CN110343038B - Borojo monomer, Borojo extract, and preparation method and application thereof - Google Patents

Borojo monomer, Borojo extract, and preparation method and application thereof Download PDF

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CN110343038B
CN110343038B CN201810842071.4A CN201810842071A CN110343038B CN 110343038 B CN110343038 B CN 110343038B CN 201810842071 A CN201810842071 A CN 201810842071A CN 110343038 B CN110343038 B CN 110343038B
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bordeaux
bordea
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叶文才
范春林
王英
梅炬铭
刘俊珊
黄晓君
许琳
赵轩
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Jinan University
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/105—Plant extracts, their artificial duplicates or their derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • A—HUMAN NECESSITIES
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    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
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    • C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Abstract

The invention belongs to the technical field of natural medicinal chemistry, and relates to pelargonic acid 1-pelargonic acid 13 separated from Nanmei fruit pelargonic acid (Borojo) and a preparation method and application thereof. Experiments prove that the compound prepared by the invention has antioxidant, anti-inflammatory and hypoglycemic activities.

Description

Borojo monomer, Borojo extract, and preparation method and application thereof
Technical Field
The invention belongs to the field of natural medicinal chemistry, and particularly relates to a monomeric compound and an extract in Borax fruit, and a preparation method and application thereof.
Background
Borojoa is the mature fruit of Borojoa patitinous Cuatrec and Borojoa sorbilis Cuatrec, plants of the genus Linguus of the family Rubiaceae. Distributed in the iridescent rainforest of the amazon river basin, native to Columbia, iridescent and Panama. The Bordeaux mixture is rich in fructose and glucose, water-soluble B vitamins, amino acids and proteins, and has great development and utilization values. Local native residents believe that the consumption of the bola fruits can eliminate fatigue, enhance immunity, strengthen yang, improve respiratory inflammation symptoms and resist inflammation. The tylophora has antioxidant (International pharmaceutical research journal, 2013:817-821) and hypoglycemic activities, and the polysaccharide component in the tylophora can enhance immunity, but the anti-inflammatory, antioxidant and hypoglycemic effects of the monomer compound in the tylophora are not reported in the literature at present.
Disclosure of Invention
The invention aims to provide a preparation method and application of a Borojo extract and a monomeric compound thereof.
The purpose of the invention is realized by the following technical scheme:
the Borojo extract and the monomer compound thereof are prepared by the following steps:
(1) suspending Bordeaux powder with water, filtering, and adsorbing the filtrate with macroporous resin, such as AB-8, D101, D102, ZTC-1 or 1300-I type macroporous resin;
(2) eluting with water or ethanol of below 10% to remove impurities, eluting with 20% -80% ethanol water, collecting eluate, and concentrating to dry; the Bordeaux extract is obtained
(3) The Bordetella extract was subjected to silica gel column chromatography (petroleum ether-ethyl acetate gradient elution, 100:0 → 0:100), analyzed by TLC and fractions of similar composition were combined to give 10 major fractions (Fr.1-Fr.10). Fr.4 is subjected to medium-low pressure ODS column chromatography and methanol-water gradient elution (90:10 → 100:0), so as to obtain 7 sub-fractions (Fr.4a-Fr.4g). Wherein Fr.4c, Fr.4d and Fr.4e are respectively subjected to Sephadex LH-20 gel column chromatography, preparative HPLC and recrystallization to obtain compounds of the jewelleric acid-1, the jewelleric acid-2, the jewelleric acid-7 and the jewelleric acid-10. Fr.6 is subjected to medium-low pressure ODS column chromatography, and methanol-water gradient elution (95:5 → 100:0) to obtain 6 sub-fractions (Fr.6a-Fr.6f). The compounds of the musical instrument-8 and the musical instrument-9 are respectively obtained from Fr.6c and Fr.6d through Sephadex LH-20 gel column chromatography and preparative HPLC. Performing medium and low pressure ODS column chromatography on Fr.7, and performing methanol-water gradient elution (95:5 → 100:0) to obtain 8 subflows (Fr.7a-7J). Fr.7d, Fr.7e and Fr.7f are respectively passed through Sephadex LH-20 gel column
The invention discloses a method for analyzing the components of a Borojo extract: the main components of the Boraginaceae extract are identified by structure, and the main components are determined to be 11 new compounds and 2 known iridoid glycosides, and the chemical formula of the Boraginaceae extract is as follows:
Figure BDA0001744982800000021
the invention also provides the application of the tylophora fruit extract or the monomer in preparing anti-inflammatory or hypoglycemic drugs.
The invention also provides the application of the tylophora fruit extract or the tylophora fruit monomer in preparing the functional food for resisting oxidation/aging or reducing blood sugar.
The invention also provides a pelargonic acid extract of pelargonic, which comprises the following compounds:
Figure BDA0001744982800000031
the extract further comprises the following compounds:
Figure BDA0001744982800000032
Figure BDA0001744982800000041
the invention also provides a tylophora acid extract of tylophora, which comprises the following preparation steps:
taking fresh Bordeaux mixture as raw material, adding water, mixing, pulping or adding water, mixing, filtering, extracting the filtrate with ethyl acetate, mixing ethyl acetate layers, and concentrating under reduced pressure to obtain Bordeaux acid extract.
