CN101381360A - Grafts of plant polyphenol and weathered coal humic acid degradation product and grafting method - Google Patents
Grafts of plant polyphenol and weathered coal humic acid degradation product and grafting method Download PDFInfo
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- CN101381360A CN101381360A CNA2008102017001A CN200810201700A CN101381360A CN 101381360 A CN101381360 A CN 101381360A CN A2008102017001 A CNA2008102017001 A CN A2008102017001A CN 200810201700 A CN200810201700 A CN 200810201700A CN 101381360 A CN101381360 A CN 101381360A
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Abstract
The invention provides a graft for plant polyphenol and a weathered humic acid degradation product and a grafting method thereof. As shown by experiments, the graft for the plant polyphenol and the weathered humic acid degradation product has the efficacy of improving cardiovascular diseases, has the advantages of improving precipitation of cholesterol in vascular endothelium, avoiding damage of vascular endothelial cells and preventing and treating arteriosclerosis, and has wide pharmacological accommodation range and more obvious treatment effect. The structural formula of the graft is as shown in a formula (1a) or a formula (1b).
Description
Technical field
The present invention relates to the grafts and the grafting method of plant polyphenol and weathered coal humic acid degradation product.
Background technology
Plant polyphenol is the general name of aldehydes matters such as Grape Procyanidins, tea-polyphenol, mainly is made up of materials such as pyrocatechol, flavanol compound and polycondensation tannin.Functions such as that Grape Procyanidins, tea-polyphenol have is significantly anti-lipid, preventing cardiovascular disease, promotion microcirculation in human body, (procyanidolic oligomers is called for short OPC, the catechin of different quantities or l-Epicatechol be combined into Semen Vitis viniferae Central Plains flower cyanines element.The dimer that the simplest former colored cyanines element is a catechin, tripolymer, the tetramer etc.) function of class polyphenol is inseparable, also with Grape Procyanidins class thing in, the electron transport effect of " ubiquinone " coenzyme (ubiquinone ∽ semiquinone ∽ quinhydrones) structure is inseparable.
Weathered coal is the coal that is developed by higher plant, near or be exposed to the face of land, be subjected to effect such as sunlight, sleet, freezing and dust storm over a long time and the class oxidized coal that forms.According to 10% of 10,025 hundred million tons of total reservess of coal in China total amount, estimate at about 1,000 hundred million tons of weathered coal reserves.Xinjiang is disregarded in the new coalfield of discoveries such as " Changji ", and only just there are 3.5 hundred million tons of weathered coal resources in coalfield, " Hami " geographic South Lake.The weathered coal in coalfield, South Lake, Xinjiang is based on leonardite, weathered bituminite, and wherein humic acids is up to 65-85%, and ash content is lower, generally in the scope of 5 ∽ 12%.
The existing nearly 20 years history of conditioning that is used for cardiovascular disorder as the coal humic acid of polyelectrolyte.As, Yuan Shen unit of Beijing Tongren Hospital, Zhu Liangxiang, Ni Huilan, the effective constituent that Chinese Academy of Medical Sciences's pathology, physiological Study chamber Xue Quan good fortune, Dai Shunling, Wu Yunqing etc. loose with the Chinese medicine coal " fulvic acid sodium (Sodium Fulvate; be called for short SF) " is made clinical and experimental study and found: SF can increase mouse cardiac muscle nutrient flow amount, can reduce tame rabbit whole blood and plasma viscosity, can make patients with hypertension with the effect such as obviously slow down of nail fold microvascular blood flow velocity.Yuan Shenyuan etc. have adhered to years of researches, think that fulvic acid sodium does not have " carcinogenic ", " mutagenesis " etc. three and causes effect, and myocardial nutrition is had improvement effect (Chinese microcirculation, 2000,4 (2).Li Baocai is in recent years to the Polyphenols in the yunnan puer tea (catechin, theoflavin, thearubigins, theabrownin) and humic acids relatively. tea pigment and the humic acids in the Leaf of Assam Tea proposed. and especially theabrownin and xanthohumic acid, there is certain similarity in (structure and functional group) aspect chemical property.Yet, because yellow humic acid composition diversity (as, structural characterization through Chinese Academy of Sciences's chemistry institute beginning of the nineties to certain medicinal yellow humic acid: carbon containing 55.23%, hydrogen 2.32%, nitrogen 0.75%, oxygen 38.35%, the content of various functional groups are respectively carboxyl 7.96mmol/g, phenolic hydroxyl group 1.43mmol/g, alcoholic extract hydroxyl group 0.11mmol/g, methoxyl group 0.04mmol/g quinonyl 2.4mmol/g, molecular-weight average 1035.. select from: Zheng Ping Wang Xing shore etc. the application of yellow humic acid class material in agricultural and medicine. Chemical Industry Press, 1993), cause bioactive otherness, cause medicinal progress with strong points extremely slow.
