CN111423360A - Acrolein-serine adduct and preparation method and application thereof - Google Patents

Acrolein-serine adduct and preparation method and application thereof Download PDF

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CN111423360A
CN111423360A CN202010343353.7A CN202010343353A CN111423360A CN 111423360 A CN111423360 A CN 111423360A CN 202010343353 A CN202010343353 A CN 202010343353A CN 111423360 A CN111423360 A CN 111423360A
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acrolein
serine
adduct
serine adduct
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欧仕益
邹照佳
黄才欢
欧隽滢
刘付
张延杰
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Jinan University
University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • G01—MEASURING; TESTING
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Abstract

The invention belongs to the technical field of food detection, and discloses an acrolein-serine adduct and a preparation method and application thereof. The preparation method of the acrolein-serine adduct comprises the following steps: heating acrolein and serine in water at constant temperature for reaction, and performing subsequent treatment to obtain an acrolein-serine adduct; the molar ratio of acrolein to serine is 1: (1-3). The method is simple, and the obtained product has high yield and high purity. The acrolein-serine adduct is applied to the field of food detection.

Description

Acrolein-serine adduct and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic compound synthesis, and particularly relates to an acrolein-serine adduct and a preparation method and application thereof.
Background
Acrolein, the most active aldehyde of the α -unsaturated carbonyl structure, is widely present in environmentally and thermally processed foods and also can be produced by endogenous metabolism studies have shown that acrolein is very reactive with nucleophilic macromolecules in organisms, interfering with DNA replication and transcription, leading to protein cross-linking and ultimately causing various diseases (L D50 in mice and rats at 30 and 50mg/kg body weight.) furthermore, it can also reduce intracellular Glutathione (GSH) levels and interfere with cellular signaling pathways, making acrolein a safety concern widespread.
It has been found that after frying food products such as potatoes, the acrolein content in the fried potato chips is much lower (2-3 orders of magnitude) than the sum of the acrolein content in the frying oil and the acrolein content in the potatoes, while after digestion, the acrolein content in the human body is much higher (more than 200 times) than that in the potato chips, which is very likely to cause food safety hazards because the acrolein reacts with food ingredients during frying, so that the actual exposure level of the acrolein in the food is covered.
The serine is also called β -hydroxy alanine, which plays an important role in the metabolism of fat and fatty acid and the growth of muscle, and is also essential for the maintenance of healthy immune system because it helps the generation of immune globulin and antibody, the human body can obtain serine from a large amount of plant and animal protein, and serine can be synthesized from glycine if necessary.
There is a need for further studies on how to obtain adducts in high yield, high purity and as standards for the detection of acrolein reaction products in foods.
Disclosure of Invention
In order to overcome the disadvantages and drawbacks of the prior art, it is an object of the present invention to provide an acrolein-serine adduct and a method for preparing the same. The method is simple, and the obtained product has high yield and high purity.
It is another object of the present invention to provide the use of the above acrolein-serine adduct. The application of the acrolein-serine adduct in the field of food detection is used as a standard substance for detecting acrolein reaction products in food so as to analyze the performance and the content of the acrolein adduct in the food more quickly.
The purpose of the invention is realized by the following technical scheme:
a method for preparing an acrolein-serine adduct comprising the steps of: heating acrolein and serine in water at constant temperature for reaction, and performing subsequent treatment to obtain acrolein-serine adduct.
The molar ratio of acrolein to serine is 1: (1-3).
The temperature of the heating reaction is 20-60 ℃, and preferably 45-55 ℃; the heating reaction time is 3-12 h, preferably 4-6 h.
The reaction is carried out with stirring. The stirring speed is 100-200 rpm.
The dosage ratio of the acrolein to the water is (1-3) mmol, (1-50) m L.
And the subsequent treatment refers to concentrating the reacted system, filtering with a filter membrane, and purifying by a reverse phase silica gel chromatography to obtain a purified product. The filter membrane is a 0.45 mu m filter membrane; the concentration is a reduced pressure concentration.
The reverse phase silica gel chromatography specifically comprises the following steps: selecting reverse phase silica gel ODS resin, loading, eluting with 5% methanol water solution, collecting target adduct by 2, 4-dinitrophenylhydrazine solution color development method, detecting purity by high performance liquid detection method, collecting eluent, and freeze drying to obtain purified sample. The freeze drying condition is preferably-70 to-40 ℃ and 1 to 100 Pa.
According to the high performance liquid chromatography detection result and the nuclear magnetic resonance spectrum result, the purity of the adduct prepared by the method is up to 99%, wherein the peak purity of a target single peak under each display wavelength (200-400 nm) of the high performance liquid chromatography is up to 99%.
The HP L C method comprises the following steps of carrying out gradient elution for 25min under the conditions that a chromatographic column Zorbax SB-Aq C18(4.6mm × 250mm, 5 mu m), a mobile phase A is pure water, a mobile phase B is methanol, the detection wavelength is 220nm, the flow rate is 0.6m L/min, the column temperature is 40 ℃, the sample injection amount is 2 mu L, the volume fraction of the mobile phase A is 95%, and the volume fraction of the mobile phase B is 5%.
Under the detection method, the retention time of the target is 5.635min, and the target presents a good peak pattern which is repeatable, high in separation degree and sharp without tailing.
The acrolein-serine adduct has the formula: c9H13O4N, molecular weight: 199, structural formula:
Figure BDA0002469269880000031
the application of the acrolein-serine adduct in the field of food detection is used as a standard substance for detecting acrolein reaction products in food so as to analyze the performance and the content of the acrolein adduct in the food more quickly.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a preparation method of an acrolein-serine adduct, which has high yield, the purity of the prepared adduct is up to 99%, wherein the peak purity of a target single peak under each display wavelength (200-400 nm) of a high performance liquid chromatogram is up to 99%, and the adduct in food can be detected by using the adduct as a standard substance.
Drawings
FIG. 1 is a first order mass spectrum (positive ion mode) of an acrolein-serine adduct prepared in example 1;
FIG. 2 is a first order mass spectrum (negative ion mode) of an acrolein-serine adduct prepared in example 1;
FIG. 3 is a secondary mass spectrum (positive ion mode) of the acrolein-serine adduct prepared in example 1;
FIG. 4 is a secondary mass spectrum (negative ion mode) of the acrolein-serine adduct prepared in example 1;
FIG. 5 is a schematic representation of the acrolein-serine adduct prepared in example 113C NMR nuclear magnetic spectrum;
FIG. 6 is a Dept-135 NMR spectrum of an acrolein-serine adduct prepared in example 1;
FIG. 7 is a schematic representation of the acrolein-serine adduct prepared in example 11H NMR nuclear magnetic spectrum;
FIG. 8 is a high performance liquid chromatogram of the acrolein-serine adduct prepared in example 1;
FIG. 9 is a UV spectrum of an acrolein-serine adduct prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of an acrolein-serine adduct comprises the following steps of carrying out light-shielding heating reaction on acrolein and serine according to a molar ratio of 1:2 in water (reaction at 50 ℃ for 5 hours and rotation speed of 130rpm), carrying out reduced pressure concentration on the acrolein and serine for 1-2 m L, filtering the mixture through a 0.45-micron filter membrane to obtain a filtrate, and purifying the filtrate by using a reverse phase silica gel chromatography to obtain the acrolein-serine adduct with a yield of 83%.
Reversed phase silica gel chromatography (C18 reversed phase silica gel resin chromatography) comprises selecting reversed phase silica gel ODS resin 250m L, specification of chromatographic column 30 × 500mm, passing the sample after evaporation concentration through 0.45 μm filter membrane, loading, eluting with 5% methanol water solution as eluent at constant flow rate, determining existence of adduct by 2, 4-dinitrophenylhydrazine solution color development method, detecting purity by high performance liquid chromatography (HP L C method), collecting target adduct, freeze drying to obtain high purity target adduct of 50mg, and freeze drying at-70-40 deg.C under 1-100 Pa for 48 h.
The characterization diagrams of the acrolein-serine adduct prepared in this example are shown in FIGS. 1 to 9. FIG. 1 is a primary mass spectrum (positive ion mode); FIG. 2 is a primary mass spectrum (negative ion mode); FIG. 3 is a secondary mass spectrum (positive ion mode); FIG. 4 is a secondary mass spectrum (negative ion mode); FIG. 5 is a drawing showing13C NMR nuclear magnetic spectrum; FIG. 6 is a Dept-135 NMR spectrum; FIG. 7 is a drawing showing1H NMR nuclear magnetic spectrum; FIG. 8 is a high performance liquid chromatogram; FIG. 9 is a UV spectrum. According to the high performance liquid chromatography results and the nuclear magnetic resonance spectrum results shown in fig. 1 to fig. 9, the purity of the adduct prepared by the method of the present invention is as high as 99%, wherein the peak purity of the target single peak under each display wavelength (200 to 400nm) of the high performance liquid chromatogram is as high as 99%. Under the detection method, the retention time of the target is 5.635min, and the target presents a good peak shape which is repeatable, high in separation degree and sharp without tailing.
Example 2
A preparation method of an acrolein-serine adduct comprises the following steps of carrying out light-shielding heating reaction on acrolein and serine according to a molar ratio of 1:1 in water (reaction at 45 ℃ for 6 hours and rotation speed of 130rpm), carrying out reduced pressure concentration on the acrolein and serine for 1-2 m L, filtering the mixture through a 0.45-micrometer filter membrane to obtain a filtrate, and purifying the filtrate by using a reverse phase silica gel chromatography to obtain the acrolein-serine adduct.
Example 3
A preparation method of an acrolein-serine adduct comprises the following steps of carrying out light-shielding heating reaction on acrolein and serine according to a molar ratio of 1:3 in water (reaction at 60 ℃ for 5 hours and rotation speed of 130rpm), carrying out reduced pressure concentration on the acrolein and serine for 1-2 m L, filtering the mixture through a 0.45-micron filter membrane to obtain a filtrate, and purifying the filtrate by using a reverse phase silica gel chromatography to obtain the acrolein-serine adduct.
Comparative example 1 (too long or too short reaction time)
A preparation method of an acrolein-serine adduct comprises the following steps of carrying out light-shielding heating reaction on acrolein and serine according to a molar ratio of 1:2 in water (reaction is carried out for 1h or 8h at 50 ℃ and rotation speed of 130rpm respectively), carrying out reduced pressure concentration for 1-2 m L, filtering through a 0.45-micron filter membrane to obtain a filtrate, and purifying by using a reverse phase silica gel chromatography to obtain the acrolein-serine adduct.
Comparative example 2 (serine excess)
A preparation method of an acrolein-serine adduct comprises the following steps of reacting acrolein and serine at a molar ratio of 1:5 in water at 60 ℃ for 5 hours at a rotation speed of 130rpm, concentrating under reduced pressure by 1-2 m L, filtering with a 0.45 mu m filter membrane to obtain a filtrate, and purifying by using a reverse phase silica gel chromatography to obtain the acrolein-serine adduct.
Comparative example 3 (reaction temperature too high)
A preparation method of an acrolein-serine adduct comprises the following steps of carrying out light-shielding heating reaction on acrolein and serine according to a molar ratio of 1:3 in water (reaction at 70 ℃ for 8 hours and rotation speed of 130rpm), carrying out reduced pressure concentration on the acrolein and serine for 1-2 m L, filtering the mixture through a 0.45-micron filter membrane to obtain a filtrate, and purifying the filtrate by using a reverse phase silica gel chromatography to obtain the acrolein-serine adduct.
Application examples
Acrolein reaction product in fried potatoes was analyzed by detection using the acrolein-serine adduct prepared in example 1 as a standard.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A process for the preparation of an acrolein-serine adduct characterized by: the method comprises the following steps: heating acrolein and serine in water at constant temperature for reaction, and performing subsequent treatment to obtain acrolein-serine adduct.
2. The process for preparing an acrolein-serine adduct according to claim 1, characterized in that: the molar ratio of acrolein to serine is 1: (1-3).
3. The process for preparing an acrolein-serine adduct according to claim 1, characterized in that: the temperature of the heating reaction is 20-60 ℃; the heating reaction time is 3-12 h.
4. The process for preparing an acrolein-serine adduct according to claim 3, characterized in that: the temperature of the heating reaction is 45-55 ℃; the heating reaction time is 4-6 h.
5. The process for preparing an acrolein-serine adduct according to claim 1, characterized in that: the reaction is carried out under the condition of stirring; the stirring speed is 100-200 rpm.
6. The process for preparing an acrolein-serine adduct according to claim 1, characterized in that:
and the subsequent treatment refers to concentrating the reacted system, filtering with a filter membrane, and purifying by a reverse phase silica gel chromatography to obtain a purified product.
7. The process for preparing an acrolein-serine adduct according to claim 6, characterized in that: the filter membrane is a 0.45 mu m filter membrane; the concentration is reduced pressure concentration;
the reverse phase silica gel chromatography specifically comprises the following steps: selecting reverse phase silica gel ODS resin, loading, eluting with 5% methanol water solution, collecting target adduct by 2, 4-dinitrophenylhydrazine solution color development method, detecting purity by high performance liquid detection method, collecting eluent, and freeze drying to obtain purified sample.
8. An acrolein-serine adduct obtained by the production method according to any one of claims 1 to 7.
9. The acrolein-serine adduct according to claim 8, characterized in that: the molecular formula is as follows: c9H13O4N, molecular weight: 199, structural formula:
Figure FDA0002469269870000011
10. use of the acrolein-serine adduct according to claim 8 or 9, characterized in that: the acrolein-serine adduct is applied to the field of food detection.
CN202010343353.7A 2020-04-27 2020-04-27 Acrolein-serine adduct and preparation method and application thereof Pending CN111423360A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112617092A (en) * 2020-12-07 2021-04-09 暨南大学 Acrolein-amino acid adduct and preparation method and application thereof
CN114931202A (en) * 2022-04-21 2022-08-23 东莞思朗食品有限公司 Method for reducing glyoxal and formaldehyde in food, adduct generated by method and detection method