The Borojoa palustrine is a mature fruit derived from Borojoa patitinoi Cuatrec and Borojoa sorbilis Cuatrec which belong to the genus Rubiaceae.
Drawings
FIG. 1 shows high resolution mass spectrum of Bordeaux acid-1
FIG. 2 NMR spectrum of pelargonic acid-1
FIG. 3 nuclear magnetic resonance carbon spectrum of pelluconic acid-1
FIG. 4 high resolution mass spectrum of Bordeaux acid-2
FIG. 5 nuclear magnetic resonance hydrogen spectrum of pelargonic acid-2
FIG. 6 nuclear magnetic resonance carbon spectrum of pelargonic acid-2
FIG. 7 high resolution mass spectrum of Bordeaux acid-3
FIG. 8 NMR spectrum of pelluconic acid-3
FIG. 9 nuclear magnetic resonance carbon spectrum of pelargonic acid-3
FIG. 10 high resolution mass spectrum of pelluconic acid-4
FIG. 11 NMR spectrum of pelargonic acid-4
FIG. 12 nuclear magnetic resonance carbon spectrum of pelluconic acid-4
FIG. 13 high resolution mass spectrum of pelycolic acid-5
FIG. 14 NMR spectrum of pelargonic acid-5
FIG. 15 nuclear magnetic resonance carbon spectrum of pelargonic acid-5
FIG. 16 high resolution mass spectrum of pelycolic acid-6
FIG. 17 NMR spectrum of pelluconic acid-6
FIG. 18 NMR carbon spectra of pelluconic acid-6
FIG. 19 high resolution mass spectrum of Bordeaux acid-7
FIG. 20 NMR spectrum of pelargonic acid-7
FIG. 21 nuclear magnetic resonance carbon spectrum of pelargonic acid-7
FIG. 22 high resolution mass spectrum of Bordeaux acid-8
FIG. 23 NMR spectrum of pelargonic acid-8
FIG. 24 nuclear magnetic resonance carbon spectrum of pelargonic acid-8
FIG. 25 high resolution mass spectrum of Bordeaux acid-9
FIG. 26 nuclear magnetic resonance hydrogen spectrum of pelargonic acid-9
FIG. 27 NMR carbon spectra of pelargonic acid-9
FIG. 28 high resolution mass spectrum of Bordeaux acid-10
FIG. 29 nuclear magnetic resonance hydrogen spectrum of pelluconic acid-10
FIG. 30 nuclear magnetic resonance carbon spectrum of pelluconic acid-10
FIG. 31 high resolution mass spectrum of Bordeaux acid-11
FIG. 32 NMR spectrum of pelargonic acid-11
FIG. 33 NMR carbon spectra of pelluconic acid-11
FIG. 34 Single Crystal X-ray diffraction Structure of Bordeac acid-1
FIG. 35 Single Crystal X-ray diffraction Structure of Bordeac acid-12
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
EXAMPLE 1 preparation of Bordeaux extract
Taking 50kg of fresh Bordeaux mixture, peeling and mixing seeds, adding 200L of water into pulp, stirring, grinding into pulp, mixing uniformly, and filtering. Adding 100L water into the fruit residue, stirring, grinding into slurry, mixing, and filtering.
The two filtrates were combined, 300L of ethyl acetate was added for extraction, and the ethyl acetate layer was separated. 300L of ethyl acetate was added to the aqueous layer, and the ethyl acetate layer was separated. The aqueous layer was extracted with 300L of ethyl acetate, and the ethyl acetate layer was separated.
And combining the ethyl acetate layers for 3 times, and concentrating under reduced pressure to dryness to obtain 650g of the Bordeaux extract.
EXAMPLE 2 preparation of Bordeaux extract
Adding 50L water into 5kg Bordeaux powder, stirring, mixing, and filtering. Adding 50L water into the filter residue, stirring, mixing, and filtering.
The two filtrates were combined, 100L of ethyl acetate was added for extraction, and the ethyl acetate layer was separated. The aqueous layer was extracted 3 more times with 100L ethyl acetate each time, and the ethyl acetate layer was separated each time.
And combining the ethyl acetate layers for 4 times, and concentrating under reduced pressure to dryness to obtain 480g of the Bordeaux extract.
EXAMPLE 3 Compound preparation and Structure identification
Dissolving 500g of Bordeaux extract in methanol, stirring the mixture with 80-100 meshes of silica gel, performing 200-300-mesh silica gel column chromatography, performing gradient elution with petroleum ether-ethyl acetate at a ratio of 95:5, 90:10, 85:115, 80:20, 75:25, 70:30, 60:40, 50:50 and 0:100 in sequence, detecting by TLC, and combining fractions with similar thin-layer spots to obtain 9 components Fr.1-Fr.9.
Fr.4 is subjected to medium-low pressure ODS column chromatography and methanol-water gradient elution (90:10 → 100:0), so as to obtain 7 sub-fractions (Fr.4a-Fr.4g). Wherein Fr.4c, Fr.4d and Fr.4e are respectively subjected to Sephadex LH-20, Pre-HPLC and recrystallization to obtain compounds of tylophoric acid 1(171mg), tylophoric acid 2(163mg), tylophoric acid 7(201mg) and tylophoric acid 10(167 mg).