Summary of the invention
The object of the present invention is to provide the grafts and the grafting method of a kind of plant polyphenol and weathered coal humic acid degradation product, to cure the mechanism of action in cardiovascular disorder still indeterminate to overcome medicinal humic acids that prior art exists, act on very for a short time, can't satisfy the defective of clinical application.
The grafts of plant polyphenol of the present invention and weathered coal humic acid degradation product, for having suc as formula the compound shown in (1a) or the formula (1b):
Wherein, R
1Represent H or OH; R
2Represent H or
The preparation method of the grafts of plant polyphenol shown in formula (1a) or the formula (1b) and weathered coal humic acid degradation product comprises the steps:
(1) with the weathered coal humic acid raw material pulverizing to the 80-200 order, be that the nitric acid of 20-50% mixes with weight concentration then, separate weathered coal humic acid at 50-105 ℃ of oxygen, oxygen was separated time 2-10 hour, by the nascent oxygen that nitric acid generates in oxidising process, had impelled the aromatic structure initial oxidation on the raw material humic acids to become phenolic hydroxyl group, pass through the ring scission of quinonyl fragrance again, oxygen is separated and is generated more carboxyl, weathered coal humic acid: nitric acid=100: 5～20, weight ratio;
(2) then, adding weight concentration in above-mentioned oxygen hydrolysis products is the sulfuric acid of 50-98%, reacts, and temperature of reaction is 70-125 ℃, time 0.5-5 hour, introduces sulfonic group (SO in humic acids functional group
3H), water-soluble to improve it, obtain activatory weathered coal humic acid (SNHA), weathered coal humic acid: sulfuric acid=100: 1～5, weight ratio;
(3) then, described activatory weathered coal humic acid in the presence of the quaternary ammonium salt of catalytic amount, was reacted 0.5～3 hour down at 30～65 ℃ with methyl alcohol and sodium methylate, obtain weathered coal humic acid degradation product;
The weight ratio of methyl alcohol and sodium methylate is 2～5:1, and the adding weight of methyl alcohol is 20～100% of weathered coal humic acid;
Described quaternary ammonium salt is selected from Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride, and the ratio of adding is 0.1～1% of an activatory weathered coal humic acid;
Preferably, step (1), (2) and (3) are carried out in frequency is the ultrasonic wave of 0.25-650KHz;
The weathered coal humic acid degradation product that obtains adopts HG/T 3289-1999 standard analysis, productive rate 75.20%, and purity reaches 99.0%; Through the VPO determining molecular weight is 274, shows through ultimate analysis, EDS energy spectrum analysis: do not detect harmful inorganics and radioelement, adopt analysis demonstrations such as capillary electrochromatography, this weathered coal humic acid degradation product structural formula is shown in (2):
(4) grafting of plant polyphenol and weathered coal humic acid degradation product:
Weathered coal humic acid degradation product with plant polyphenol and step (3) acquisition, place microwave reactor, at microwave frequency 915～2450MHz, under microwave power 300～500W, add catalyzer, 15～50 ℃ of thermotonus 5～15min, the grafts of acquisition plant polyphenol and weathered coal humic acid degradation product;
The mol ratio of plant polyphenol and weathered coal humic acid degradation product is 0.9～1.1: 1, is preferably 1: 1;
Described catalyzer is the mixture of methyl alcohol, potassium hydroxide and epoxy chloropropane, and the weight ratio of methyl alcohol, potassium hydroxide and epoxy chloropropane is:
Methyl alcohol: potassium hydroxide: epoxy chloropropane=28～35: 1.0: 60～70;
Adopt VPO osmotic pressure method to analyze, molecular weight is in 875～3280 scope.
