CN116672916A - Chromatograph with mixed wave reduction device and detection method thereof - Google Patents
Chromatograph with mixed wave reduction device and detection method thereof Download PDFInfo
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/40—Static mixers
- B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
- B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
- B01F25/433—Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
- B01F25/4331—Mixers with bended, curved, coiled, wounded mixing tubes or comprising elements for bending the flow
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/23—Mixing of laboratory samples e.g. in preparation of analysing or testing properties of materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention belongs to the field of chromatographic instruments, and provides a chromatograph with a mixed wave reduction device, which can effectively reduce liquid shock waves and compress the amplitude to a very stable state on the premise of fully and uniformly mixing multiple liquids at the same time, thereby being beneficial to reducing the background noise of liquid chromatography, improving the signal-to-noise ratio and the sensitivity and reducing the lower limit of quantification; in addition, the mixed wave reduction device of the chromatograph provided by the invention is designed by a spiral metal tube, the fatigue life is far longer than that of a diaphragm or a metal diaphragm, and the mixed wave reduction device is economical, practical, durable and convenient to replace; finally, the mixed wave reduction device of the chromatograph provided by the invention can calculate corresponding pipe diameter, external diameter and spiral turns according to the liquid inlet amount, and the use requirements of various liquid inlet amounts can be adapted to the greatest extent; the sensitivity and the accuracy of blood sample detection can be pertinently improved.
Description
Technical Field
The invention belongs to the field of chromatographic instruments, and particularly relates to a chromatograph with a mixed wave reduction device for reducing the lower limit of sample detection.
Background
In the mass spectrum liquid phase field, most of the mixing modes after various liquid sample injection at present adopt multi-hole backflow mixing, the mixing effect of the mixing mode is insufficient, the background noise in a chromatogram is increased, even peak displacement occurs, and therefore the lower limit of detection of a sample is higher.
Meanwhile, the liquid flows to generate oscillation water waves, a group of wave reduction devices are added to eliminate the oscillation waves as much as possible in the market, and the mode of using a diaphragm or a metal diaphragm is adopted to eliminate the oscillation to reduce the wave form; the methods have limitations on the elimination of the oscillating waves, the elimination of the oscillating waves is insufficient, and the amplitude retention value is larger; in addition, the diaphragm or the metal diaphragm has fatigue life and is troublesome to replace.
Therefore, a new technology for liquid chromatography is needed to be found, which can mix the liquid feed sufficiently, reduce the background noise and lower the detection limit of the sample.
Disclosure of Invention
In order to solve the problems, the invention provides a chromatograph with a mixed wave reducing device for reducing the detection lower limit of a sample, which can effectively reduce liquid oscillation waves and compress the amplitude to a very stable state on the premise of fully and uniformly mixing the sample and other liquid such as flowing liquid based on the elastic buffer principle of liquid turbulence and spiral gaps, so that the detection lower limit of the sample can be obviously reduced. The mixed wave reducing device of the chromatograph is designed as a spiral tube, and the fatigue life is far longer than that of a diaphragm or a metal diaphragm, so that the mixed wave reducing device is durable and convenient to replace.
The mixing wave reduction device of the chromatograph comprises a spiral mixing damper (1), wherein the spiral mixing damper (1) comprises a spiral pipeline, the pipe diameter and the outer diameter of the spiral pipe are calculated and designed according to the liquid inlet amount, so that the mixing wave reduction device has great suitability in the aspect of the liquid inlet amount.
Meanwhile, a gap is reserved between each two spiral sections, so that the ductility of the metal and the buffering effect of the spiral structure can be utilized, and the vibration wave generated by liquid flow can be effectively eliminated, so that the amplitude of the vibration wave is compressed to an extremely gentle state.
The inner wall of the metal pipe is regularly provided with inclined flow blocking surfaces, various high-pressure liquids are pumped into the metal spiral pipe from the inlet and then touch the flow blocking surfaces uniformly distributed on the inner wall of the pipe, so that an irregular turbulence phenomenon is formed, and various liquids are effectively and fully mixed; finally, the evenly mixed liquid flows out from the flushing outlet.
Liquid turbulence is formed in the pipe, so that various liquids are effectively mixed uniformly; meanwhile, the metal spiral structure can reduce the shock wave generated by liquid flow to an extremely gentle range, and can calculate the corresponding pipe diameter, the outer diameter and the spiral number of turns according to the liquid inlet amount, so that the use requirements of various liquid inlet amounts can be met to the greatest extent.
In one aspect, the invention provides a chromatograph comprising a mixing wave reduction device for reducing the lower limit of sample detection, which is characterized by comprising a spiral mixing damper (1), wherein the spiral mixing damper (1) comprises a spiral pipeline, the inner wall of the spiral pipeline is provided with roughness, the spiral pipeline is provided with at least two spiral coils, a space is reserved between the spiral coils, and the sample is a blood sample.
Researches prove that the chromatograph with the mixed wave reduction device provided by the invention can obviously reduce the detection lower limit of a blood sample, but has no obvious influence on a urine sample.
Further, the spiral pipeline is made of one or more of PP, PVC, PTFE, PEEK, silica gel and stainless steel.
Further, the roughness of the spiral pipeline is 0.4-2.0.
Further, the inner diameter of the spiral pipe is 0.5-1.0 mm, and the outer diameter of the spiral pipe is 1.0-2.0 mm.
Further, the spiral outer diameter of the spiral ring is 3-5 mm.
Further, the interval between the spiral coils is 0.1-0.5 mm.
In some aspects, the helical tubing is of stainless steel S32750.
In some embodiments, the helical tubing has a roughness of 0.8 μm.
In some aspects, the spacing between the turns is 0.2mm.
In some embodiments, the helical tube has a tube inner diameter of 0.8mm and the helical tube has a tube outer diameter of 1.6mm.
In some aspects, the helical turns have a helical outer diameter of 4mm.
In some embodiments, the number of turns of the spiral metal tube is 5 when the feed rate is 25. Mu.L.
In some embodiments, the number of turns of the spiral metal tube is 10 when the feed rate is 50. Mu.L.
On the other hand, the invention provides a method for reducing the lower limit of sample detection of the chromatograph, which comprises the steps of uniformly mixing liquid by the mixing wave reduction device of the chromatograph, and then entering a chromatographic column after uniformly mixing.
In a further aspect, the present invention provides the use of a chromatograph as described above for reducing the lower detection limit of a sample, said sample being a blood sample.
The invention has the following beneficial effects:
1. the chromatograph with the mixed wave reduction device can effectively reduce liquid shock waves on the premise of fully and uniformly mixing multiple liquids, compresses the amplitude to a very stable state, and is favorable for reducing the background noise of liquid chromatography and improving the signal to noise ratio, so that the detection sensitivity of a blood sample can be obviously improved, and the lower limit of quantification can be reduced.
2. The mixed wave reduction device of the chromatograph provided by the invention is designed as a spiral metal tube, and the fatigue life is far longer than that of a diaphragm or a metal diaphragm, so that the mixed wave reduction device is economical, practical, durable and convenient to replace.
3. The mixed wave reduction device of the chromatograph provided by the invention can calculate the corresponding pipe diameter, the external diameter and the spiral turns according to the liquid inlet amount, and can adapt to the use requirements of various liquid inlet amounts to the greatest extent.
4. The chromatograph provided by the invention can pertinently improve the sensitivity and accuracy of blood sample detection.
Drawings
Fig. 1 is a schematic structural diagram of a hybrid wave reduction device of a chromatograph.
Fig. 2 is a schematic diagram of a structure of a chromatograph with a housing removed by a hybrid wave reduction device.
Fig. 3 is a schematic diagram of a housing structure of a hybrid wave reduction device of a chromatograph.
Fig. 4 is a disassembled view of the hybrid wave reduction device of the chromatograph.
Fig. 5 is a schematic diagram of the position of the hybrid wave reduction device on a liquid chromatograph.
Fig. 6 is a pure water chromatogram of a chromatograph using a hybrid wave reduction device.
Fig. 7 is a pure water chromatogram of a chromatograph without using a hybrid wave reduction device.
Detailed Description
The invention is further described below with reference to the drawings and examples. It should be noted that the embodiments are only detailed description of the present invention, and not intended to limit the scope of the present invention, and all the features disclosed in the embodiments of the present invention, or all the steps in the methods or processes disclosed, except mutually exclusive features and/or steps, can be combined in any way, and are within the scope of the present invention. The technology not related to the invention can be realized by the prior art.
The turbulence-based hybrid wave reduction device is shown in figures 1-4.
As shown in fig. 1, the turbulence-based mixing wave reduction device provided by the invention comprises a spiral mixing damper 1, a bottom fastening mounting plate 2, an O-shaped sealing ring 3 and an external connection shell 4. The spiral mixing damper 1 is a section of spiral pipeline and is provided with a sample inlet 11, a sample outlet 12, an inlet gasket 13 and an outlet gasket 14. The spiral mixing damper 1 is tightly and hermetically connected with the sample inlet 48 and the sample outlet 49 of the external connection shell 4 through the sample inlet sealing ring 31 and the sample outlet sealing ring 32 of the O-shaped sealing ring 3 respectively, and the spiral mixing damper 1 and the bottom fastening mounting plate 2 are mutually fixed through the sample inlet fixing column 29 and the sample outlet fixing column 210. The inlet gasket 13 and the outlet gasket 14 of the spiral mixing damper 1 are respectively clamped between the sample injection sealing ring 31 and the sample injection fixing column 29, and between the sample discharge sealing ring 32 and the sample discharge fixing column 210, so as to play a role in fixing. The bottom fastening mounting plate 2 is reserved with screw holes 23, 24, 27 and 28, and is connected with the external connection shell 4 through screws, and the screws are driven into screw grooves 42, 43, 44 and 45 from the screw holes of the bottom fastening mounting plate 2.
As shown in fig. 2, the bottom fastening mounting plate 2 includes a reserved fixing hole 21, a reserved fixing hole 22, a reserved fixing hole 25, and a reserved fixing hole 26 for fixing the hybrid wave reduction device in the liquid chromatograph. There are also screw holes 23, 24, 27, 28 for connection with the external connection housing 4. There are also a sample introduction fixing column 29 and a sample discharge fixing column 210 for fixing with the spiral mixing damper 1.
As shown in fig. 3, the external connection housing 4 includes a housing 41, a screw groove 42, a screw groove 43, a screw groove 44, a screw groove 45, a sample introduction passage 46, a sample discharge passage 47, a sample introduction fine passage 48, a sample discharge fine passage 49, and a hollow groove 410. The casing 41 is approximately cylindrical, two sides of the casing are provided with a sample inlet channel 46 and a sample outlet channel 47, the bottom of the sample inlet channel 46 is tapered and narrowed to a sample inlet fine channel 48 along with the flowing direction of the liquid, and the bottom of the same sample outlet fine channel 49 is tapered and expanded to the sample outlet channel 47 along with the flowing direction of the liquid. The bottom is provided with a screw groove 42, a screw groove 43, a screw groove 44 and a screw groove 45 for fixing, and a hollow groove 410 is reserved for placing and fixing the screw mixing damper 1.
Fig. 4 is a disassembled view of the turbulence-based hybrid wave reduction device provided by the invention, which comprises a spiral mixing damper 1, a bottom fastening mounting plate 2, an O-shaped sealing ring 3 and an external connection shell 4.
The position diagram of the turbulence-based mixed wave reduction device on the liquid chromatograph is shown in fig. 5, fig. 5 also shows the flowing sequence of liquid in sample injection, which is marked by an arrow, 101 is a mobile phase, 102 is a sample to be detected, and 103 is a chromatographic column. The liquid chromatograph comprises a mixing wave reducing device 100, a liquid phase outer housing 5, a liquid inlet valve 6, a liquid degassing device 7, a booster pump 8 and a three-way switching valve 9. When liquid is sampled, the sequence of flowing in sequence is as follows: the device comprises a liquid inlet valve, a liquid degassing device, a booster pump, a three-way switching valve and a mixing wave reducing device.
In some modes, the spiral mixing damper 1 of the mixing and wave reducing device selects the spiral pipe as follows: stainless steel S32750 pipe with inner diameter of 0.8mm and outer diameter of 1.6mm is processed by spiral treatment with laser etching control roughness of 0.8 μm in the pipe to obtain spiral pipe with outer diameter of 4mm, number of turns of 5 and spiral interval of 0.2mm. The method for manufacturing the spiral tube only needs to adjust part of parameters in the manufacturing method of the spiral tube with other specifications comprises the following steps:
(1) The inner wall of the pipeline is etched by a laser etching method to reach the inner wall roughness of 0.8, and the conditions of the laser etching are as follows: the power of the light source is 120W; the laser wavelength is 10.64 mu m; the pulse width is 250ns; the pulse repetition frequency is 50KHz;
(2) And carrying out spiral treatment on a punching machine according to the set parameters of the outer diameter, the number of turns and the spiral spacing of the spiral.
The spiral pipe manufactured by the method is cut off from different sections, and the surface roughness measuring instrument is used for measuring the roughness of the inner wall, wherein the surface roughness measuring instrument is BRUKER ® The three-dimensional optical profilometer concourX-100 is purchased from Bruce (Beijing) technology Co., ltd. According to the equipment instruction, the roughness is found to be 0.8+/-0.0075 mu m, and the roughness is proved to be satisfactory.
Example 2: preparation, pretreatment and liquid phase detection of blood samples using mass spectrometry with mixed wave reduction device
1. Sample preparation
1. Preparation of calibration material and quality control sample
Will VK 1 (vitamin K1), MK-4 (one of vitamin K2) and MK-7 (one of vitamin K2) standard substances are prepared into mixed solution, the mixed solution is used as stock solution of standard working solution and quality control working solution, the stock solution of the standard working solution is mixed with 4% BSA according to the volume ratio of 1:19, and the stock solution of the quality control working solution is mixed with the volume ratio of 1:99 of mixed blank serum, so that a calibration curve and a quality control sample are respectively prepared. Preparing 7 series of concentrations (C1-C7) by using a calibration curve, and preparing 2 series of concentrations (LQC and HQC) by using a quality control sampleTables 1 and 2 below show, respectively.
Table 1: VK (vK) 1 MK-4 and MK-7 in the calibration curve (C1-C7) series concentrations
Table 2: VK (vK) 1 MK-4 and MK-7 in quality control samples were labeled in 2 series (LQC and HQC)
2. Preparation of internal standard solution
(1) Preparation of working solution for internal standard
Preparing mixed internal standard working solution, VK 1 The concentrations of d4, MK-4-d7 and MK-7-d7 were 1. Mu.g/mL, 2. Mu.g/mL and 6. Mu.g/mL, respectively.
(2) Preparation of protein precipitant
Respectively weighing 900mL of ethanol, 50mL of acetonitrile and 50mL of isopropanol to prepare a mixed solution containing 90% of ethanol, 5% of acetonitrile and 5% of isopropanol; 576mL of the above mixed solution was taken and 384mL of ultrapure water and 40mL of trichloroacetic acid solution were added to prepare 1000mL of a protein precipitant.
(3) Preparation of internal standard working solution
And adding 1mL of an internal standard substance working solution into the prepared 1000mL of protein precipitant to obtain the internal standard working solution.
2. Sample pretreatment
The human serum sample to be tested, the calibrator and the quality control product are pretreated by the following method:
(1) 200 mu L of calibrator/quality control/human serum sample to be tested is taken and added into a 2mL centrifuge tube; 600. Mu.L of internal standard working solution was added and the mixture was shaken at 2000rpm for 5min.
(2) Adding 1mL of isooctane, carrying out vortex oscillation at 2000rpm for 10min, centrifuging at 12000rpm for 5min, adding 700 mu L of an upper organic phase into a corresponding hole of a FastRemotrover phospholipid removal plate, and standing for 5min;
(3) The positive pressure instrument regulates the pressure to control the liquid to flow down at the flow speed of 1 drop/second, the liquid is dried for 1min by positive pressure, 1000 mu L of isooctane is added for leaching, 150 mu L of 80% ethanol is re-dissolved after the leaching liquid nitrogen is collected and dried, and the detection is carried out.
3. Sample detection
Liquid chromatography tandem mass spectrometry system: the CalQuant-S liquid chromatograph tandem mass spectrometry detection system with the hybrid wave reduction device described in example 1 is shown in fig. 5, wherein the spiral mixing damper of the hybrid wave reduction device is a stainless steel S32750 pipe with an inner diameter of 0.8mm, an outer diameter of 1.6mm and a pipe length of 100mm (volume of 50 μl), the inside of the pipe is subjected to spiral treatment (the spiral pipe with an outer diameter of 4mm, a number of turns of 5 turns, and a spiral pitch of 0.2 mm) by adopting laser etching to control roughness of 0.8 μm;
chromatographic column: phenyl-Hexyl (2.6 μm, 3.0X10 mm, phenomenex);
mobile phase a: water: methanol: isopropanol=8:1:1 (0.1% fa), mobile phase B: methanol: isopropanol=9:1 (0.1% fa);
flow rate: 0.6mL/min, column temperature: 40 ℃, injector temperature: 15 ℃, sample injection volume: 25. Mu.L.
Gradient elution conditions are shown in table 3 below.
Table 3: gradient elution conditions
Mass spectrometry detection conditions: the ion source is an atmospheric pressure chemical ionization source (APCI), the positive ion mode, and the ion source parameters are as follows: the desolvation Gas (GS 1) was 55psi, the ion source heating temperature was 350 ℃, the Curtain Gas (CUR) was 25psi, the Collision Gas (CAD) was 9psi, and the atomizing current NC was 3. Mu.A. The scanning mode is a multi-reaction monitoring (M mu Ltiple Reaction Monitoring, MRM) mode.
The mass spectrum parameters of the compounds are shown in table 4:
table 4: mass spectral parameters of compounds
4. Data processing and analysis
Drawing a standard curve: and (3) performing linear fitting on the standard curve by taking the concentrations of the vitamin K2 and the vitamin K1 calibrator as the abscissa and the area ratio of the vitamin K2 and the vitamin K1 to the peak area of each internal standard as the ordinate to obtain a linear regression equation. The linear equation and the correlation coefficient r are shown in table 5. Vitamin K1, vitamin K2 (MK-4) and vitamin K2 (MK-7) are in the concentration range of 0.025-5.0ng/mL, the linearity is good, and the correlation coefficient r is larger than 0.9900.
Table 5: linear equation and correlation coefficient r
The signal-to-noise ratio is the ratio of the peak height of a target object to be detected to the peak height of a background peak, wherein the background peak is generated by the baseline noise and is a continuously up-and-down fluctuation peak, the signal-to-noise ratio is calculated and obtained by software calculation, and the signal-to-noise ratio is obtained by calculation (software version: analyst 1.7.2); the quantitative detection lower limit refers to the lowest value of a target object to be detected in a sample, which can be accurately and quantitatively measured, the recovery rate is in the range of 85% -115%, and the lowest concentration point of the signal to noise ratio S/n=10 is the quantitative lower Limit (LOQ) of the invention; the labeling recovery rate is the ratio of the measured value of the serum quality control (LQC) to the theoretical value, and the average labeling recovery rate is calculated repeatedly for 5 times. The results are shown in Table 6.
Table 6: VK (vK) 1 Quantitative limit detection data for MK-4 and MK-7 methods
A control test was set up, and the sample introduction channel was a stainless steel S32750 tube having an inner diameter of 0.8mm, an outer diameter of 1.6mm, a tube length of 100mm (volume 50. Mu.L), a tube inner wall roughness of 0.8 μm, without any spiral treatment, and the tube was a straight tube, according to the method described in example 1; another group of devices provided by the present invention were added, where the devices were 0.8mm inside diameter, 1.6mm outside diameter,stainless steel S32750 pipe with pipe length of 100mm and pipe inner wall roughness of 0.8 mu m; performing spiral treatment (preparing spiral pipe with outer diameter of 4mm, number of turns of 5 and spiral interval of 0.2 mm), and detecting quality control product LQC in example 1 under the same conditions as in example 1 to obtain VK 1 The signal to noise ratios, lower quantification limits, and labeled recovery of MK-4 and MK-7 are shown in Table 7.
Table 7: VK (vK) 1 Quantitative limit detection data for MK-4 and MK-7 methods
The results show that: after the device provided by the invention is used, the background noise can be obviously reduced, the signal to noise ratio is improved, the quantitative lower limit is reduced, the peak area size is more accurately detected, and the standard adding recovery rate is close to 100%.
Meanwhile, the chromatograph is filled with the two sample injection channels for the test, background noise of the chromatograph under the two sample injection channels is further studied, pure water is pumped in, and data are collected, as shown in fig. 6 and 7: fig. 6 shows background noise after using the device provided by the present invention, and fig. 7 shows background noise after not using the device provided by the present invention, it can be found that the fluctuation value (maximum value-minimum value) after using the device is reduced from 123 to 92.3, and is reduced by 25%, and the fluctuation is smoother, so that the oscillation wave of the liquid can be effectively eliminated, and further, the noise is reduced, the signal to noise ratio is improved, and the lower limit of quantification is reduced.
The material of the pipe will influence the conduction and reflection of the wave generated by the liquid flow, and thus will influence the liquid flow, and further influence the wave reducing effect of the device provided by the invention.
In the embodiment, the method of the embodiment 2 is adopted, and a sample injection tube with the inner diameter of 0.8mm, the outer diameter of 1.6mm, the length of the tube of 100mm and the roughness of the inner wall of the tube of 0.8 mu m is selected; performing spiral treatment (preparing a spiral pipe with an outer diameter of 4mm, a circle number of 5 circles and a spiral interval of 0.2 mm); the spiral pipes of the spiral mixing damper are made of different materials, such as silica gel, PP, PVC, PTFE, PEEK and stainless steel, and the VK in the test index example 1 is measured 1 Signal-to-noise ratio, quantitative lower limit, quality control product LQC,The results of the addition of the standard recovery rate and the fluctuation value of pure water are shown in Table 8.
Table 8: pipeline material
The chemical components of the materials are disclosed. Among the above stainless steels: 2205 has high strength, good impact toughness, and good overall and local stress corrosion resistance; 304 has good processability and high toughness; 316L has wide application in the chemical industry due to its excellent corrosion resistance; 3010S has corrosion resistance; s25554 is stainless steel with higher fatigue strength, and is suitable for high-load and high-wear-resistance application; s32101 is a nitrogen-containing duplex stainless steel capable of providing high strength and good resistance to chloride stress corrosion cracking; s32750 combines the high strength plasticity of austenitic stainless steel with the corrosion resistance of ferritic stainless steel; s32760 is high-alloy super duplex stainless steel, has stronger steel strength and corrosion resistance, and has excellent comprehensive performance.
The silica gel material is purchased from Shenzhen China Feng Yuangui rubber products Co., ltd; PP material was purchased from Jiangsu and Chengsu valve parts limited; PVC material was purchased from Kunshan Huashui plastics Co., ltd; PTFE and PEEK materials are purchased from Buddha three-benefit plastic materials Co., ltd; stainless steel 2205, stainless steel 304, stainless steel 316L, stainless steel 3010S tubing purchased from the company of non-tin Xingbei stainless steel limited; stainless steel S25554, stainless steel 32101, stainless steel S32750, stainless steel S32760 pipe were purchased from Shanghai Jiujin Steel New Material Co.
The results show that: the spiral pipeline is made of stainless steel, so that the effect is good; wherein the effect is best when stainless steel S32750 is selected, and VK can be ensured 1 The detection peak area in the detection process is the largest, the signal-to-noise ratio is the highest, the quantitative lower limit is the lowest, the standard adding recovery rate is the closest to 100%, the fluctuation value of pure water detection is the smallest, and the effect is the best in a plurality of materials. In principle, the method comprises the following steps: s32750 is a duplex stainless steel with excellent strength and corrosion resistance, good creep resistance, and stable under sustained loadingThe liquid phase sampling device has good pitting resistance, can keep stable at the maximum point of the pressure of the spiral tube, and is beneficial to liquid phase sampling mixing wave reduction.
Example 5: roughness of inner wall of pipeline
As can be obtained from example 4, stainless steel S32750 works best as a pipe material, so this example further investigated the effect of the inner wall roughness of stainless steel S32750 pipe on the hybrid wave reduction device provided by the present invention.
Similarly, the VK in the detection index example 1 was measured by performing spiral treatment (forming a spiral pipe having an outer diameter of 4mm, a number of turns of 5 turns, and a pitch of 0.2 mm) using a pipe having an inner diameter of 0.8mm, an outer diameter of 1.6mm and a pipe length of 100mm (volume of 50. Mu.L), using stainless steel S32750 as a material, and modifying the roughness of the inner wall of the pipe by laser etching to change the laser parameters 1 The signal-to-noise ratio, lower limit of quantification, standard recovery, and fluctuation value of pure water of the quality control product LQC are shown in Table 9.
Table 9: roughness of inner wall of pipeline
The results show that: when the roughness of the inner wall is too small, the fluctuation value of pure water is large due to small resistance to the flow of liquid, and the flow rate is high for VK 1 The detection effect of (2) is also poor; when the roughness of the inner wall is too large, VK can be caused due to too large flow resistance of the liquid 1 The detection effect is poor, and the effect of reducing the background noise is lost; therefore, we analyze the above table, the roughness of the inner wall is preferably 0.4-2.0 μm, and VK can be obtained 1 The area of a detection peak in the detection process is increased, the signal-to-noise ratio is improved, the quantitative lower limit is reduced, the standard adding recovery rate is close to 100%, and the fluctuation value of pure water detection is reduced; of these, the inner wall roughness of 0.8 μm is most effective.
Example 6: pipe inner diameter, outer diameter and spiral outer diameter
According to the pipeline inner diameter calculation formula: wherein d is the inner diameter of the pipeline and the unit is m; q (Q) m The flow rate is kg/h; c is the flow rate in m/s.
Substituting the water into the water to obtain the inner diameter of the pipeline of 0.8mm; according to the nominal pipe specification, an outer diameter of 1.6mm is further selected.
In practical use, the obtained pipe is required to be subjected to spiral treatment, so that the size of the outer diameter of the spiral is critical, the embodiment is fixed to form 5 circles, the interval between the spiral circles is 0.2mm, and the VK in the detection index embodiment 1 is measured only by changing the outer diameter of the spiral 1 The signal-to-noise ratio, lower limit of quantification, standard recovery, and fluctuation value of pure water of the quality control product LQC are shown in Table 10.
Table 10: coil pitch
The results show that: the spiral outer diameter is preferably 4mm, at this time, the VK is maximized 1 The area of a detection peak in the detection process is increased, the signal-to-noise ratio is improved, the quantitative lower limit is reduced, the standard adding recovery rate is close to 100%, and the fluctuation value of pure water detection is reduced; when the outer diameter of the spiral is too small, the fluctuation value is increased, and the signal to noise ratio is reduced; when the outer diameter of the spiral is too large, the spiral returns to the effect similar to a straight pipe, and the signal to noise ratio is reduced.
From the above examples, we obtained stainless steel S32750 tubes having an inner diameter of 0.8mm, an outer diameter of 1.6mm and a tube length of 100mm (volume 50. Mu.L), an inner wall roughness of 0.8 μm, and were subjected to a spiral treatment (to produce a spiral tube having an outer diameter of 4mm and 5 turns). Obviously, the interval of the spiral rings can influence the effect of mixing and wave reduction: the interval is too large, the spiral effect is reduced until almost disappears, the liquid returns to a laminar state, the mixing effect is poor, and the wave reduction effect is poor; the interval is too small, the liquid flows in disorder, the wave reduction effect is reduced, and the fluctuation value is increased, so that the detection is not facilitated.
In this example, the VK in example 1 was measured by changing the pitch between the turns, which is the distance between the outer portions of the two turns 1 The signal-to-noise ratio, lower limit of quantification, standard recovery, and fluctuation value of pure water of the quality control product LQC are shown in Table 11.
Table 11: coil pitch
The results show that: the coil pitch is preferably 0.2mm, so that VK can be maximized 1 The area of the detection peak in the detection process is increased, the signal-to-noise ratio is improved, the quantitative lower limit is reduced, the standard adding recovery rate is close to 100%, and the fluctuation value of pure water detection is reduced.
In principle, the method comprises the following steps: proper distance is left between the spiral rings, and the ductility of the metal and the buffering effect of the spiral structure can be utilized to effectively eliminate the shock wave generated by the liquid flow, so that the amplitude of the shock wave is compressed to an extremely gentle state.
Example 8: number of turns of spiral
The influence of the number of spiral turns on the wave reduction effect of the device provided by the invention is researched, and the wave reduction effect is weakened when the number of spiral turns is too small. Stainless steel S32750 pipe with inner diameter of 0.8mm, outer diameter of 1.6mm and pipe length of 100mm (volume of 50 mu L) is adopted, and the roughness of the inner wall is 0.8 mu m; the spiral treatment (spiral tube with outer diameter of 4mm and spiral pitch of 0.2 mm) was performed, the number of spiral turns was changed, the amount of liquid fed was 25. Mu.L, and the VK in example 1 was measured 1 The signal-to-noise ratio, lower limit of quantification, standard recovery, and fluctuation value of pure water of the quality control product LQC are shown in Table 12.
Table 12: spiral turns under 25 mu L of liquid
The results show that: when the number of spiral turns is less than 5, the fluctuation value is still very high; when the number of turns is 5, the VK can be maximized 1 The area of the detection peak in the detection process is increased, the signal-to-noise ratio is improved, the quantitative lower limit is reduced, the standard adding recovery rate is close to 100%, and the fluctuation value of pure water detection is reduced. The number of turns of the spiral was more than 5, and the effect was not obvious, and it was found that the inner diameter of the stainless steel S32750 tube having an inner diameter of 0.8mm, an outer diameter of 1.6mm and a tube length of 100mm (volume of 50. Mu.L) had an inner wall roughness of 0.8. Mu.m, and the spiral treatment was carried out (spiral tube having an outer diameter of 4mm and a spiral pitch of 0.2mm was produced)Under the condition of (2), the number of spiral turns reaches the upper limit, and 5 turns are preferable.
When the content of the detected substance is low or the sensitivity is low, 50 mu L of liquid inlet amount is often adopted, and the device provided by the invention also needs to be correspondingly adjusted; the VK in example 1 was measured by adjusting the feed rate to 50. Mu.L, using different numbers of spiral turns in sequence, and the other parameters were the same, using the same method as described above 1 The signal-to-noise ratio, lower limit of quantification, standard recovery, and fluctuation value of pure water of the quality control product LQC are shown in Table 13.