Fr.6 is subjected to middle and low pressure ODS column chromatography, and methanol-water gradient elution (95:5 → 100:0) to obtain 6 sub-fractions (Fr.6a-Fr.6f). The compounds of Bordeaux 8(195mg) and Bordeaux 9(218mg) were obtained from Fr.6c and Fr.6d by Sephadex LH-20 and Pre-HPLC, respectively.
Fr.7(2.5g) was subjected to medium-low pressure ODS column chromatography, and eluted with methanol-water gradient (95:5 → 100:0) to give 8 subflows (Fr.7 a-7J). Fr.7d, Fr.7e and Fr.7f were subjected to Sephadex LH-20 and Pre-HPLC respectively to give compounds (146 mg), pelargonic acid 4(160mg), pelargonic acid 5(185mg), pelargonic acid 6(260mg), pelargonic acid 11(136mg), pelargonic acid 12(564mg) and pelargonic acid 13(428 mg).
1((1R,5S) -5-methycylilopent-2-ene-1, 2-dicarboxylic acid) colorless fine needle crystal, and the chemical structure formula is as follows:
Figure BDA0001744982800000061
the spectral data are as follows: HR-ESI-MS M/z 193.0479[ M + Na ]]+ESI-MS is shown in FIG. 1.1H NMR(CD3OD,400MHz) δ: 1.19(3H, d, J ═ 6.5Hz, H-8), 2.16(1H, ddt, J ═ 18.5,5.5,2.5Hz, H-4a), 2.81(1H, ddt, J ═ 18.5,8.0,2.5Hz, H-4b), 2.57(1H, m, H-1), 3.26(1H, qd, J ═ 5.7,2.0Hz, H-5), 6.83(1H, dd, J ═ 4.5,2.4Hz, H-3), and the nmr hydrogen spectrum is shown in fig. 2.13C NMR(CD3OD,100MHz) δ: 21.4(C-8), 40.1(C-5), 41.7(C-4), 58.8(C-1), 136.4(C-2), 146.4(C-3), 167.9(C-7), 178.2(C-6), and the NMR spectrum is shown in FIG. 3. The absolute configuration of the tylophorbide-1 was determined by single crystal X-ray diffraction method, see fig. 34.
According to the spectral data, the pelycolepent-1 is identified as a new cyclopentene compound and named as (1R,5S) -5-methycyliopennt-2-ene-1, 2-dicarboxylic acid.
Boragic acid-2 ((1S,5S) -5-methycylilopent-2-ene-1, 2-dicarboxylic acid) white amorphous powder, the chemical structural formula is as follows:
Figure BDA0001744982800000071
the spectral data are as follows: HR-ESI-MS: m/z 193.0479[ M + Na ]]+ESI-MS is shown in FIG. 4.1H NMR(CD3OD,500MHz) δ: 1.10(3H, d, J ═ 7.1Hz, H-8), 2.25(1H, ddt, J ═ 18.0,8.2,2.4Hz, H-4a), 2.65(1H, ddd, J ═ 18.0,8.1,2.8Hz, H-4b), 2.78(1H, dq, J ═ 16.1,7.1Hz, H-5), 3.64(1H, d, J ═ 9.3Hz, H-1), 6.92 (1H, br, H-3), and the nmr hydrogen spectrum is shown in fig. 5.13C NMR(CD3OD,125MHz) δ: 16.6(C-8), 37.1 (C-5), 41.6(C-4), 54.7(C-1), 136.9(C-2), 148.1(C-3), 167.8(C-7), 176.3(C-6), and the NMR spectrum is shown in FIG. 6.
According to the spectral data, the pelycolepent-2 is identified as a new cyclopentene compound and named as (1S,5S) -5-methycyliopennt-2-ene-1, 2-dicarboxylic acid.
The pure-yellow oil of the tylosin-3 ((1R,5R) -5- (carboxymethyl) cyclopent-2-ene-1,2-dicarboxylic acid) has the chemical structural formula:
Figure BDA0001744982800000072
the spectral data are as follows: HR-ESI-MS: m/z 237.0377[ M + Na ]]+ESI-MS is shown in FIG. 7.1H NMR (CD3OD,400MHz) δ: 2.31(1H, dt, J ═ 13.1,2.3Hz, H-4b), 2.48(1H, dd, J ═ 16.0,8.3Hz, H-8b), 2.61(1H, dd, J ═ 16.0,5.6Hz, H-8a), 2.86(1H, m, H-5), 2.93(1H, dt, J ═ 8.3,2.5Hz, H-4a), 3.44(1H, m, H-1), 6.85(1H, m, H-3), and the nuclear magnetic resonance hydrogen spectrum is shown in fig. 8.13C NMR(CD3OD,100MHz) δ: 39.7(C-4), 40.3(C-8), 41.2(C-5), 56.5(C-1), 136.1(C-2), 146.2(C-3), 167.5(C-7), 175.6(C-9), 177.6(C-6), and the NMR spectrum is shown in FIG. 9.
According to the spectral data, the pelavonic acid-3 is identified as a new cyclopentene compound and named as (3R,4R) -4- (carboxymethyl) cyclopent-1-ene-1,3-dicarboxylic acid.
