CN114324672A - Method for analyzing betaine containing different ethoxy groups - Google Patents
Method for analyzing betaine containing different ethoxy groups Download PDFInfo
- Publication number
- CN114324672A CN114324672A CN202210026606.7A CN202210026606A CN114324672A CN 114324672 A CN114324672 A CN 114324672A CN 202210026606 A CN202210026606 A CN 202210026606A CN 114324672 A CN114324672 A CN 114324672A
- Authority
- CN
- China
- Prior art keywords
- betaine
- ethoxy groups
- mass
- containing different
- different numbers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses an analysis method of betaine containing different ethoxy groups, which adopts a liquid chromatography-mass spectrometry combined technology and uses hydrophobic C8Or C18Bonded silica gel is used as a separation material, acetonitrile and water are used as mobile phases, gradient elution is carried out, and mass spectrum positive ion mode detection is carried out. The result shows that betaine samples containing different numbers of ethoxy groups can be effectively separated on a chromatogram, the peak emergence time of different components is related to the number of ethoxy groups, and the larger the number of ethoxy groups, the shorter the retention time of the corresponding betaine. Qualitative analysis can be carried out on the betaine according to mass spectrograms corresponding to different retention times; according to chromatographic peaks in the total ion current chromatogram, the betaine can be quantitatively analyzed by an area normalization method. The invention can separate betaine samples with complex structural composition into systemsThe single compounds in the column provide technical support for mastering the distribution and content of each component containing different numbers of ethoxy groups in the betaine.
Description
Technical Field
The invention relates to an analysis method of betaine, in particular to an analysis method of a betaine mixed sample system containing different numbers of ethoxy groups, belonging to the analysis and detection technology of a surfactant in the technical field of oilfield chemical flooding enhanced recovery.
Background
In the process of improving the recovery ratio by chemical flooding of the oil field, the surfactant has excellent interface performance and is widely applied. Betaine serving as a zwitterionic surfactant has good foam stability and interface activity, and is often used as a compound chemical agent to improve the oil washing efficiency of an oil displacement formula. The types of betaines are various, including alkyl betaines, alkyl amidopropyl betaines, alkyl hydroxy betaines, sulfobetaines, amidopropyl sulfobetaines and the like, and the distribution range of carbon chains is relatively wide. When the alkyl carbon chain of betaine is longer, the water solubility of the sample is reduced, and even the sample is difficult to dissolve. In order to increase the water solubility of the long-carbon-chain betaine and improve the hydrophilic and lipophilic properties of the betaine, researchers also add an ethoxy group in the process of preparing the betaine so that the betaine has better physicochemical properties.
Betaine is analyzed and detected by a plurality of methods, including colorimetry, gravimetric method, titration method, chromatography and the like, and the structural composition of an analysis object is relatively single. For betaine containing ethoxy, the number of ethoxy groups contained in the finally generated betaine is different due to different polymerization degrees in the sample synthesis process, and no efficient and accurate analysis method exists for the analysis and detection of the betaine. Therefore, the development of a novel analysis method capable of accurately and sensitively detecting the betaines with different numbers of ethoxy groups in the sample is a research work which has a wide application prospect and needs to be solved.
Disclosure of Invention
The invention aims to provide an analysis and detection method aiming at the defects and the technical blank of the analysis and detection of betaine mixed samples containing different numbers of ethoxy groups, and the method can effectively identify the quantity distribution range and the relative content result of the ethoxy groups in the samples.
The invention relates to a method for analyzing betaine containing different ethoxy groups, which comprises the following steps:
(1) chromatography-mass spectrometry analysis: analyzing and detecting betaine samples containing different ethoxy groups by adopting a chromatography-mass spectrometry combined technology to obtain a total ion current chromatogram and a mass spectrogram of the samples;
chromatographic separation conditions: by inverting C8Or C18A (5 mu m, 4.6 multiplied by 150 mm) chromatographic column is used as an analysis column, acetonitrile and water are used as mobile phases, a gradient elution mode is adopted for separation, the gradient condition is 0-20 min, 80% -100% of acetonitrile, the flow rate is 0.6mL/min, the temperature is 20-30 ℃, the sample injection volume is 5-20 mu L, and the sample concentration is 1000-4000 mg/L;
mass spectrometry conditions: the mass spectrum type is a flight time mass spectrum, the gas temperature is 350 ℃, the drying gas flow rate is 6-8L/min, and the atomization gas pressure is 30-35 psi; the scanning range is 50-1700 Dr, and the detection mode is positive ion mode.
