CN104910230A - Preparation method of scutellarin rare earth metal complex - Google Patents
Preparation method of scutellarin rare earth metal complex Download PDFInfo
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- CN104910230A CN104910230A CN201510181407.3A CN201510181407A CN104910230A CN 104910230 A CN104910230 A CN 104910230A CN 201510181407 A CN201510181407 A CN 201510181407A CN 104910230 A CN104910230 A CN 104910230A
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- scutellarin
- metal
- lanthanum
- metal complexes
- cerium
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Abstract
The invention relates to a preparation method of a scutellarin rare earth metal complex. A raw material scutellarin respectively reacts with lanthanum and cerium metal ions under weakly alkaline conditions to form the metal complex. The preparation method of the scutellarin rare earth metal complex is simple, and the above obtained product has the advantages of high yield and high purity.
Description
Technical field
The present invention relates to scutellarin is raw material, prepares scutellarin rare earth metal complex.
Background technology
Scutellarin, has another name called lamp-dish flower acetic, is that one is used for the treatment of cardiovascular and cerebrovascular diseases, and the natural product organic drug of anticancer growth, its main source is feverfew Herba Erigerontis herb, Herba Scutellariae Barbatae herb.
Recent research shows, rare earth metal many-sidedly has similarity with the biological activity of flavonoid compound antitumor, antibacterial, antiviral etc., but rare earth metal itself has again certain toxic action to organism, and the developing of flavonoid rare earth compound, not only can reduce the toxicity of rare earth ion, also can strengthen the activity of flavonoid compound.If by above-mentioned many kinds of metal ions and some biological active constituents from natural medicines with the use of playing synergy possibly.As the important branch of flavonoid natural product derivative, its metal complexes is subject to the attention of investigator always.Due in flavonoid compound molecule mostly containing Sauerstoffatom, especially the structure such as its 4 carbonyls, has strong coordination ability, can form title complex with metallic element.And Recent study also shows, some metal is not only the necessary element maintaining human life activity, and also can have scavenging free radicals after itself and flavonoid compound form metal complexes, strengthen immunologic function, antibacterial, antiviral, suppress the effect such as lipoxygenase, anti-inflammatory anti-allergic, and flavonoid metallic compound often can play and heightens the effect of a treatment, even produce new pharmacological action.Therefore, exploitation scutellarin metal complexes is also studied its biological activity, will contribute to the application market of opening up scutellarin, also by the development of power-assisted traditional Chinese medicine industry.
In scutellarin Study on Complexes, only having the patent CN03135215.4 of the people such as Bai Yongcheng to report at present adopts boric acid, Sodium Tetraborate, aluminum chloride or alum to be complexing agent, after coordinating in the basic conditions, acid solvent regulates pH, and add acetone and other organic solvent and make it precipitate, obtain solid complex salt.
Summary of the invention
For the deficiency in above-mentioned field, the invention provides the scutellarin rare earth metal complex of novel texture.
Present invention also offers the preparation method of scutellarin rare earth metal complex, the method is simple, and easy to control, and final product purity is high simultaneously.
For achieving the above object, the invention provides following scutellarin rare earth metal complex, general molecular formula is (C
21h
17o
12)
xm (H
2o)
y, M in formula
1for being 0 for La (III) or Ce (III), x are 3, y, its structural formula is as shown in Fig. 1 .1.Described La (III), Ce (III) represent trivalent lanthanum ion, trivalent cerium ion respectively.
Fig. 1 .1 scutellarin metal M
1complex structure formula (M
1=La, Ce)
For achieving the above object, scutellarin metal complexes preparation method, be take a certain amount of scutellarin to add in deionized water, drip weakly alkaline solution to just dissolving completely, adding lanthanum, cerium metal solion according to a certain percentage, constant temperature stirs certain hour, generate yellow, greyish-green precipitation respectively, filter, with deionized water wash, drying, obtains metal complexes.Described weakly alkaline solution is sodium bicarbonate, saleratus, sodium formiate, potassium formiate, sodium acetate, potassium acetate, Sodium phosphate dibasic, dipotassium hydrogen phosphate, sodium phosphate or potassium phosphate solution.