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WO2004087641A1 (en) * 2003-03-31 2004-10-14 Daiichi Pharmaceutical Co., Ltd. Hydrazone derivative
CN106872233A (en) * 2017-02-27 2017-06-20 暨南大学 A kind of 5 hydroxymethylfurfural cysteine adducts and preparation method and application and detection method
CN107652226A (en) * 2017-11-15 2018-02-02 上海皓伯化工科技有限公司 A kind of preparation method of the piperidinealdehydes of N Boc 4

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CN111423361A (en) * 2020-04-27 2020-07-17 暨南大学 Acrolein-alanine adduct and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
WO2004087641A1 (en) * 2003-03-31 2004-10-14 Daiichi Pharmaceutical Co., Ltd. Hydrazone derivative
CN106872233A (en) * 2017-02-27 2017-06-20 暨南大学 A kind of 5 hydroxymethylfurfural cysteine adducts and preparation method and application and detection method
CN107652226A (en) * 2017-11-15 2018-02-02 上海皓伯化工科技有限公司 A kind of preparation method of the piperidinealdehydes of N Boc 4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112617092A (en) * 2020-12-07 2021-04-09 暨南大学 Acrolein-amino acid adduct and preparation method and application thereof
CN112617092B (en) * 2020-12-07 2024-01-23 暨南大学 Acrolein-amino acid adducts, and preparation method and application thereof
CN114931202A (en) * 2022-04-21 2022-08-23 东莞思朗食品有限公司 Method for reducing glyoxal and formaldehyde in food, adduct generated by method and detection method

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