Table 13: spiral turns under 50 mu L of liquid
The results show that: when the liquid inlet amount is 50 mu L, the optimal spiral turns are 10 turns; when the number of turns is less than 10, the fluctuation value is higher, and the VK is higher 1 The detection peak area is lower, the signal-to-noise ratio is low, the quantitative lower limit is high, and the recovery rate is low; when the number of turns is greater than 10, the optimizing effect of each effect is not obvious, which indicates that the number of turns reaches the upper limit, and the effect is optimal when the number of spiral turns is 10.
In the embodiment 2, the human serum sample, the quality control product and the standard product are detected, wherein the quality control product is obtained by mixing the standard product with serum, approximately simulating a real blood sample, and obtaining good effects; the quality control LQC was used to simulate blood samples, and the quality control LQC-2 was used to simulate urine samples.
In the embodiment, whether samples from different sources can be well detected in the chromatograph provided by the invention is studied through detection of quality control substances LQC and LQC-2. The chromatograph provided by the invention and the chromatograph with conventional straight tube sample injection are used for measuring and calculating the VK in quality control products LQC and LQC-2 according to the same method in the embodiment 2 to the embodiment 8 1 Is the detection peak area, signal to noise ratio, VK of (2) 1 A lower limit of quantification of (2),VK 1 The results of the addition of the standard recovery and the fluctuation value are shown in Table 14.
Table 14: blood sample and urine sample detection
The results show that: the common chromatograph with straight tube sample injection has no obvious difference on the detection results of the blood quality control product LQC and the urine quality control product LQC-2, but the chromatograph with the mixed wave reduction device provided by the invention is used for detection, so that the detection peak area of the blood quality control product LQC is obviously improved, the signal to noise ratio is improved, the quantitative lower limit is reduced to 0.001 ng/mL, the standard adding recovery rate is close to 100%, and the fluctuation value is reduced by 25%; meanwhile, the detection result of the urine quality control product LQC-2 is not obviously improved; the chromatograph with the mixed wave reduction device provided by the invention has the beneficial effects on the detection of blood samples, and has no obvious improvement on the detection of urine samples.
The possible reason is that the blood sample is more complicated in structure and the molecules are not well distributed in serum, so that better effect can be achieved through the chromatograph detection containing the mixed wave reduction device; the urine sample is dispersed uniformly, the interference existing in the urine sample is less, the fluidity is good, and the spiral tube cannot have a targeted beneficial effect on the urine sample detection, so that the remarkable increase of the urine sample detection effect cannot be realized.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.
Claims (9)
1. The chromatograph with the mixed wave reduction device is characterized in that the mixed wave reduction device comprises a spiral mixing damper (1), the spiral mixing damper (1) comprises a spiral pipeline, and the inner wall of the spiral pipeline is provided with roughness; the spiral pipeline is provided with at least two spiral rings; the spiral rings are spaced; the sample is a blood sample.
2. The chromatograph of claim 1, wherein the material of the spiral conduit is any one or more of PP, PVC, PTFE, PEEK, silica gel, stainless steel; the roughness of the spiral pipeline is 0.4-2.0; the inner diameter of the spiral pipeline is 0.5-1.0 mm, and the outer diameter of the spiral pipeline is 1.0-2.0 mm; the outer diameter of the spiral ring is 3-5 mm; the distance between the spiral rings is 0.1-0.5 mm.
3. The chromatograph of claim 2, wherein the helical tube is of stainless steel S32750.
4. A chromatograph according to claim 3, wherein the helical tubing has a roughness of 0.8 μm.
5. The chromatograph of claim 4, wherein the spacing between the coils is 0.2mm.
6. The chromatograph of claim 5, wherein the helical tube has a tube inner diameter of 0.8mm and the helical tube has a tube outer diameter of 1.6mm.
7. The chromatograph of claim 6, wherein the helical turn has a helical outer diameter of 4mm.
8. The chromatograph of claim 7, wherein the number of turns of the spiral metal tube is 5 when the feed is 25 μl; when the amount of the feed liquid was 50. Mu.L, the number of spiral turns of the spiral metal pipe was 10.
9. A detection method of a chromatograph comprising a mixed wave reduction device, characterized in that a sample is mixed with a mobile phase by the chromatograph according to any one of claims 1 to 8, and the mixture is introduced into a chromatographic column, wherein the sample is a blood sample.
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