Preferably, the mol ratio of described lanthanum ion or cerium ion and scutellarin is 1:3.
Preferably, the temperature of reaction of described scutellarin and rare earth ion is between 50 DEG C ~ 70 DEG C.
Preferably, the reaction times of affiliated scutellarin and rare earth ion is between 0.5 ~ 1.5h.
Accompanying drawing explanation
Fig. 1 .1 is scutellarin metal M
1complex structure formula (M
1=La, Ce) figure.
Fig. 1 .2 scutellarin metal M
1complex structure formula (M
1=La, Ce) figure.
Embodiment
In order to make the object, technical solutions and advantages of the present invention clearly, will be described in detail the preferred embodiments of the present invention below.
The preparation of [embodiment 1] scutellarin lanthanum, cerium complexes
Taking a certain amount of scutellarin adds in deionized water, drips 1%NaHCO
3to just dissolving completely, be that 3:1 adds lanthanum trichloride or cerous compounds solution according to the mol ratio of scutellarin and lanthanum trichloride or cerous compounds, 60 DEG C are stirred 1 hour, generate yellow or greyish-green precipitation respectively, filter, with deionized water wash, drying, obtains title complex.
The ultraviolet spectroscopy of [embodiment 2] scutellarin metal complexes
Take scutellarin and metal complexes 5.0g thereof respectively, join in DMSO and dissolve, be quantitatively transferred in 10mL volumetric flask, and be diluted to scale with DMSO, shake up, for subsequent use.Pipette respectively in scutellarin and metal complexes DMSO solution thereof and cuvette, in the interscan of wavelength 200 ~ 500nm scope, gained ultra-violet absorption spectrum data, in table 1.1.
Table 1.1 scutellarin and metal complexes ultraviolet-visible absorption spectroscopy data sheet thereof
Table 1.1 scutellarin and metal complexes ultraviolet-visible absorption spectroscopy data sheet thereof
Interval in 200nm ~ 500nm, measure the ultra-violet absorption spectrum of scutellarin and scutellarin lanthanum, cerium complexes, scutellarin has two absorption peaks at 286nm and 335nm, and π ~ π * transition that the former can be attributed to conjugation in ligand molecular produces, and is II band; N ~ π * transition that the latter can be attributed in ligand molecular produces, and is I band.
As shown above, scutellarin Lanthanide complex, scutellarin cerium complexes characterize superiors in uv-absorbing and are with I, II all without significantly variation.
Title complex infared spectrum characterizes
Spectroscopically pure KBr (100 ~ 200mg) is ground to form the fine powder of um level with scutellarin and metal complexes (1 ~ 2mg) thereof respectively in agate mortar, adopt special sheeting equipment, be pressed into diameter 13mm, thickness is about the transparent sheet of 1mm, load on solid sample testing jig, in the interscan of wavelength 4000 ~ 400cm scope.Record scutellarin and metal complexes solid preform diffuse reflectance infrared spectroscopy group spectral data table thereof, as shown in table 1.2.
Table 1.2 scutellarin and metal complexes IR vibrational wave number thereof and characteristic group synopsis (cm
-1)
The Infrared spectroscopy of part and title complex
In scutellarin molecular structure, at 3350cm
-1~ 3400cm
-1there is wide and strong associate hydrogen bond absorption peak at place, and that is because 5 phenolic hydroxyl groups and 4 carbonyls can form intramolecular hydrogen bond in scutellarin molecular structure, and comparatively stable, and its absorption peak is 3367.2cm
-1, and in scutellarin lanthanum, cerium complexes infrared spectra synopsis, can find out that its corresponding absorption peak moves to 3382.6 respectively, 3372.9cm
-1, illustrate that coordination reaction makes intramolecular hydrogen bond structure be destroyed, create coordination, create reaction with title complex.