Bordeaux acid-4 ((1R,5S) -5- (carboxymethyl) cyclopent-2-ene-1,2-dicarboxylic acid) brown amorphous powder with the chemical structural formula:
Figure BDA0001744982800000081
the spectral data are as follows: HR-ESI-MS: m/z 237.0377[ M + Na ]]+ESI-MS is shown in FIG. 10.1H NMR (CD3OD,400MHz) δ: 2.33(1H, dd, J ═ 18.0,9.4Hz, H-4b), 2.42(1H, dd, J ═ 16.6,8.6Hz, H-8b), 2.57(1H, dd, J ═ 16.6,6.9Hz, H-8a), 2.74(1H, ddd, J ═ 18.0,8.1,2.8Hz, H-4a), 3.05(1H, m, H-5), 3.75(1H, d, J ═ 9.0Hz, H-1), 6.95(1H, br s, H-3), and the nmr hydrogen spectrum is shown in fig. 11.13C NMR(CD3OD,100MHz) δ: 36.7(C-8), 39.0(C-5), 39.5(C-4), 53.5(C-1), 137.5(C-2), 147.5 (C-3), 167.5(C-7), 175.7(C-9), 175.8(C-6), the NMR spectrum is shown in FIG. 12.
According to the spectral data, the pelavonic acid-4 is identified as a new cyclopentene compound and named as (1R,5S) -5- (carboxymethyl) cyclopent-2-ene-1,2-dicarboxylic acid.
5((1R,5R) -5- (2-methoxy-2-oxoethyl) cyclopent-2-ene-1,2-dicarboxylic acid) of tylosin, the chemical structural formula is:
Figure BDA0001744982800000082
the spectral data are as follows: HR-ESI-MS: m/z 251.0520[ M + Na ]]+ESI-MS is shown in FIG. 13.1H NMR (CD3OD,400MHz)δ：2.31(1H,m,H-4b), 2.50(1H, dd, J ═ 16.0,7.7Hz, H-8b), 2.57(1H, dd, J ═ 16.0,6.0Hz, H-8a), 2.84(1H, m, H-5), 2.86(1H, m, H-4a), 3.48(1H, m, H-1), 3.68(3H, s, H-10), 6.86(1H, br s, H-3), and the nmr spectrum is shown in fig. 14.13C NMR(CD3OD,100MHz) δ: 39.7(C-4), 40.1(C-8), 41.4(C-5), 52.6(C-10), 56.5(C-1), 136.1(C-2), 146.4(C-3), 167.2(C-7), 175.5(C-6), 176.3(C-9), and the NMR spectrum is shown in FIG. 15.
According to the spectral data, the Calycolic acid-5 is identified as a new cyclopentene compound and named as (1R,5R) -5- (2-methoxy-2-oxoethyl) cyclopent-2-ene-1,2-dicarboxylic acid.
1, 6((1S,5R) -5- (2-methoxy-2-oxoethyl) cyclopent-2-ene-1,2-dicarboxylic acid) of tylosin acid, wherein the chemical structural formula is as follows:
Figure BDA0001744982800000091
the spectral data are as follows: HR-ESI-MS: m/z 251.0520[ M + Na ]]+ESI-MS is shown in FIG. 16.1H NMR (CD3OD,300MHz) δ 2.32(1H, ddt, J ═ 18.0,9.4,2.4Hz, H-4b), 2.54(2H, qd, J ═ 16.6,7.8Hz, H-8), 2.73(1H, ddd, J ═ 18.0,8.1,3.0Hz, H-4a), 3.07(1H, m, H-5), 3.68(3H, s, H-10), 3.74(1H, dd, J ═ 9.3,1.5Hz, H-1), 6.94(1H, br s, H-3), and the nmr hydrogen spectrum is shown in fig. 17.13C NMR(CD3OD,75MHz) δ: 36.6(C-8), 39.0(C-5), 39.3(C-4), 52.1(C-10), 53.5(C-1), 137.3(C-2), 147.1(C-3), 167.5(C-7), 174.2(C-9), 175.7(C-6), the NMR spectrum is shown in FIG. 18.
According to the spectral data, the Calycolic acid-6 is identified as a novel cyclopentene compound and is named as (1S,5R) -5- (2-methoxy-2-oxoethyl) cyclopent-2-ene-1,2-dicarboxylic acid.
Boragic acid-7 ((1R,5S) -1-methoxybutyryl-5-methoxylocent-2-enecarboxylic acid) yellow oil, the chemical structural formula is as follows:
Figure BDA0001744982800000092
the spectral data are as follows: HR-ESI-MS: m/z 207.0635[ M + Na ]]+ESI-MS is shown in FIG. 19.1H NMR (CD3OD,500MHz) δ 1.18(3H, d, J ═ 6.0Hz, H-8), 2.16(1H, ddt, J ═ 18.4,5.8,2.3Hz, H-4b), 2.53 (1H, m, H-5), 2.81(1H, ddt, J ═ 18.4,8.2,2.5Hz, H-4), 3.30(1H, m, H-1), 3.68(3H, s, H-9), 6.83(1H, dd, J ═ 4.2,2.4Hz, H-3), and the nmr hydrogen spectrum is shown in fig. 20.13C NMR(CD3OD,125MHz) delta 21.3 (C-8), 40.2(C-5), 41.8(C-4), 52.5(C-9), 53.8(C-1), 136.7(C-2), 146.4(C-3), 168.4(C-7), 176.8(C-6), and NMR C spectra are shown in FIG. 21.