Described plant polyphenol is the extract of Pericarpium Vitis viniferae, Semen Vitis viniferae or green tea, can adopt " research of Grape Procyanidins material extracting method " of Wang Chengdong, Zhang Zhen's literary composition etc. northwest Botany Gazette, 2004,11; Peng Youyuan, Ye Jiannong, " capillary electrophoresis with electrochemical detection is measured the polyphenol in the tobacco " assay office 2006,25 (6) of Li Guoqing: the method for bibliographical informations such as 92-96 is extracted, is analyzed, the present invention repeats no more, and its general structure is shown in (3):
Wherein: R
1Represent H or OH; R
2Represent H or
The integer of n=1～4 when n is 1, is catechin compounds, when n=2～4, is the catechin oligopolymer.
Evidence, the grafts of plant polyphenol of the present invention and weathered coal humic acid degradation product, the effect of improving cardiovascular disorder is arranged, have and improve the precipitation of cholesterol at blood vessel endothelium, avoid vascular endothelial cell damage, prevent and treat arteriosclerotic effect aspect, the pharmacology regulation range is wideer, and curative effect is more obvious.
Description of drawings
Fig. 1 is the capillary electrochromatography figure of embodiment 1 weathered coal humic acid degradation product.
Fig. 2 is the grafts of embodiment 2 tea-polyphenol weathered coal humic acid degradation products
13C-NMR figure.
Fig. 3 is that the infrared spectra (IR) of the grafts of embodiment 4 is analyzed collection of illustrative plates.
Fig. 4 is the IC of catechin-weathered coal humic acid degraded-grafts
50
Embodiment
The preparation of embodiment 1 weathered coal humic acid degradation product
(1) with 100g weathered coal humic acid raw material pulverizing to 160 order, under ultrasonic wave 200KHz, be that 50% nitric acid mixes with the 5g weight concentration, separate weathered coal humic acid at 50 ℃ of oxygen, oxygen is separated 2 hours time;
(2) then, adding 2g weight concentration is 90% sulfuric acid in above-mentioned oxygen hydrolysis products, and temperature of reaction is 70 ℃, 0.5 hour time, obtains the activatory weathered coal humic acid;
(3) with described activatory weathered coal humic acid in the presence of Dodecyl trimethyl ammonium chloride, with methyl alcohol and sodium methylate 65 ℃ of reactions 1 hour down, obtain weathered coal humic acid degradation product, as the formula (2);
The weight ratio of methyl alcohol and sodium methylate is 5:1, and the adding weight of methyl alcohol is 20% of weathered coal humic acid;
The ratio that Dodecyl trimethyl ammonium chloride adds is 1% of a weathered coal humic acid;
Through the VPO determining molecular weight is 274, through HG/T 3289-1999 standard analysis, and weathered coal humic acid degradation product productive rate 75.20%, purity reaches 99.0%; Show through ultimate analysis, EDS energy spectrum analysis: do not detect harmful inorganics and radioelement.
(1) with 100g weathered coal humic acid raw material pulverizing to 160 order, under ultrasonic wave 200KHz, be that 20% nitric acid mixes with the 20g weight concentration, separate weathered coal humic acid at 105 ℃ of oxygen, oxygen is separated 10 hours time;
(2) then, adding 5g weight concentration is 50% sulfuric acid in above-mentioned oxygen hydrolysis products, and temperature of reaction is 125 ℃, 5 hours time, obtains the activatory weathered coal humic acid;
(3) with described activatory weathered coal humic acid in the presence of palmityl trimethyl ammonium chloride, with methyl alcohol and sodium methylate 30 ℃ of reactions 3 hours down, obtain weathered coal humic acid degradation product, as the formula (2);
The weight ratio of methyl alcohol and sodium methylate is 2:1, and the adding weight of methyl alcohol is 100% of weathered coal humic acid;
The ratio that palmityl trimethyl ammonium chloride adds is 0.1% of a weathered coal humic acid;
Through the VPO determining molecular weight is 274, through HG/T 3289-1999 standard analysis, and weathered coal humic acid degradation product productive rate 75.50%, purity reaches 99.1%; Show through ultimate analysis, EDS energy spectrum analysis: do not detect harmful inorganics and radioelement.
The grafting of embodiment 3 tea-polyphenol and weathered coal humic acid degradation product
Weathered coal humic acid degradation product with 50 moles of plant polyphenols and 50 moles of embodiment 1 places microwave reactor, at microwave frequency 2450MHz, under the microwave power 300W, add catalyzer, 50 ℃ of thermotonus 5min, the grafts of acquisition plant polyphenol and weathered coal humic acid degradation product;
Catalyzer is the mixture of methyl alcohol, potassium hydroxide and epoxy chloropropane, and the weight ratio of methyl alcohol, potassium hydroxide and epoxy chloropropane is: methyl alcohol: potassium hydroxide: epoxy chloropropane=32: 1.0: 68;
Adopt VPO osmotic pressure method to analyze, molecular weight is 875, and structural formula is as follows,
The analysis collection of illustrative plates of NMR is seen Fig. 2.
The grafting of embodiment 4 catechin oligopolymer and weathered coal humic acid degradation product
At microwave frequency 915MHz, add earlier structural formula in the microwave reactor of microwave power 500W as 50 moles of the weathered coal humic acid degradation products of (2), the catechin oligopolymer that adds 50 moles of lixiviates from Semen Vitis viniferae/Pericarpium Vitis viniferae polyphenol again, structural formula is suc as formula (3), the catechin oligopolymer of n=2, catalyzer is the mixture of methyl alcohol, potassium hydroxide and epoxy chloropropane, and the weight ratio of methyl alcohol, potassium hydroxide and epoxy chloropropane is: methyl alcohol: potassium hydroxide: epoxy chloropropane=28: 1.0: 60; Temperature of reaction is 35 ℃, and the reaction times is 15min, obtains the grafts of plant polyphenol and weathered coal humic acid degradation product, molecular weight 1476, and infrared spectra (IR) is analyzed collection of illustrative plates such as Fig. 3, and structural formula is as follows:
Embodiment 5
The tea-polyphenol that embodiment 3 is made and the grafts of weathered coal humic acid degradation product add dimethyl sulfoxide (DMSO) (DMSO), are made into the mother liquor that concentration is 100mg/ml, be 1000 μ g/ml with the dilution of 24 well culture plates again, 500 μ g/ml, 250 μ g/ml, the clinical experiment liquid of 125 μ g/ml.Simultaneously, will take from HeLa cell that rabbit aortic tunica intima layer cultivates with tryptic digestion after, be that the substratum of 10% calf serum is made into the individual cells suspension with containing weight concentration; In 96 orifice plates, adding contains in the experiment liquid of different concns with cell suspension inoculation, and relatively the blank group is established three parallel holes for every group, in 37 ℃, and volumetric concentration 5%CO
2Cultivated 24 hours in the incubator, press MTT (tetrazole) method then, on microplate reader, measure its optical density value (OD value), and according to, the calculating formula of inhibiting rate=(1-experimental group OD value)/control group OD value * 100%, the grafts of observation tea-polyphenol and weathered coal humic acid degradation product advances the inhibition situation to vascular smooth muscle cell.The results are shown in Figure 4.
Fig. 4 shows: catechin-weathered coal humic acid degraded-grafts is in the concentration of 100ug/ml, and inhibiting rate has reached IC
50Index, the arteriosclerosis to hypercholesterolemia, hemorheology change etc. causes has good inhibitory effect.
Claims (7)
1. the grafts of plant polyphenol and weathered coal humic acid degradation product is characterized in that, for having suc as formula the compound shown in (1a) or the formula (1b):
Wherein, R
1Represent H or OH; R
2Represent H or
2. the preparation method of the grafts of plant polyphenol according to claim 1 and weathered coal humic acid degradation product is characterized in that, comprises the steps:
(1), separates with nitric acid mixing oxygen then with the weathered coal humic acid raw material pulverizing;
(2) then, in above-mentioned oxygen hydrolysis products, add sulfuric acid and react, obtain the activatory weathered coal humic acid;
(3) then, described activatory weathered coal humic acid in the presence of the quaternary ammonium salt of catalytic amount, with methyl alcohol and sodium methylate reaction, is obtained weathered coal humic acid degradation product;
(4) grafting of plant polyphenol and weathered coal humic acid degradation product:
Weathered coal humic acid degradation product with plant polyphenol and step (3) acquisition places microwave reactor, adds catalyzer, reaction, the grafts of acquisition plant polyphenol and weathered coal humic acid degradation product;
Described catalyzer is the mixture of methyl alcohol, potassium hydroxide and epoxy chloropropane.
3. method according to claim 1, it is characterized in that, in the step (1), weathered coal humic acid is pulverized, be that the nitric acid of 20-50% mixes with weight concentration then, separate weathered coal humic acid at 50-105 ℃ of oxygen, oxygen was separated time 2-10 hour, weathered coal humic acid: nitric acid=100: 5～20, weight ratio.
4. method according to claim 1 is characterized in that, in the step (2), the sulfuric acid that adds weight concentration and be 50-98% in the oxygen hydrolysis products reacts, and temperature of reaction is 70-125 ℃, time 0.5-5 hour, weathered coal humic acid: sulfuric acid=100: 1～5, weight ratio.
5. method according to claim 1 is characterized in that, in the step (3), described activatory weathered coal humic acid reacted 0.5～3 hour down at 30～65 ℃ with methyl alcohol and sodium methylate in the presence of the quaternary ammonium salt of catalytic amount;
The weight ratio of methyl alcohol and sodium methylate is 2～5:1, and the adding weight of methyl alcohol is 20～100% of weathered coal humic acid;
Described quaternary ammonium salt is selected from Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride, and the ratio of adding is 0.1～1% of an activatory weathered coal humic acid weight.
6. method according to claim 1, it is characterized in that, in the step (4), microwave frequency 915～2450MHz, under microwave power 300～500W, 15～50 ℃ of thermotonus 5～15min;
The mol ratio of plant polyphenol and weathered coal humic acid degradation product is 0.9～1.1: 1;
The weight ratio of methyl alcohol, potassium hydroxide and epoxy chloropropane is: methyl alcohol: potassium hydroxide: epoxy chloropropane=28～35: 1.0: 60～70.
7. according to each described method of claim 1～5, it is characterized in that step (1), (2) and (3) are carried out in frequency is the ultrasonic wave of 0.25-650KHz.
8. method according to claim 1 is characterized in that, described plant polyphenol is the extract of Pericarpium Vitis viniferae, Semen Vitis viniferae or green tea, and its general structure is shown in (3):
Wherein: R
1Represent H or OH; R
2Represent H or
The integer of n=1～4 when n is 1, is catechin compounds, when n=2～4, is the catechin oligopolymer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012807A (en) * | 2012-12-21 | 2013-04-03 | 贵州大学 | Preparation method and application of modified humic acid quaternary ammonium salt |
| CN113796378A (en) * | 2021-09-23 | 2021-12-17 | 新疆圣大一方生物科技有限公司 | Preparation method of agricultural and forestry antibacterial bactericide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012807A (en) * | 2012-12-21 | 2013-04-03 | 贵州大学 | Preparation method and application of modified humic acid quaternary ammonium salt |
| CN113796378A (en) * | 2021-09-23 | 2021-12-17 | 新疆圣大一方生物科技有限公司 | Preparation method of agricultural and forestry antibacterial bactericide |
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