In the infrared spectra of scutellarin, glucuronic acid ν (C=O) wave number is higher than carbonyl ν (C=O), this is because the effect of hydroxyl on glucuronic acid, C=O electrophilic inductive effect is increased, C=O double bond strengthens, compare carbonyl ν (C=O) to move to high wave number, so 1741.4cm
-1for the carboxylic carbonyl absorption peak on glucuronic acid in molecular structure, 1720.0cm
-1for 4 carbonyl absorption peaks in molecular structure.In scutellarin lanthanum, cerium complexes infrared spectra, the carboxylic carbonyl absorption peak in molecular structure on glucuronic acid moves to 1616.1,1724.1 respectively, and in molecular structure, 4 carbonyl absorption peaks disappear substantially, and that is because add 1%NaHCO in experimentation
3solution, glucal acidic group in molecular structure is made to be converted into Sodium D-glucuronate, make its C=O bond absorption peak position red shift, carbonyl bonding electrons density is caused more to depart from the geometric centre of key and shift to Sauerstoffatom after the lone-pair electron of oxygen and the unoccupied orbital of metal complexes form coordinate bond on 4 carbonyls simultaneously, the cloud density of C=O bond is caused to reduce, its force constant is diminished, so also there is red shift or absorption intensity reduction.So in scutellarin structure, the C=O absorption peak that two of appearance are different, may occur the overlap of C=O absorption peak, and cause the disappearance of 4 carbonyl absorption peaks at each metal complexes, scutellarin and lanthanum are also described, the coordination sites of cerium is 4 carbonyls.
In scutellarin molecular structure, C=C group vibrational frequency district is 1450cm
-1-1670cm
-1, also in relevant range, there is corresponding absorption peak in lanthanum, the cerium complexes of scutellarin, and the trend of the substantially all oriented low frequency direction movement of the absorption peak corresponding with scutellarin.Infer that this may be because when metal complexes is formed after, form a new structural system, thus the conjugative effect being enhancing.
Vibrational frequency (the 1240cm of the C-O-C key in scutellarin and metal complexes molecule thereof
-1-1370cm
-1) only have and change slightly, showing that C-O-C key is less by metal ion complexation effect, also illustrating that C cyclic ethers key is for participating in mating reaction.
600cm
-1the absorption of following low frequency fingerprint region can think that the stretching vibration of ligating atom-metal and flexural vibration absorb.
The metal ion content of scutellarin metal complexes measures
The scutellarin metal complexes of accurate weighing certainweight, through 400 DEG C of roastings 5 hours in retort furnace, after drying is stable, through each metal content of EDTA titration measuring.Concrete data are in table 1.3:
Table 1.3 scutellarin metal complexes chart
Scutellarin and metal complexes structure thereof
In sum, by the absorption peak mutation analysis of the ultra-violet absorption spectrum to scutellarin and metal complexes thereof, infrared absorption spectrum, can infer that scutellarin and lanthanum, cerium coordination reaction occur, and main coordination sites is scutellarin 4-position carbonyl and 5-position phenolic hydroxyl group.Comparing again according to Determination of Metals value and theoretical value.
Scutellarin metal complexes structure can be obtained as follows, see Fig. 1 .2:
Fig. 1 .2 scutellarin metal M
1complex structure formula (M
1=La, Ce)
Claims (7)
1. scutellarin rare earth metal complex, is characterized in that taking scutellarin as raw material, under weak basic condition, prepares scutellarin rare earth metal complex.Its general structure is (C
21h
17o
12)
xm (H
2o)
y, M in formula
1for being 0 for La (III) or Ce (III), x are 3, y, its structural formula is as shown in Fig. 1 .1.
2. scutellarin metal complexes preparation method according to claim 1, it is characterized in that, taking a certain amount of scutellarin adds in deionized water, dripping weakly alkaline solution to just dissolving completely, adding the metal ion solution such as lanthanum, cerium according to a certain percentage, constant temperature stirs certain hour, generate yellow, greyish-green precipitation respectively, filter, with deionized water wash, drying, obtains metal complexes.Described weakly alkaline solution is sodium bicarbonate, saleratus, sodium formiate, potassium formiate, sodium acetate, potassium acetate, Sodium phosphate dibasic, dipotassium hydrogen phosphate, sodium phosphate or potassium phosphate solution.
3. scutellarin metal complexes preparation method according to claim 2, it is characterized in that, described constant temperature whipping temp is between 40 DEG C ~ 80 DEG C.