According to the above spectral data, the pelycolic acid-7 is identified as a new cyclopentene compound and named as (1R,5S) -1-methoxycarboxyl-5-methoxycarboxyl-2-enecarboxylic acid.
1, 8(tans-2-oxo-3,3a,4,6a-tetrahydro-2H-cyclopenta [ b ] furan-5-carboxylic acid) light yellow amorphous powder with the chemical structural formula:
Figure BDA0001744982800000101
the spectral data are as follows: HR-ESI-MS: m/z 191.0316[ M + Na ]]+ESI-MS is shown in FIG. 22.1H NMR(CD3OD,500MHz) δ:2.56(1H, ddt, J ═ 19.0,4.0,2.5Hz, H-4 '), 2.95(1H, dddd, J ═ 19.0,9.0,2.5,1.5Hz, H-4 "), 3.47 (1H, m, H-3a), 3.95(1H, ddd, J ═ 9.0,4.2,1.8Hz, H-6a), 4.05(1H, dd, J ═ 9.5,5.0Hz, H-3'), 4.56(1H, dd, J ═ 9.5,8.0Hz, H-3"), 6.83(1H, dd, J ═ 4.5,2.4Hz, H-6), and the nmr spectrum is shown in fig. 23.13C NMR(CD3OD,125MHz) delta 39.8(C-4), 40.2(C-3a), 51.4(C-6a), 74.7(C-3), 134.6(C-5), 146.2(C-6), 166.7(C-7), 178.1(C-1), and NMR C spectra are shown in FIG. 24.
According to the above spectral data, the bolaconic acid-8 is identified as a novel fused ring compound and named as tan-2-oxo-3, 3a,4,6a-tetrahydro-2H-cyclopenta [ b ] furan-5-carboxylic acid.
Boragic acid-9 (cis-2-oxo-3,3a,4,6a-tetrahydro-2H-cyclopenta [ b ] furan-5-carboxylic acid) yellow oil with the chemical structural formula:
Figure BDA0001744982800000106
the spectral data are as follows: HR-ESI-MS: m/z 191.0318[ M + Na ]]+ESI-MS is shown in FIG. 25.1H NMR(CD3OD,500MHz) δ: 2.43(1H, dd, J ═ 18.5,4.2Hz, H-3'), 2.49(1H, m, H-4), 2.96(1H, dd, J ═ 18.5,10.5Hz, H-3 ″), 3.31(1H, m, H-3a), 2.97(1H, ddd, J ═ 19.6,8.8,2.4Hz, H-4), 5.69(1H, dd, J ═ 7.5,2.1Hz, H-6a), 7.10(1H, t, J ═ 2.4Hz, H-5), and the nmr hydrogen spectrum is shown in fig. 26.13C NMR(CD3OD,125MHz) δ: 36.3(C-3), 37.1(C-3a), 40.5(C-4), 89.2(C-6a), 136.3(C-6), 151.0(C-5), 166.6(C-7), 179.6(C-2), NMR spectrum is shown in FIG. 27.
According to the above spectral data, pelycolic acid-9 was identified as a novel fused ring compound and named as cis-2-oxo-3,3a,4,6a-tetrahydro-2H-cyclopenta [ b ] furan-5-carboxylic acid.
Pellitorin-10 (cis-3,3a,4,6a-tetrahydro-2H-cyclopenta [ b ] furan-6-carboxylic acid) yellow amorphous powder with the chemical structural formula:
Figure BDA0001744982800000111
the spectral data are as follows: HR-ESI-MS with M/z 177.0529[ M + Na ]]+ESI-MS is shown in FIG. 28.1H NMR(CD3OD,500MHz) δ:1.68(1H, m, H-3 '), 2.07(1H, m, H-3 "), 2.81(1H, ddd, J ═ 19.6,8.8,2.2Hz, H-4 '), 2.32(1H, m, H-4), 3.05(1H, m, H-3a), 3.56(1H, m, H-2 '), 3.81(1H, m, H-2"), 5.22(1H, d, J ═ 6.0Hz, H-6a), 6.87(1H, t, J ═ 2.4Hz, H-5), and the nmr hydrogen spectrum is shown in fig. 29.13C NMR(CD3OD,125MHz)δ:35.7(C-3)，40.1(C-4)， 41.3(C-3a)，67.1(C-2),88.0(C-6a)，1372(C-6), 148.1(C-5), 168.3(C-7), NMR spectrum is shown in FIG. 30.
According to the spectral data, the pelavonic acid-10 is identified as a novel fused ring compound and is named as cis-3,3a,4,6 a-tetrahydroo-2H-cyclopenta [ b ] furan-6-carboxylic acid.
Boragic acid-11 (bicyclo [3.1.0] hex-3-ene-1,3-dicarboxylic acid) yellow oil with the chemical structural formula:
Figure BDA0001744982800000117
the spectral data are as follows: m/z 191.0316[ M + Na ]]+ESI-MS is shown in FIG. 31.1H NMR(CD3OD,500MHz) δ 0.67(1H, t, J ═ 5.0Hz, H-6 '), 1.84(1H, dd, J ═ 8.5,4.2Hz, H-6 "), 2.19(1H, m, H-5), 2.50(1H, dd, J ═ 19.7, 2.0Hz, H-2'), 2.84(1H, ddd, J ═ 19.7,7.0,2.0Hz, H-2"), 6.43(1H, m, H-4), and the nmr hydrogen spectrum is shown in fig. 32.13C NMR(CD3OD,125MHz) delta 24.1(C-6), 29.7(C-5), 35.9(C-2), 37.4(C-1), 140.1(C-3), 143.1(C-4), 167.4(C-8), 175.7(C-7), and the NMR spectrum is shown in FIG. 33.