(2) And (3) qualitative analysis: extracting mass spectrograms corresponding to different retention times in the total ion current chromatogram, and carrying out qualitative analysis on the betaine components according to mass-to-charge ratios of the mass spectrograms to obtain structures of the betaine components containing different numbers of ethoxy groups; qualitative analysis can be carried out on the betaine according to the mass spectrograms corresponding to different retention times, the mass-to-charge ratios corresponding to the betaine containing different numbers of ethoxy groups are regularly distributed in the mass spectrograms, and the difference between the mass-to-charge ratios is 44 molecular weights; the corresponding mass-to-charge ratio of betaine is generally M +23 molecular ion peak, so that subtracting 23 from the mass-to-charge ratio is the molecular weight of the betaine component, and the structure of betaine is determined.
(3) Quantitative analysis: integrating chromatographic peaks in the total ion current chromatogram, and normalizing the chromatographic peak areas corresponding to betaine components containing different numbers of ethoxy groups to obtain the relative content result of each betaine component.
The result shows that betaine samples containing different numbers of ethoxy groups can be effectively separated on a chromatogram, the peak emergence time of different components is related to the number of ethoxy groups, and the larger the number of ethoxy groups, the shorter the retention time of the corresponding betaine. Qualitative analysis can be carried out on the betaine according to the mass spectrograms corresponding to different retention times, the mass-to-charge ratios corresponding to the betaine containing different numbers of ethoxy groups are regularly distributed in the mass spectrograms, and the difference between the mass-to-charge ratios is 44 molecular weights; the corresponding mass-to-charge ratio of betaine is generally M +23 molecular ion peak, so that subtracting 23 from the mass-to-charge ratio is the molecular weight of the betaine component. According to chromatographic peaks in the total ion current chromatogram, the betaine can be quantitatively analyzed by an area normalization method.
In conclusion, the betaine analysis method established by the invention can separate the betaine sample with complex structural composition into a series of single compounds, can effectively identify the quantity distribution range of the ethoxy groups in the sample, and can obtain the relative content results of the betaines with different numbers of ethoxy groups. The results provide a material evaluation basis for deeply knowing the role of the structural composition of the betaine in the chemical flooding tertiary oil recovery process.
Drawings
FIG. 1 is a total ion current chromatogram of a betaine sample according to the invention;
FIG. 2 is a mass spectrum corresponding to the retention time of the present invention in the range of 9-12 min;
FIG. 3 is a mass spectrum corresponding to the components with retention time of 11min in the present invention.
Detailed Description
The method of analyzing betaine containing different numbers of ethoxy groups according to the present invention is illustrated by the following specific examples.
The apparatus used was: liquid chromatography-time of flight mass spectrometer, agilent G6500 series, usa; inverse phase C18Chromatographic column (5μm, 4.6X 150 mm), developed by Lanzhou chemical and physical research institute of Chinese academy of sciences.
Reagent: acetonitrile, chromatographically pure, beijing mai ruida science and technology ltd; alkyl betaine containing ethoxy, synthetic product, and institute of chemico-physical, Lanzhou, academy of sciences of China.
(1) Preparation of a chromatographic column: filling a chromatographic column by adopting a high-pressure homogenizing method, wherein the homogenizing liquid is carbon tetrachloride, the displacing liquid is n-hexane, and the pressure is 40 Mpa;the filler is reversed phase C18The particle size of the chromatographic packing is 5 mu m, the specification of the chromatographic column is 4.6cm in inner diameter and 15cm in length.
