CN115219635B - Detection method of pinacol diboron based on gas chromatography - Google Patents
Detection method of pinacol diboron based on gas chromatography Download PDFInfo
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Abstract
The application provides a detection method of pinacol ester diborate based on gas chromatography. By exploring sample pretreatment and gas chromatography conditions and adopting a medium-polarity gas chromatography column combined mass spectrometry detection method, the thermal stability of the to-be-detected pinacol ester diboron in the analysis and detection process can be prolonged, so that the accuracy and the sensitivity of the detection method are improved, and the technical problem of poor evaluation index of the detection method caused by poor thermal stability of a target due to hydrolysis reaction of the pinacol ester diboron in liquid detection or sample matrix in gas detection is solved. The specificity, linearity, detection limit, accuracy and stability of the detection method are verified, and the method is confirmed to be suitable for content determination of the diboron pinacol ester.
Description
Technical Field
The application belongs to the technical field of compound analysis, and particularly relates to a gas chromatography-based detection method of pinacol ester diboron.
Background
The diboron pinacol ester is a common medical intermediate and is also a genotoxic impurity. Genotoxic impurities are impurities that react with DNA, cause DNA damage, induce gene mutations at very low levels, and are possibly carcinogenic, thus requiring strict control of the limits of such impurities in a sample.
At present, liquid chromatography is mostly adopted in a detection method for the diboron borate ester, but due to the fact that a borate ester compound contains a borate ester structure, hydrolysis reaction is easy to occur with water and alcohols, different borate ester reaction rates are different, water or alcohols are used for a liquid phase or a liquid mobile phase, and detection of a target substance is not facilitated. The gas chromatography has high requirement on the thermal stability of the compound, and the detection method has certain limitation because the target object has poor thermal stability in the gasification process of the sample inlet due to the existence of the sample matrix.
Disclosure of Invention
In view of this, the application provides a method for detecting pinacol ester diborate based on gas chromatography, which can prolong the thermal stability of an object to be detected and improve the accuracy and sensitivity of the detection method.
The specific technical scheme of the application is as follows:
a method for detecting pinacol ester diborate based on gas chromatography adopts a medium-polarity gas chromatography column as a chromatographic column of the gas chromatography, and the sample pretreatment conditions are as follows: dissolving by using a small amount of dimethyl sulfoxide, and then adding a mixed solution of cyclohexane and ultrapure water for extraction.
Further, the ratio of the amount of the sample to the amount of dimethyl sulfoxide was (50 to 100) mg: (0.1 to 0.2) ml.
Further, the volume ratio of cyclohexane to ultrapure water in the mixed solution is 1 (0.1 to 0.2).
Further, the dosage ratio of the sample to the mixed solution is (50 to 100) mg: (2 to 2.5) ml.
Furthermore, the carrier gas of the gas chromatography is He, and the split ratio is (3 to 4): 1.
Further, the temperature rise program of the gas chromatography is (50 to 70 ℃) and is kept for (1 to 2) min; heating to 240-250 ℃ at 30-40 ℃/min, and keeping for 2-8 min.
Furthermore, the flow rate of the gas chromatography is (0.8 to 1.2) ml/min, and the injection volume is (1 to 5) microliter.
Further, the gas chromatography adopts mass spectrometry detection, and the mass spectrometry parameters are as follows: the collection type is as follows: MRM, ion source: EI, transmission line temperature: (250 to 300 ℃ C., quadrupole temperature: 150 ℃, ion source temperature: at 250 deg.c.
Further, gas chromatography adopts mass spectrometry detection, mass spectrometryThe scanning parameters are: parent ion 239 (m/z) Daughter ion 57/85: (m/z），CE（5~25）（eV）。
Further, samples include chemicals, biologicals, and pharmaceuticals.
The application provides a gas chromatography-based detection method of pinacol ester diboron, which comprises the steps of dissolving a sample by dimethyl sulfoxide, then adding cyclohexane and water for extraction, layering the dissolved dimethyl sulfoxide and the water with cyclohexane, and reducing the retention time of the pinacol ester diboron in an aqueous phase by a rapid extraction mode and rapidly entering the cyclohexane phase from the aqueous phase to reduce the hydrolysis of the pinacol ester diboron; meanwhile, the liquid-liquid extraction can remove the sample matrix, and the optimized gas chromatography conditions can be utilized to greatly improve the thermal stability of the target object in the gasification process of the diboron pinacol ester at the gas injection port, so that the detection of the diboron pinacol ester by using the gas chromatography-tandem mass spectrometry becomes possible. The detection method is high in accuracy and sensitivity, and the technical problem that evaluation indexes of the detection method are poor due to poor thermal stability of a target object caused by a sample matrix in liquid phase detection or gas phase detection of the diboron pinacol ester is solved. The specificity, linearity, detection limit, accuracy and stability of the detection method are verified, and the method is confirmed to be suitable for content determination of the diboron pinacol ester.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a chromatogram of specificity of example 1 of the present application;
FIG. 2 is a linear graph of example 1 of the present application;
FIG. 3 is a chromatogram of comparative example 1 of the present application;
FIG. 4 is a chromatogram of comparative example 2 of the present application;
FIG. 5 is a chromatogram of comparative example 4 of the present application;
FIG. 6 is a linear graph of comparative example 5 of the present application.
Detailed Description
In order to make the objects, features and advantages of the present application more obvious and understandable, the technical solutions in the embodiments of the present application are clearly and completely described, and it is obvious that the embodiments described below are only a part of the embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The reagents and raw materials used in the examples of the present application are commercially available or self-made.
Example 1
Gas chromatography conditions: a chromatographic column: VF-624ms column (30 m × 0.25mm,1.4 μm); flow rate: 1.0ml/min; sample introduction volume: 1 mul; shunting mode: split, split ratio 4:1; and (3) control mode: a constant flow rate; carrier gas: he; temperature rising procedure: maintaining at 70 deg.C for 1min; heating to 250 deg.C at 30 deg.C/min, and maintaining for 3min.
Mass spectrum parameters: the collection type is as follows: MRM, ion source: EI, transmission line temperature: 250 ℃, quadrupole temperature: 150 ℃, ion source temperature: at 250 deg.c.
Impurity scanning parameters: parent ion 239 (m/z) Daughter ion 57/85 (m/z) Dwell time 160 (ms), CE15/25 (eV).
Preparing a test solution: weighing about 50mg of sample, placing the sample in a 10ml centrifuge tube, accurately adding 0.1ml of dimethyl sulfoxide, swirling until the sample is completely dissolved, precisely adding 2ml of cyclohexane and 0.2ml of ultrapure water in sequence, swirling for 1min, standing for layering, taking supernatant, and filtering to obtain the product.
Preparing a detection limiting solution: accurately weighing a reference substance of the pinacol ester diboron, placing the reference substance into a 10ml volumetric flask, adding cyclohexane to dissolve and dilute the reference substance to a scale, shaking up, and preparing a reference substance stock solution. Taking a sample of about 50mg, placing the sample in a 10ml centrifuge tube, accurately adding 0.1ml of dimethyl sulfoxide, swirling until the sample is completely dissolved, adding 0.02ml of reference substance stock solution, swirling and oscillating, sequentially and precisely adding 2ml of cyclohexane and 0.2ml of ultrapure water, swirling for 1min, standing for layering, taking supernatant, and filtering to obtain the product.
Preparing a standard curve solution: weighing about 50mg of sample, placing the sample in different 10ml centrifuge tubes, accurately adding 0.1ml of dimethyl sulfoxide, and vortexing until the sample is completely dissolved; precisely measuring 0.02ml of each standard curve stock solution respectively, placing the stock solution into the centrifuge tube, performing vortex oscillation, precisely adding 2ml of cyclohexane and 0.2ml of ultrapure water in sequence, performing vortex oscillation for 1min, standing for layering, taking supernate, and filtering to obtain a series of standard curve solutions with different concentrations.
Preparing an accurate solution: weighing about 50mg of sample, placing the sample in a 10ml centrifuge tube, accurately adding 0.1ml of dimethyl sulfoxide, carrying out vortex oscillation until the sample is completely dissolved, adding 0.02ml of reference substance stock solution, carrying out vortex oscillation, sequentially and precisely adding 2ml of cyclohexane and 0.2ml of ultrapure water, carrying out vortex for 1min, standing for layering, taking supernatant, and filtering to obtain the product.
(1) The specificity is as follows:
the test solution, the 100% limiting concentration control solution (concentration of 316.96 ng/ml) and the accuracy solution were separately collected and analyzed according to the test conditions. The result shows that no target peak is detected in the chromatogram of the test solution; a target peak is displayed in a chromatogram of the 100% limit concentration reference solution, and the degrees of separation from adjacent peaks with peak areas larger than LOQ are both larger than 1.5; target peaks are shown in accuracy solution chromatograms (shown in figure 1), and the degrees of separation from adjacent peaks with peak areas larger than LOQ are all larger than 1.5; the results are all in accordance with the regulations, and the method has good specificity.
(2) Linearity:
taking a standard curve solution, and carrying out sample injection detection according to an analysis method. The results are shown in FIG. 2 and show that: in the range of 4.75ng/ml to 633.93ng/ml, the concentration is equivalent to 1.5% -200% of the limit concentration, the peak area of the diboron pinacol ester has good linearity with the concentration, the correlation coefficient r is not less than 0.990, the ratio of the absolute value of the y-axis intercept to the 100% limit concentration response value is 0.2%, and the linearity meets the regulation.
(3) Detection limit:
and (4) continuously injecting the detection limit solution for 3 times respectively, and recording a chromatogram map. The results show that: the concentration of the pinacol ester diboron in the continuous 3-pin detection limit solution is 2.38ng/ml, which is equivalent to 0.75 percent of the limit concentration, the S/N is within the range of 7.6 to 10.9, and the detection limit result of the method conforms to the regulation.
(4) The accuracy is as follows:
and (3) taking the accuracy solution, respectively injecting samples for 3 times according to the test conditions, analyzing, recording a chromatogram and calculating a recovery rate result. The recovery rate of the diboron acid pinacol ester in 3 portions of the added standard test solution with the limit concentration of 100 percent ranges from 89.0 percent to 104.5 percent, the RSD (n = 3) of the recovery rate is less than 6 percent, and the accuracy result meets the specification.
(5) Stability:
respectively taking the test solution, the 100% limit concentration reference solution and the accuracy solution, standing at room temperature for different times, performing sample injection analysis according to an analysis method, and recording a chromatogram. Standing at room temperature for 11.5h until no pinacol ester of diboronic acid is detected in the test solution; the ratio of the detection concentration of the pinacol ester diboron to the initial (0 h) detection concentration in the control solution with 100% of limit concentration is 88.4-92.3%; the ratio of the detection concentration of the pinacol ester diboron to the initial (0 h) detection concentration in the accuracy solution is between 86.4% and 88.3%; thus, the test solution, the 100% limiting control solution, and the accuracy solution are stable for at least 11.5 hours at room temperature.
Comparative example 1
The sample analysis was performed on the accurate solution under the conditions of gas chromatography and mass spectrometry according to example 1, except that in the preparation of the accurate solution, the sample was dissolved with an equal amount of acetone, and then 2ml of cyclohexane and 2ml of ultrapure water were added to the sample, and the other conditions were not changed. The result is shown in fig. 3, the peak time of the object to be detected is 7.744min, the recovery rate is about 87%, but the recovery rate falls to 60% after 5 hours, and the stability is not satisfactory.
Comparative example 2
Sampling analysis was performed on the exact solution with reference to the gas chromatography and mass spectrometry conditions of example 1, except that in the gas chromatography conditions, the split ratio was adjusted to 2: maintaining at 70 deg.C for 1min; heating to 250 deg.C at 50 deg.C/min, and maintaining for 5min under the same conditions. The result is shown in FIG. 4, the peak-off time of the sample is 6.373min, the recovery rate is only 67%, and the accuracy does not meet the requirement.
Comparative example 3
The sample analysis was performed on the exact solution with reference to the gas chromatography and mass spectrometry conditions of example 1, except that in the exact solution formulation, 2ml cyclohexane, 0.2ml sodium hydroxide solution was vortexed, and the other conditions were not changed. The results show that the peak-to-peak area of the target is small and basically no response is generated.
Comparative example 4
The exact solution was sampled and analyzed with reference to the gas chromatography and mass spectrometry conditions of example 1, except that in the exact solution preparation, the same amount of 1% tetrabutylammonium bromide-acetone solution was used for dissolution, 2ml of cyclohexane and 2ml of 1mol/L HCl were added for vortex oscillation, and the other conditions were not changed. The results are shown in FIG. 5, which shows that the separation degree of the analyte from the adjacent peak is poor, and the recovery rate and the stability are not qualified.
Comparative example 5
A series of solutions with different scalar addition degrees are sampled and analyzed according to the conditions of gas chromatography and mass spectrum of example 1, and the difference is only that in the preparation of the solutions with different degrees of accuracy, a sample is dissolved by adopting equal amount of N-methylpyrrolidone, then 2ml of cyclohexane and 5ml of ultrapure water are precisely transferred, vortex oscillation is carried out, and other conditions are not changed. The results are shown in FIG. 6, where the linearity of the analyte was poor and the RSD% recovery in 6 parallel assays exceeded 15%.
The above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.
Claims (5)
1. A detection method of pinacol ester diboron based on gas chromatography is characterized in that a gas chromatography column adopts a VF-624ms column, the gas chromatography adopts mass spectrometry, carrier gas of the gas chromatography is He, the split ratio is (3 to 4): 1, the temperature rise program of the gas chromatography is (50 to 70) ° C, and the temperature rise program is kept for (1 to 2) min; heating to 240-250 ℃ at 30-40 ℃/min and keeping for 2-8 min;
the sample pretreatment conditions are as follows: dissolving a small amount of dimethyl sulfoxide, adding a mixed solution of cyclohexane and ultrapure water, and extracting, wherein the dosage ratio of the sample to the dimethyl sulfoxide is (50 to 100) mg: (0.1 to 0.2) ml, wherein the volume ratio of cyclohexane to ultrapure water in the mixed solution is 1 (0.1 to 0.2), and the dosage ratio of the sample to the mixed solution is (50 to 100) mg: (2 to 2.5) ml.
2. The gas chromatography-based detection method of pinacol diboron ester according to claim 1, wherein the flow rate of the gas chromatography is (0.8 to 1.2) ml/min, and the injection volume is (1 to 5) μ l.
3. The gas chromatography-based detection method of pinacol ester diborate according to claim 1, characterized in that the mass spectrometry parameters are: the collection type is as follows: MRM, ion source: EI, transmission line temperature: (250 to 300 ℃ C., quadrupole temperature: 150 ℃, ion source temperature: at 250 ℃ to obtain a mixture.
4. The gas chromatography-based detection method of pinacol ester diborate according to claim 1, characterized in that the mass spectrometry scan parameters are: parent ion 239 (m/z) Daughter ion 57/85 (m/z），CE（5~25）（eV）。
5. The gas chromatography-based detection method of pinacol ester diborate according to claim 1, wherein the sample comprises chemicals, biologicals and drugs.
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| CN102558209A (en) * | 2012-01-11 | 2012-07-11 | 海门瑞一医药科技有限公司 | Bis(pinacolato)diboron production process |
| CN105198911A (en) * | 2015-10-20 | 2015-12-30 | 华侨大学 | Catalyzed synthesis method of alkyl boric acid ester |
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| CN102558209A (en) * | 2012-01-11 | 2012-07-11 | 海门瑞一医药科技有限公司 | Bis(pinacolato)diboron production process |
| CN105198911A (en) * | 2015-10-20 | 2015-12-30 | 华侨大学 | Catalyzed synthesis method of alkyl boric acid ester |
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| 2-氟-4-甲基吡啶-5-硼酸频那醇酯的合成工艺研究;吴省付等;《广东化工》;20141231;第41卷(第17期);第8页 * |
| Selective quantitation of B2Pin2 and B2(OH)4 in active pharmaceutical ingredients by gas chromatography-mass spectrometry;Armen Shamirian等;《Journal of Pharmaceutical and Biomedical Analysis》;20210223;第198卷;第1-5页 * |
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