The above spectral data are consistent with those reported in the literature (Prinzbach H, et al. Chemische Berichte,1965,98(7):2201-2220), and thus, Bordeac acid-11 was identified as a bicyclo [3.1.0] hex-3-ene-1,3-dicarboxylic acid.
Boracoic acid-12 (ixoside) light yellow needle crystal, the chemical structural formula is:
Figure BDA00017449828000001112
the spectral data are as follows: HR-ESI-MSm/z 411.0903[ M + Na ]]+。1H NMR(CD3OD,300MHz)δ:2.45 (1H,br d,J＝18.6Hz,H-6b)，2.95(1H,dd,J＝18.6,8.1Hz,H-6a)，3.22(2H,m,H-5,H-9),5.67(1H,d, J＝5.1Hz,H-1)，6.93(1H,m,H-7)，7.51(1H,s,H-3)，3.22(1H,m,H-2′)，3.34(1H,m,H-4′)，3.36 (1H,m,H-5′)，3.37(1H,m,H-3′)，3.71(1H,m,H-6′)，3.87(1H, d, J ═ 11.4Hz, H-6 ') and 4.65 (1H, d, J ═ 7.8Hz, H-1').13C NMR(CD3OD,75MHz) δ 35.0(C-5), 40.1(C-6), 47.2(C-9), 96.3(C-1), 112.4(C-4), 136.1(C-8), 147.8(C-7), 153.6(C-3), 168.1(C-10), 170.5(C-11), 62.5(C-6 '), 71.2 (C-4'), 74.4(C-2 '), 77.6 (C-5'), 78.0(C-3 '), and 100.2 (C-1'). The absolute configuration of pelluconic acid-12 was determined by single crystal X-ray diffraction and is shown in figure 35.
The above spectral data are consistent with those reported in the literature (Yoshio T, et al, chemical Pharmaceutical Bulletin,1976,24(6): 1216-1218), and thus, Bordetemic acid-12 was identified as ixoside.
Bordeaux acid-13 yellow oily substance, the chemical structural formula is:
Figure BDA0001744982800000121
the spectral data are as follows: HR-ESI-MS: m/z 415.1218[ M + Na ]]+。1H NMR(CD3OD,400MHz) δ:1.28 (1H, s, H-10), 1.85(1H, dd, J ═ 13.2,6.0Hz, H-7a), 2.05(1H, dd, J ═ 13.2,6.8Hz, H-7b), 2.62(1H, dd, J ═ 10.0,2.4Hz, H-9), 2.97(1H, dd, J ═ 10.0,3.2Hz, H-5), 5.57(1H, d, J ═ 2.4Hz, H-1), 7.42(1H, s, H-3), 3.19(1H, m, H-2 '), 3.27(1H, m, H-4 '), 3.33(1H, m, H-5 '), 3.38(1H, m, H-3.65 (1H, 3.65, H-2 '), 3.6H-6H ', 6, d, 6H-6, d, J ═ 2,6, H-1, 6, d, j ═ 8.0Hz, H-1').13C NMR(CD3OD,100MHz) Δ 24.8(C-10), 41.4(C-5), 49.1(C-7), 51.4(C-9), 77.7(C-6), 79.0(C-8), 94.8(C-1), 111.6(C-4), 152.6(C-3), 171.3(C-11), 62.9(C-6 '), 71.7 (C-4'), 74.5(C-2 '), 78.0 (C-3'), 78.3(C-5 '), and 99.8 (C-1').
The above spectral data are consistent with those reported in the literature (Masateru O, et al, chemical Pharmaceutical Bulletin,2007,55(4):632-634), so that tylophorbide-13 was identified as shanzhiside.
Example 4 in vitro antioxidant assay
1. Materials and methods
1.1 materials:
a sample to be tested: the extract of tylophora fruits prepared in example 1 was mixed with 13 monomeric compounds, standard antioxidant vitamin C.
Reagent: ABTS (2, 2-diaza-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt), DPPH (diphenylpicrylhydrazyl) were purchased from Sigma company. Other reagents are domestic analytical purifiers.
1.2 scavenging of free radicals in DPPH
DPPH, a stable nitrogen-centered radical, with strong absorption at 517 nm. When an antioxidant is present in the reaction system, it can be paired with DPPH.single electron to gradually decrease the absorption peak at 517nm, and the absorbance value decreases. Moreover, the degree of this decrease is quantitatively related to the degree of radical scavenging.
Dissolving DPPH0.0246g in about 100mL solvent methanol, ultrasonic treating for 5min, and shaking to make upper and lower parts uniform. Preparing a series of concentrations of sample with methanol, adding 0.1ml sample solution into 2ml DPPH methanol solution, mixing well, and measuring the absorbance at 515nm after 30 min; the absorbance value of the blank was determined by the same method using methanol instead of the sample. Each sample was run in parallel 3 times and the mean was calculated.
DPPH clearance (%) - (a)Blank space-ASample (I))/ABlank space]×100％
IC50: the semi-inhibitory amount, which represents the concentration of the sample required to scavenge 50% of the free radicals or inhibit 50% of the oxidation, is often used to represent the magnitude of antioxidant activity.
1.3 pairs of ABTS+Determination of scavenging Capacity
ABTS generates stable blue-green cationic free radical ABTS after being oxidized by active oxygen+When an antioxidant is added to it, the substance will react with ABTS+The reaction takes place to fade the color of the reaction system, i.e. the absorbance value is reduced, and the degree of the reduction can reflect the antioxidant capacity of the antioxidant.
Mixing 0.4ml of 7.4mmol/L ABTS and 1.43ml of 2.6mmol/L potassium persulfate, reacting at room temperature in the absence of light, and standing overnight to obtain ABTS+Free radical reserveAnd (4) liquid. Preparing the sample with methanol to a series of concentrations, adding 0.8ml ABTS into 0.2ml sample solution+Uniformly oscillating the free radical working solution for 10s, carrying out water bath reaction at 30 ℃ for 10min, and measuring the absorbance value of the free radical working solution at 734 nm; the absorbance value of the blank was determined by the same method using methanol instead of the sample. Each sample was run in parallel 3 times and the mean was calculated.
ABTS clearance (%) - (a)Blank space-ASample (I))/ABlank space]×100％
IC50: the semi-inhibitory amount, which represents the concentration of the sample required to scavenge 50% of the free radicals or inhibit 50% of the oxidation, is often used to represent the magnitude of antioxidant activity.
1.4 scavenging effect on superoxide radical
Utilizes pyrogallol to generate autoxidation chain reaction in alkaline environment and release a large amount of O2-，·O2-Further accelerate the oxidation of pyrogallol to generate a series of intermediate products with characteristic absorption in the visible light region. If the anti-oxidation substance is added into the reaction system, the autoxidation rate of the pyrogallol can be reduced, and the generated O can be removed2-And the generation of intermediate products is inhibited, so that the absorbance of the reaction solution at 320nm is reduced, and the reduction degree can reflect the antioxidant capacity of the antioxidant.
Preparing a sample into a series of concentrations by using methanol, adding 0.2ml of sample solution into 4ml of sample solution with a certain concentration and 4.5ml of 0.1mol/L Tris-HCl buffer solution (pH 8.2), adding 0.2ml of 3mmol/L pyrogallol solution after 20min of water bath at 25 ℃, uniformly mixing, reacting for 5min in the water bath at 25 ℃, adding 1mol/LHCl to terminate the reaction, and measuring the absorbance at 325 nm; the absorbance value of the blank was determined by the same method using distilled water instead of the sample.
Clearance (%) [ (a blank-a sample)/a blank ] × 100%
IC50: the semi-inhibitory amount, which represents the concentration of the sample required to scavenge 50% of the free radicals or inhibit 50% of the oxidation, is often used to represent the magnitude of antioxidant activity.
2. Statistical treatment
Results of the experiment to
Figure BDA0001744982800000141
And (4) showing.
3. Results
Using IC50The antioxidant activity of the tylophora extract and the 13 monomeric compounds was evaluated. The antioxidant results are shown in the table below.
TABLE 1 antioxidant Activity of Bordeaux extracts and monomeric Compounds thereof
Figure BDA0001744982800000142
As can be seen from the above table, compared with vitamin C, the monomeric compounds all showed good antioxidant activity, and the activity was better than that of the bola extract.
Example 5 anti-inflammatory assay
Sample preparation: bordeaux extract and 13 monomeric compounds prepared in examples 1 and 3
1. Experimental methods
Lipopolysaccharide (LPS) is utilized to stimulate RAW264.7 cells, an in vitro inflammation model is established, the influence of the Bordeaux extract and 14 monomer compounds on the production of an inflammatory factor TNF-alpha is discussed, and the specific operation is as follows:
(1) cell culture: RAW264.7 cells were cultured in DMEM medium containing 10% fetal calf serum, penicillin 100U/mL and streptomycin 100U/mL at 37 ℃ with 5% CO2Subculturing under the condition. And (4) carrying out passage after the cells grow to 70-80% of fusion, wherein the liquid is changed once in 1-2 days, and the passage is carried out once in 4-6 days.
(2) 1X 10 of RAW264.7 cell suspension5Inoculating 100 μ L/well of the suspension in a 96-well plate at 37 deg.C under 5% CO2Culturing for 12h in an incubator, adding samples to be detected with different concentrations, inoculating 4 holes of each concentration sample in parallel, placing at 37 ℃ for continuous culture for 24h, adding 100ng/mL LPS, continuing to culture for 9h, taking 200 mu l of supernatant from each hole, and detecting the content of TNF-alpha according to the operation method of the TNF-alpha ELISA kit. Meanwhile, an LPS control group was established.
2. Statistical treatment
Results of the experiment to
Figure BDA0001744982800000151
The comparison among groups adopts t test, and the difference represented by P < 0.05 has statistical significance.
3. Results
The results are shown in the following table.
TABLE 2 inhibition of TNF-alpha inflammatory factor production in RAW264.7 cells by LPS using Bordeaux extract and monomeric compounds thereof
Figure BDA0001744982800000152
Figure BDA0001744982800000161
Compared with the group in which LPS alone acted,**P<0.01；***P<0.001。
as can be seen from the above table, the monomeric compounds all showed good anti-inflammatory activity compared to the tylophora extract.