(2) Chromatographic-mass spectrometry conditions: carrying out chromatography-mass spectrometry on betaine samples containing different ethoxy groups to obtain a total ion current chromatogram of the sample, which is shown in figure 1;
the analysis conditions were as follows:
the chromatographic separation uses acetonitrile and water as mobile phases, and adopts a gradient elution mode to carry out separation, wherein the gradient condition is 0-20 min, 80% -100% of acetonitrile, the flow rate is 0.6mL/min, the temperature is 25 ℃, and the sample injection volume is 20 muL. In the mass spectrum parameters, the gas temperature is 350 ℃, the drying gas flow rate is 8L/min, the atomization gas pressure is 35psi, the scanning range is 50-1700 Dr, and the detection mode is a positive ion mode.
(3) And (3) qualitative analysis: and extracting a mass spectrogram corresponding to the retention time of 9-12 min in the total ion current chromatogram, wherein the result is shown in figure 2, and the figure shows a mixed mass spectrogram of betaine components contained in the sample. Extracting mass spectrograms corresponding to different chromatographic peaks in the total ion current chromatogram, such as chromatographic peaks with retention time of 11.0min, 11.5min, 12.0min, etc., to obtain the mass spectrograms of components corresponding to the chromatographic peaks. For simplicity of description, a mass spectrum of the fraction with a retention time of 11.0min was extracted, as an example, as the betaine fraction in the sample was more, see fig. 3.
(4) Quantitative analysis: integrating chromatographic peaks with retention time within 9-12 min to obtain peak areas of each chromatographic peak, processing according to an area normalization method to obtain relative content results of each betaine, and calculating the results shown in table 1.
As can be seen from FIG. 1, betaines with different numbers of ethoxy groups appear in a chromatogram as a series of chromatographic peaks, the chromatographic peaks corresponding to most betaine components can obtain good chromatographic separation effect, and the area of the chromatographic peak of betaine with higher polymerization degree, i.e. more ethoxy groups, is relatively lower. As can be seen from FIG. 2, the betaine sample has a complex structure composition and is a mixed sample system composed of a series of different compounds; if the structure of the sample is directly analyzed, signals in a mass spectrogram are various, and more obstacles are brought to the structure identification result. As can be seen from FIG. 3, the chromatographic peak with retention time of 11.0min corresponds to a compound, the mass spectrum signal is simpler, the signal interference of other coexisting components is eliminated, and the accurate analysis of the structure is facilitated.
According to the experimental results, a series of chromatographic peaks can be obtained after the betaine sample is subjected to chromatographic separation, each chromatographic peak represents a compound, and the structural information of the compound can be accurately judged according to the corresponding mass-to-charge ratio of the compound. Because a single standard betaine control substance containing different numbers of ethoxy groups cannot be obtained, in the practical application process, the distribution result of the ethoxy groups with different numbers is difficult to predict; according to the method, after the betaine sample is subjected to chromatography-mass spectrometry analysis and detection, the relative content result of each betaine can be obtained by combining an area normalization method, and great help is brought to the understanding of the polymerization degree and content distribution result of ethoxy in the betaine production process.
TABLE 1 crude oil component content test results
As can be seen from Table 1, the betaine with the ethoxy number of 1-4 in the sample is relatively high in content, the percentage content is more than 10%, and the sample contains more betaine without ethoxy; with the increase of the degree of polymerization of the ethoxy group, the content of betaine is gradually reduced, and the distribution range of the number of the ethoxy group is between 0 and 12.
Claims (2)
1. A method for analyzing betaines containing different numbers of ethoxy groups comprises the following steps:
(1) chromatography-mass spectrometry analysis: analyzing and detecting betaine samples containing different ethoxy groups by adopting a chromatography-mass spectrometry combined technology to obtain a total ion current chromatogram and a mass spectrogram of the samples; the analysis conditions were as follows:
chromatographic separation conditions: the chromatographic column is a hydrophobic analytical column, the mobile phase is water and acetonitrile, gradient elution is carried out, the flow rate is 0.6mL/min, the temperature is 20-30 ℃, and the sample injection volume is 5-20 muL;
mass spectrometry conditions: the mass spectrum type is a flight time mass spectrum, the gas temperature is 350 ℃, the drying gas flow rate is 6-8L/min, and the atomization gas pressure is 30-35 psi; the scanning range is 50-1700 Dr, and the detection mode is a positive ion mode;
(2) and (3) qualitative analysis: extracting mass spectrograms corresponding to different retention times in the total ion current chromatogram, and carrying out qualitative analysis on the betaine components according to mass-to-charge ratios of the mass spectrograms to obtain structures of the betaine components containing different numbers of ethoxy groups;
(3) quantitative analysis: integrating chromatographic peaks in the total ion current chromatogram, and normalizing the chromatographic peak areas corresponding to the betaine components containing different numbers of ethoxy groups to obtain the relative content results of the betaine components containing different numbers of ethoxy groups.