4. scutellarin metal complexes preparation method according to claim 2, it is characterized in that, described constant temperature churning time is between 0.2 ~ 2h.
5. scutellarin metal complexes preparation method according to claim 2, is characterized in that, describedly adds the metal ion solution such as lanthanum, cerium according to a certain percentage, and the molar mass ratio of adding scutellarin and lanthanum or cerium metal ion described in it is: 2 ~ 4:1.
6. scutellarin metal complexes preparation method according to claim 2, it is characterized in that, the described lanthanum ion source added according to a certain percentage is the trivalent lanthanum ion metal-salts such as lanthanum trichloride.
7. scutellarin metal complexes preparation method according to claim 2, it is characterized in that, the described cerium metal ion source added according to a certain percentage is the trivalent cerium ion metal-salts such as cerous compounds.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108659082A (en) * | 2018-05-25 | 2018-10-16 | 武汉轻工大学 | A kind of preparation method for treating grice diarrhoea scutelloside Zn complex |
| CN108727452A (en) * | 2018-05-26 | 2018-11-02 | 武汉轻工大学 | A kind of preparation method of scutelloside lanthanum or cerium complexes in buffer solution medium |
| CN108794554A (en) * | 2018-05-25 | 2018-11-13 | 武汉轻工大学 | The preparation method of one boar mixed feeding scutelloside manganese complex |
| CN108794553A (en) * | 2018-05-25 | 2018-11-13 | 武汉轻工大学 | A kind of preparation method for pig mixed feed scutelloside aluminum complex |
| CN109988208A (en) * | 2019-04-29 | 2019-07-09 | 武汉轻工大学 | A kind of preparation method and application of metal-scutelloside complex |
| CN110003294A (en) * | 2019-04-30 | 2019-07-12 | 武汉轻工大学 | A kind of preparation method of copper cobalt nickel-scutelloside complex |
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| CN102516341A (en) * | 2011-11-16 | 2012-06-27 | 西南大学 | Baicalin metal complex and preparation method and application thereof |
Non-Patent Citations (1)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108659082A (en) * | 2018-05-25 | 2018-10-16 | 武汉轻工大学 | A kind of preparation method for treating grice diarrhoea scutelloside Zn complex |
| CN108794554A (en) * | 2018-05-25 | 2018-11-13 | 武汉轻工大学 | The preparation method of one boar mixed feeding scutelloside manganese complex |
| CN108794553A (en) * | 2018-05-25 | 2018-11-13 | 武汉轻工大学 | A kind of preparation method for pig mixed feed scutelloside aluminum complex |
| CN108659082B (en) * | 2018-05-25 | 2021-09-24 | 武汉轻工大学 | Preparation method of baicalin zinc complex for treating piglet diarrhea |
| CN108794553B (en) * | 2018-05-25 | 2022-02-15 | 武汉轻工大学 | Preparation method of baicalin aluminum complex for pig mixed feed |
| CN108727452A (en) * | 2018-05-26 | 2018-11-02 | 武汉轻工大学 | A kind of preparation method of scutelloside lanthanum or cerium complexes in buffer solution medium |
| CN109988208A (en) * | 2019-04-29 | 2019-07-09 | 武汉轻工大学 | A kind of preparation method and application of metal-scutelloside complex |
| CN110003294A (en) * | 2019-04-30 | 2019-07-12 | 武汉轻工大学 | A kind of preparation method of copper cobalt nickel-scutelloside complex |
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Inventor after: Shi Gaofeng Inventor after: Yao Ruixing Inventor after: Wang Guoying Inventor after: Chen Fuwen Inventor before: Yao Ruixing Inventor before: Shi Gaofeng Inventor before: Wang Guoying Inventor before: Chen Fuwen Inventor before: Zhao Guochao Inventor before: Tian Ge |
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Effective date of registration: 20170919 Address after: 730050 Qilihe, Gansu Province Lan Ping Ping Road, No. 287, No. Applicant after: Lanzhou University Of Technology Address before: 730900 Gansu Baiyin hi tech Economic Development Zone biological medicine intermediate incubator Applicant before: Yao Ruixing |
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Application publication date: 20150916 |