Example 6 hypoglycemic experiments
Sample preparation: bordeaux extract and 13 monomeric compounds prepared in examples 1 and 3
1. Experimental methods
170 ICR male mice (6 weeks old, 30-35 g in weight) were randomly divided into 10 normal control groups and 160 diabetes model groups, the normal groups were given basal diet, and the model groups were given high-fat diet. Feeding for 4 weeks, fasting for 12h, injecting streptozotocin into abdominal cavity at a dose of 100mg/kg (solvent is citric acid-sodium citrate buffer solution, pH is 4.5), measuring glucose tolerance of mice for 2h after 3 days, and screening mice with blood sugar value of more than 11.1mmol/mL as mice successfully modeled. The mice that were modelled were randomly divided into 1 model group and 14 experimental groups. The experimental group was orally administered at 2mg/kg by gavage 1 time daily for 2 weeks. After the experiment is finished, fasting blood glucose value and fasting body weight of the mice fasted overnight are detected.
2. Statistical treatment
Results of the experiment to
Figure BDA0001744982800000162
The comparison among groups adopts t test, and the difference represented by P < 0.05 has statistical significance.
3. Results
The results of the experiment are shown in the following table:
TABLE 3 hypoglycemic action of Bordeaux extract and monomeric compound
Figure BDA0001744982800000163
Figure BDA0001744982800000171
In comparison with the normal group,##P<0.01；###P<0.001; in comparison to the set of models,*P<0.05；**P<0.01；**P<0.001。
as can be seen from the above table, the monomeric compounds all showed good hypoglycemic activity compared to the tylophora extract.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.

Claims (8)

1. The tylophorbide compound prepared from tylophorbide is characterized by being selected from one of the following structural compounds:
Figure FDA0003491345010000011
2. a Bordeaux acid extract of Bordeaux mixture is characterized in that: which comprises the following compounds:
Figure FDA0003491345010000012
Figure FDA0003491345010000021
and
Figure FDA0003491345010000022
3. the Bordeaux acid extract of Bordeaux as claimed in claim 2, wherein: it further comprises the following compounds:
Figure FDA0003491345010000023
4. the method for preparing a pelargonic acid compound according to claim 1, wherein: the preparation method comprises the following preparation steps:
taking fresh Bora edulis as a raw material, adding water, uniformly mixing, grinding into slurry or adding water, uniformly mixing Bora edulis freeze-dried powder, filtering, adding ethyl acetate into filtrate for extraction, combining ethyl acetate layers, and concentrating under reduced pressure to obtain Bora edulis extract;
adding methanol into the Leptospermum scoparium extract for redissolving, mixing the sample with silica gel, performing silica gel column chromatography, and performing gradient elution with petroleum ether-ethyl acetate of 95:5, 90:10, 85:115, 80:20, 75:25, 70:30, 60:40, 50:50 and 0:100 in sequence to obtain 9 components Fr.1-Fr.9;
fr.4 is subjected to medium and low pressure ODS column chromatography and methanol-water gradient elution to obtain 7 sub-fractions Fr.4a-Fr.4g, wherein Fr.4c, Fr.4d and Fr.4e are subjected to Sephadex LH-20, Pre-HPLC and recrystallization respectively to obtain compounds of tylonolide 1, tylonolide 2, tylonolide 7 and tylonolide 10;
fr.6 is subjected to middle and low pressure ODS column chromatography and methanol-water gradient elution to obtain 6 sub-fractions Fr.6a-Fr.6f, Fr.6c and Fr.6d which are respectively subjected to Sephadex LH-20 and Pre-HPLC to obtain compounds of tylophoric acid 8 and tylophoric acid 9;
performing medium-low pressure ODS column chromatography on Fr.7, performing methanol-water gradient elution to obtain 10 sub-fractions Fr.7a-7 j, and performing Sephadex LH-20 and Pre-HPLC on Fr.7d, Fr.7e and Fr.7f to obtain compounds (including Bordea acid 3, Bordea acid 4, Bordea acid 5, Bordea acid 6, Bordea acid 11, Bordea acid 12 and Bordea acid 13); wherein: the structure of the fruit acid is Baoleguo acid 11
Figure FDA0003491345010000031
The structure of the fruit acid 12 is
Figure FDA0003491345010000032
The structure of the fruit acid is Baoleguo acid 13
Figure FDA0003491345010000033
5. The method for producing the pelargonic acid extract as claimed in claim 4, wherein the pelargonic acid is a mature fruit derived from Borojoa patitinous Cuatrec and Borojoa sorbilis Cuatrec, plants belonging to the genus Lingo of the family Rubiaceae.
6. Use of the tylophoronic acid compound according to claim 1 or the tylophoronic acid extract according to any one of claims 2 to 3 for the preparation of a food or health product for anti-oxidant/anti-ageing treatment.
7. Use of the tylophoronic acid compound according to claim 1 or the tylophoronic acid extract according to any one of claims 2 to 3 for the preparation of a therapeutic anti-inflammatory medicament.
8. Use of the tylonolide acid compound according to claim 1 or the tylonolide acid extract according to any one of claims 2 to 3 in the preparation of a medicament for lowering blood glucose or a health product for assisting in lowering blood glucose.
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