2. A method of analyzing betaines having different numbers of ethoxy groups as claimed in claim 1, wherein: the separating material used by the chromatographic column is hydrophobic reversed phase C8Or C18Bonding silica gel, wherein the gradient condition of a mobile phase is 0-20 min, and 80-100% of acetonitrile.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210026606.7A CN114324672B (en) | 2022-01-11 | 2022-01-11 | Method for analyzing betaine containing different ethoxy groups |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210026606.7A CN114324672B (en) | 2022-01-11 | 2022-01-11 | Method for analyzing betaine containing different ethoxy groups |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114324672A true CN114324672A (en) | 2022-04-12 |
CN114324672B CN114324672B (en) | 2022-10-04 |
Family
ID=81027343
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210026606.7A Active CN114324672B (en) | 2022-01-11 | 2022-01-11 | Method for analyzing betaine containing different ethoxy groups |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114324672B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1088251A (en) * | 1992-09-01 | 1994-06-22 | 普罗格特-甘布尔公司 | The liquid or the gel dishwashing detergent that contain alkyl ethoxy carboxylate, divalent ion and many oxyethyl groups of alkyl multi-carboxylate |
DE10134366A1 (en) * | 2001-07-14 | 2003-01-23 | Aventis Pharma Gmbh | Production of optically active 2-(2,5-dioxo-1-imidazolidinyl)acetic acid derivatives, useful as pharmaceutical intermediates, comprises stereoselective enzymatic hydrolysis of a mixture of enantiomers with an esterase |
WO2013158277A1 (en) * | 2012-04-18 | 2013-10-24 | Waters Technologies Corporation | Methods for quantifying polypeptides using mass spectrometry |
CN109030665A (en) * | 2018-10-08 | 2018-12-18 | 黑龙江大学 | The detection method of beet alkali content in hydrophilic liquid phase chromatographic tandem mass spectrometric determination red beet |
CN110954639A (en) * | 2019-12-16 | 2020-04-03 | 中国计量大学 | Analysis method of styrylphenol polyoxyethylene ether surfactant |
-
2022
- 2022-01-11 CN CN202210026606.7A patent/CN114324672B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1088251A (en) * | 1992-09-01 | 1994-06-22 | 普罗格特-甘布尔公司 | The liquid or the gel dishwashing detergent that contain alkyl ethoxy carboxylate, divalent ion and many oxyethyl groups of alkyl multi-carboxylate |
DE10134366A1 (en) * | 2001-07-14 | 2003-01-23 | Aventis Pharma Gmbh | Production of optically active 2-(2,5-dioxo-1-imidazolidinyl)acetic acid derivatives, useful as pharmaceutical intermediates, comprises stereoselective enzymatic hydrolysis of a mixture of enantiomers with an esterase |
WO2013158277A1 (en) * | 2012-04-18 | 2013-10-24 | Waters Technologies Corporation | Methods for quantifying polypeptides using mass spectrometry |
CN109030665A (en) * | 2018-10-08 | 2018-12-18 | 黑龙江大学 | The detection method of beet alkali content in hydrophilic liquid phase chromatographic tandem mass spectrometric determination red beet |
CN110954639A (en) * | 2019-12-16 | 2020-04-03 | 中国计量大学 | Analysis method of styrylphenol polyoxyethylene ether surfactant |
Non-Patent Citations (5)
Title |
---|
LUIGI S 等: "The betaine profile of cereal flours unveils new and uncommon betaines", 《FOOD CHEMISTRY》 * |
VICTORIA E 等: "Analysis of fatty alcohol derivatives with comprehensive two-dimensional liquid chromatography coupled with mass spectrometry", 《JOURNAL OF CHROMATOGRAPHY A》 * |
夏琪波 等: "聚氧乙烯化羧基甜菜碱的性能研究", 《日用化学工业》 * |
李艳荣 等: "甜菜碱脂在14种海洋微藻中的分布研究", 《海洋学报》 * |
陈晖 等: "烷基聚氧乙烯醚磺基甜菜碱的构效关系研究", 《日用化学工业》 * |
Also Published As
Publication number | Publication date |
---|---|
