i.d. x 0.365mm o.d. was used as the shunt tube 16. Starting the voltage regulator 12 to make the output voltage 60V, starting the plasma mass spectrometer 17 to switch from the 'Vacuum' state to the 'operation' state, opening the high-pressure argon steel cylinder, adjusting the output pressure of the pressure regulating valve to 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa and 0.8MPa in sequence, starting the high-pressure infusion pump 13 to deliver the mobile phase at the flow rate of 0.175mL/min, wherein the flow rate of the mobile phase in the nanofluidification chromatographic column 1 is 510nL/min, and simultaneously changing the original atomization gas flow rate of the plasma mass spectrometer 17 to make the mass spectrum signal of each detection element maximum. Collecting6Li、7Li、55Mn、59Co、89Y、111Cd、115In、159Tb、205Tl、208Pb、209Bi and238the mass spectrum signal of the U mass number, as shown in FIG. 3, indicates that the best atomization efficiency can be obtained with a backpressure of 0.6 MPa.
Further, the output pressure of the fixed regulation pressure regulating valve was 0.6MPa, and the atomizing gas flow rate of the fixed plasma mass spectrometer 17 was 0.58L/min. The transfusion flow rate of the high-pressure transfusion pump 13 is changed to be 0.05-0.30mL/min (increment of 0.05 mL/min) in sequence, and the flow phase flow rate in the nano-flow chromatographic column 1 is 59-910nL/min respectively. Collecting6Li、7Li、55Mn、59Co、89Y、111Cd、115In、159Tb、205Tl、208Pb、209Bi and238mass spectrum signal of U mass number, as shown in FIG. 4, the results indicate highThe pressure atomizer can produce good aerosol at nano-flow to micro-flow levels.
A50. mu.g/L sample of the mixed standard solution in the form of four mercury samples was used, with 10mM cysteine as the mobile phase, and a 60cm long quartz capillary tube of 0.05mM i.d.. times.0.365 mM o.d. gauge was used as the shunt tube 16. Starting the voltage regulator 12 to make the output voltage 60V, starting the plasma mass spectrometer 17 to switch from the state of "Vacuum" to the state of "operation", the output pressure of the fixed regulation pressure regulating valve is 0.6MPa, the atomization airflow rate of the fixed plasma mass spectrometer 17 is 0.58L/min, and then starting the high-pressure pump to deliver the mobile phase at the flow rate of 0.175mL/min, at this time, the flow rate of the mobile phase in the nano-flow chromatographic column 1 is 510 nL/min. Injecting 5 μ L of mercury mixture into the sample loop of the microliter injection valve 14, switching the valve position from "Load" to "Inject", and beginning collection202Mass spectrum signal of Hg mass number 10min, as shown in chromatogram c in FIG. 5. And meanwhile, collecting four mercury forms of nanoliter liquid chromatography and plasma mass spectrometry by using d-NN as a direct connection interface and a micro atomizer as a sheath liquid interface, wherein the four mercury forms are respectively shown as chromatograms a and b in fig. 5. The result shows that the high-pressure atomizer has the highest interface sensitivity and the least chromatographic broadening.
Further, 6 repeated injections of 5 μ L of mercury were mixed into the sample loop of the microliter injection valve 14, and the valve position was then switched from "Load" to "Inject" while collection was commenced202The mass spectrum signal of Hg mass number is 8min, as shown in FIG. 6, and the result shows that the combined system of the invention has good reproducibility.
The embodiments described in this specification are merely illustrative of implementations of the inventive concept and the scope of the present invention should not be considered limited to the specific forms set forth in the embodiments but includes equivalent technical means as would be recognized by those skilled in the art based on the inventive concept.
Claims (7)
1. A combined system of nano-flow chromatography separation and plasma mass spectrometry detection is characterized in that: comprises a connecting part for communicating the nano-flow chromatography separating part and the plasma mass spectrometry detecting part;
the connecting part comprises a support body and a nanoflow chromatographic column, the nanoflow chromatographic column penetrates through the inner cavity of the support body in an airtight manner, and a first interface communicated with the nanoflow chromatographic separation part and a second interface used for communicating with the plasma mass spectrometry detection part are respectively formed at two ends of the nanoflow chromatographic column exposed out of the support body;
an outer pipe is sleeved on a section of the nano-flow chromatographic column close to the second interface, and a gap is formed between the inner wall of the outer pipe and the nano-flow chromatographic column; the outer end of the outer tube is positioned outside the inner cavity of the support body, and the tube opening of the outer end of the outer tube is flush and aligned with the second interface of the nano-flow chromatographic column; the outer end of the outer tube and one end of the nano-flow chromatographic column where the second interface is located are both sharp heads, the outer end of the outer tube forms an atomized gas nozzle, and the second interface forms a sample nozzle;
the inner end of the outer tube is positioned in the inner cavity of the support body and is communicated with the inner cavity of the support body; the supporting body is provided with an air inlet, one end of the air inlet is communicated with an air source of the atomizing gas, and the other end of the air inlet is communicated with the inner cavity of the supporting body;
the second interface is communicated with the plasma mass spectrometry detection part through the atomization chamber, the outer end of the outer tube and the second interface both extend into the inner cavity of the atomization chamber in an airtight manner, and the inner cavity of the atomization chamber is communicated with the plasma mass spectrometry detection part; the atomizing chamber is also provided with a heating device and a transmission gas pipe; the outlet of the gas transmission pipe is communicated with the inner cavity of the atomization chamber, and the inlet of the gas transmission pipe is communicated with a gas source of the transmission gas.
2. A system in combination for nanofluidic separation and plasma mass spectrometry detection according to claim 1, wherein: the device also comprises a nano-flow chromatography separation part and a plasma mass spectrometry detection part.
3. A system in combination for nanofluidic separation and plasma mass spectrometry detection according to claim 2, wherein: the nano-flow chromatographic separation part comprises a sample inlet pipe, the inlet end of the sample inlet pipe is sequentially communicated with a sample source and a mobile phase source, and the mobile phase source is communicated with the sample inlet pipe through a high-pressure infusion pump; the exit end of advancing the appearance pipe communicates with first interface, shunt tubes respectively through the tee bend, and receives a class chromatographic column to be located tee bend horizontally one side, the shunt tubes is located tee bend's below, advance the appearance pipe and be located tee bend's top.
4. A system in combination for nanofluidic separation and plasma mass spectrometry detection according to claim 3, wherein: the plasma mass spectrum detection part is a plasma mass spectrometer.
5. The system of claim 4, wherein the combination of nanofluidic separation and plasma mass spectrometry comprises: the nano-flow chromatographic column is coaxially arranged with the outer tube.
6. The system of claim 5, wherein the sample comprises at least one of the following components: the heating device is a heating electric wire wound outside the atomizing chamber, and two ends of the heating electric wire are respectively connected with two voltage output ends of the voltage regulator.
7. The system of claim 6, wherein the sample comprises at least one of: the heating wire is a nickel-chromium wire.
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| CN111397984B (en) * | 2020-04-05 | 2022-01-11 | 中国海洋大学 | Element vapor generation method and device for spontaneous micro-droplet induction |
| CN112834676A (en) * | 2020-12-31 | 2021-05-25 | 杭州谱育科技发展有限公司 | Interface device for mass spectrum and chromatogram and installation method |
| CN114965831A (en) * | 2022-05-19 | 2022-08-30 | 厦门大学 | Zero dead volume interface device for combination of chromatograph and mass spectrum and application thereof |
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