CN114324672B (en) | 2022-10-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Pilařová et al. | Recent developments in supercritical fluid chromatography–mass spectrometry: is it a viable option for analysis of complex samples? | |
Harrieder et al. | Current state-of-the-art of separation methods used in LC-MS based metabolomics and lipidomics | |
SAGARA et al. | A simultaneous determination of norephedrine, pseudoephedrine, ephedrine and methylephedrine in Ephedrae Herba and oriental pharmaceutical preparations by ion-pair high-performance liquid chromatography | |
Chen et al. | Simultaneous screening for lipophilic and hydrophilic toxins in marine harmful algae using a serially coupled reversed-phase and hydrophilic interaction liquid chromatography separation system with high-resolution mass spectrometry | |
CN112903872B (en) | Separation method and application of carbazole nitride in petroleum component | |
CN110658285A (en) | Method for rapidly detecting contents of 2-methylimidazole and 4-methylimidazole in caramel color | |
CN107655991A (en) | The assay method of 6 kinds of phthalic acid esters in soil | |
Sandra et al. | Evaluation of micro-pillar array columns (µPAC) combined with high resolution mass spectrometry for lipidomics | |
CN103675175A (en) | Method for determination of pesticide residues in vegetable oils | |
Lukacs et al. | Identification and determination of fumonisin FB 1 and FB 2 in corn and corn products by high-performance liquid chromatography-electrospray-ionization tandem mass spectrometry (HPLC-ESI-MS-MS) | |
Garrido et al. | Detection of new pigments from Emiliania Huxleyi (prymnesiophyceae) by high‐performance liquid chromatography, liquid chromatography–mass spectrometry, visible spectroscopy, and fast atom bombardment mass spectrometry | |
CN109324130A (en) | The measuring method of aflatoxin in a kind of tobacco and tobacco product | |
CN108426972B (en) | Method for splitting and measuring chiral pesticide benalaxyl enantiomer by ultra-high performance combined chromatography-tandem mass spectrometry technology | |
CN114324672B (en) | Method for analyzing betaine containing different ethoxy groups | |
Weisz et al. | Preparative separation and identification of novel subsidiary colors of the color additive D&C Red No. 33 (Acid Red 33) using spiral high-speed counter-current chromatography | |
Zhao-Yong et al. | Rapid screening and identification of paralytic shellfish poisoning toxins in red tide algae using hydrophilic interaction liquid chromatography-high resolution mass spectrometry with an accurate-mass database | |
Wu et al. | Highly sensitive detection of melamine based on reversed phase liquid chromatography mass spectrometry | |
CN109884199B (en) | Method for measuring content of flavonoid components in honey | |
CN110927269A (en) | Method for quantitatively detecting DL-2-hydroxy-4-methyl ethyl valerate in wine | |
CN112697892B (en) | Method for quantitatively detecting cyclic alkyl sulfonate component and residual oil sulfonate component in petroleum production liquid | |
Yu et al. | Determination of myriocin in natural and cultured Cordyceps cicadae using 9-fluorenylmethyl chloroformate derivatization and high-performance liquid chromatography with UV-detection | |
CN105301152B (en) | A kind of biocompatibility solid phase extraction method suitable for Clenizole Hydrochloride | |
CN105158381B (en) | The detection method of single, double, triple ester in a kind of triethanol amine ester quat | |
CN109030683B (en) | A method of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid | |
CN108828102B (en) | Method for determining content of pineapple ester and jasmal in essence and flavor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |