CN100445286C

CN100445286C - Preparation method of natural phyllo-iron zinc salt

Info

Publication number: CN100445286C
Application number: CNB2007100615472A
Authority: CN
Inventors: 刘淑萍; 孙彩云; 闫路省
Original assignee: Hebei University of Science and Technology
Current assignee: Hebei University of Technology; Hebei University of Science and Technology
Priority date: 2007-02-15
Filing date: 2007-02-15
Publication date: 2008-12-24
Anticipated expiration: 2027-02-15
Also published as: CN101045730A

Abstract

This invention relates to a preparation method of natural chlorophyl iron zinc salt; belong to natural colouring matter preparation region. The method are: silkworm litter smashed by crusher, soften and lixiviation; add 10 percent NaOH solution to chlorophyl solution after lixiviation to regulate ph value of test solution, heating, reduced pressure distillation, recovery solvent; cooling solution after saponification, then add to tap funnel; join petroleum ether for oscillation, extraction, collect chlorophyl natrium salt solution and put it into reaction vessel, drop hydrochloric acid to regulate PH value, magnesium ion prolapsed from porphyrin ring, join ferrous ion solution, intensive mixing for iron substitution, and the generated black precipitate is iron chlorophyl acid , after-filtration, washing precipitation neatness; use concentrated alkali to dissolve iron chlorophyl acid completely, add salification ion then post precipitation, separate and dry. This invention possesses potential application at foodstuff, medicine and so on region.

Description

The preparation method of natural phyllo-iron zinc salt

Technical field

The present invention relates to a kind of preparation method of natural pigment, specifically a kind of preparation method of natural phyllo-iron zinc salt.

Background technology

The required chlorophyll of human survival belongs to the magnesium porphyrin compound, is a kind of nontoxic, natural pigment of having no side effect.But because chlorophyll character instability, fugitive color is rotten, makes its application be subjected to great restriction.When the magnesium ion at chlorophyll center by other metal ion (Cu ²⁺, Zn ²⁺, Fe ³⁺Fe ²⁺, Co ²⁺Deng) replace after, just form the individual layer metalloporphyrin complex.The phyllins product that prepared at present is as Copper chlorophyllin a sodium salt, zinc CHLOROPHYLLINE sodium salt, cobalt CHLOROPHYLLINE sodium salt, iron chlorophyllin sodium salt etc., has good coloring effect, promote hematopoiesis, protect the liver, antimicrobial, promote biological nature and unique pharmacological functions such as wound and ulcer healing and anti-mutation, be easily absorbed by the body and have no side effect, be widely used in medicine, food, daily-use chemical industry and clinical.In recent years development in science and technology is that the research that phyllins are applied to diagnosis, treatment and the control of malignant tumour has been obtained important breakthrough.

The structure of the protoheme in chlorophyll structure and human and the most of animal bloods is extremely similar, all is the tetrapyrrole metallic compound, and its key distinction is that chlorophyllous central atom is a magnesium and the central atom of protoheme is an iron.If for de-magging, the zine ion salify is prepared into the regeneration that natural phyllo-iron zinc salt can not only promote oxyphorase with natural phyllo-iron (II), have certain anti-anaemia effect and antioxygenation, and administration of human zinc supplementation simultaneously.The method for preparing natural phyllo-iron zinc salt is by retrieval especially extracted chlorophyll from silkworm excrement and the technical scheme that turns to iron zinc salt of deriving yet there are no report.

Summary of the invention

The purpose of this invention is to provide a kind of is raw material with the silkworm excrement, and with chlorophyll saponification, acidifying, iron (II) generation, salify, method is simple and direct, the preparation method of the natural phyllo-iron zinc salt that purification rate is high with single factor rotation method.

Realize the foregoing invention purpose by the following technical solutions:

A kind of preparation method of natural phyllo-iron zinc salt, it is raw material with the silkworm excrement, it is characterized in that, preparation as follows,

A, saponification and extracting process:

With silkworm excrement crusher in crushing, softening, mixed solvent lixiviate, adding 10%NaOH solution adjusting test solution pH in the chlorophyll solution after lixiviate is 11, and heating is 1 hour under 60 ℃ of temperature, vacuum distillation recovered solvent; To change in the separating funnel after the cooling of the solution after the saponification, add isopyknic sherwood oil vibration 1 minute, leave standstill the layering of 2-3 clock, extract 2-3 time; Collect the bottle-green chlorophyll sodium salt brine solution of lower floor;

B, acidifying and iron are for method:

Chlorophyll sodium salt brine solution behind the purification by liquid extraction is put into reaction vessel, drip after 1: 5 hydrochloric acid regulates pH=2～3, magnesium ion is deviate from porphyrin ring.Add the capacity ferrous ions soln, fully stir iron generation, the black precipitate of generation is iron pheophytin acid, and after-filtration, washing precipitation are clean;

C, salifying method:

The iron chlorophyllin that makes carefully is dissolved to fully with concentrated base, adds excessive salify ion Zn ²⁺Postprecipitation separates, and drying can obtain cyan iron pheophytin zinc salt.

Chlorophyll is the magnesium porphyrin compound, central atom magnesium links to each other with porphyrin ring with coordinate bond by covalent linkage, because the chelating instability of magnesium and porphyrin ring, under effects such as light, heat, acid, alkali, central atom magnesium very easily splits away off, generate the phoeophytin of brown, thereby make its green fade or disappear.

Chlorophyll is the high-molecular weight hydrocarbon polymer, has lipotropy, and is water insoluble.In the chlorophyll structure double carboxy acid ester is arranged, one is the esterification of methyl institute, and one is the esterification of phytol base institute.Saponification reaction takes place in basic solution, and demethylating and phytol base generate water-soluble salt.In acidic medium, the chlorophyll de-magging generates chlorophyllin.

Hydrogen in pH=2～3 hydrochloric acid solns in the chlorophyllin porphyrin ring can be replaced the generation iron chlorophyllin by ferrous ion, promptly is the porphyrin compound of central atom with iron.Can react salify with zine ion under certain condition.

Remarkable advantage of the present invention is, 1. to prepare phyllins behind the raw material silkworm excrement extraction natural chlorophyll that is easy to get--chlorophyll iron (II) zinc salt, the iron of realization administration of human, zinc are with mending and having no side effect; The iron chlorophyllin zinc salt is blackish green powdery solid, in the water insoluble and dilute hydrochloric acid, is slightly soluble in acetone, ethanol, and solution is yellow-green colour, be soluble in the basic solution emerald green solution.2. the preparation method is simple and direct, cost is low, and the purification rate height does not produce chlorophyll iron (III) zinc salt; 3. be widely used, but medicine, also foodstuff additive.At aspects such as food, medicine boundless application prospect is arranged.

Description of drawings

Fig. 1 is the UV absorption spectrum synoptic diagram of five kinds of products in the building-up process.

Fig. 2 is the IR spectrogram of pheophorbide.

Fig. 3 is the IR spectrogram of de-magging iron chlorophyllin zinc.

Fig. 4 is the IR spectrogram of iron chlorophyllin zinc.

Fig. 5 is the IR spectrogram of iron chlorophyllin.

Embodiment

The present invention will be further described below in conjunction with concrete drawings and Examples.

The key instrument that the present invention uses: HH-S digital display thermostat water bath (Jintan); 220A dual wavelength scanning spectrophotometer (Japan); The AEL-160 electronic balance; Elementar Vario EL microelement analyzer (Germany); Nicolet

Mangna-IR 750 Fourier infrared spectrometers

The main medicine that the present invention uses: acetone, ethanol, NaOH, HCl, sherwood oil, 10% zincon, ferrous sulfate.

Raw material: silkworm excrement (Tangshan)

The structural response formula of the preparation principle of iron chlorophyllin:

Represent with reaction equation:

Saponification reaction

Acidification reaction

Iron is for reaction

Salt-forming reaction

Iron chlorophyllin and zine ion react under weak basic condition and generate the iron pheophytin zinc salt.

Preparation method embodiment:

Saponification and extracting process:

With 100 kilograms of silkworm excrement crusher in crushing, the powder of broken shape added water (1:0.6) softening 5 hours, with 2 times acetone-alcohol mixed solvent lixiviate, filtered.Adding 10%NaOH solution adjusting test solution pH in the chlorophyll solution after lixiviate is 11, heats 1 hour vacuum distillation recovered solvent in HH-S digital display thermostat water bath under 60 ℃ of temperature; To change in the separatory cone funnel after the cooling of the solution after the saponification, add isopyknic sherwood oil vibration 1 minute, leave standstill layering in 2-3 minute, extract 2-3 time; Collect the bottle-green chlorophyll sodium salt brine solution of lower floor;

Acidifying and iron are for method:

Chlorophyll sodium salt brine solution behind the purification by liquid extraction is put into reactor, drip after 1: 5 hydrochloric acid regulates pH=2～3, form tawny de-magging acid solution.The ferrous ions soln that adds capacity fully stirred iron for 2 hours, and the black precipitate of generation is iron pheophytin acid, and after-filtration, water washing precipitation are totally; By the Mg in the complexometric titration solution, Fe ion content, calculate chlorophyll iron replacement rate and reach 54%.Detect with 220A dual wavelength scanning spectrophotometer and Nicolet Mangna-IR750Fourier infrared spectrometer, determine iron pheophytin acid structure, thereby method of proof is correct.

Salifying method:

The iron chlorophyllin that makes carefully is dissolved to fully with concentrated base, alkalinely can uses the hydrochloric acid adjustment when excessive, add excessive salify ion Zn ²⁺Postprecipitation separates, and drying can obtain cyan iron pheophytin zinc salt.Zn in the EDTA complexometric titration solution ²⁺Content, the salify rate that calculates iron pheophytin zinc reaches 99%.By UV, IR spectrum and Elementar Vario EL microelement analyzer (Germany), detected constitutional features and with saponification and iron for the spectrogram of product relatively, determine that product is the iron chlorophyllin zinc salt.

Iron chlorophyllin zinc salt proterties: be blackish green powdery solid, in the water insoluble and dilute hydrochloric acid, be slightly soluble in acetone, ethanol, solution is yellow-green colour, be soluble in the basic solution emerald green solution.

The salify analysis of iron chlorophyllin zinc

1. change from experimental phenomena, de-magging acid is tawny, and ferrous acid is a black, illustrates that iron participates in reaction.And during salify, iron chlorophyllin is dissolved in the alkali lye, solution colour is a brownish black, adds Zn ²⁺Reagent produces green precipitate immediately, has illustrated that novel substance generates.

2. from the character of ferrous acid, can be dissolved in apparent acidity in the alkali lye, should illustrate that iron has been embedded into the porphyrin ring center with alkali reaction, rather than side chain.

3. uv-visible absorption spectra (UV) and infrared spectra (IR)

Referring to accompanying drawing 1, iron chlorophyllin zinc 1 among Fig. 1, pheophorbide 2, iron chlorophyllin 3, chlorophyll 4, magnesium CHLOROPHYLLINE 5.From the UV spectrum analysis, the absorption curve of iron chlorophyllin zinc 1 is similar to the peak shape of chlorophyll 4 with 655nm at 415nm, and bigger with the difference of ferrous acid, illustrates that zinc has arrived side chain.Two positive charges of zinc band, its sucting electronic effect have weakened carboxylic acid group's the electronic effect of giving, and make the Q band move to 655nm from 691nm, and are comparatively approaching with the absorption peak (405nm and 650nm) of the sodium iron chlorophyllin of bibliographical information.

Referring to accompanying

drawing

2,3,4,5.Can determine from the IR spectrum analysis of figure that iron has been coordinated to and be formed centrally iron porphyrin the porphyrin ring, zine ion combines in the salify mode with iron porphyrin, is linked to the outer side chain carboxyl of ring place and has formed iron chlorophyllin zinc.

4. ultimate analysis: N, C, three kinds of element percentage compositions of H (W%) are respectively: N (6.05); C (44.17); H (3.58).

Theoretical value is inferred: encircling outer carboxyl oxygen percentage composition is 6%～11%, and the chlorophyll porphyrin ring of remaining part for being made of C, N, H etc. accounts for 51%～59%; Results of elemental analyses shows that C, N, H proportion sum are 53.8%, and is comparatively approaching with theoretical inferred value.Remaining is zinc and iron and small amount of impurities.

Claims

1, a kind of preparation method of natural phyllo-iron zinc salt, it is a raw material with the silkworm excrement, it is characterized in that, preparation as follows,

A, saponification and extracting process:

With silkworm excrement crusher in crushing, softening, lixiviate, adding 10%NaOH solution adjusting test solution pH in the chlorophyll solution after lixiviate is 11, and heating is 1 hour under 60 ℃ of temperature, vacuum distillation recovered solvent; To change in the separating funnel after the cooling of the solution after the saponification, add isopyknic sherwood oil vibration 1 minute, leave standstill the layering of 2-3 clock, extract 2-3 time; Collect the bottle-green chlorophyll sodium salt brine solution of lower floor;

B, acidifying and iron are for method:

Chlorophyll sodium salt brine solution behind the purification by liquid extraction is put into reaction vessel, drip after 1: 5 hydrochloric acid regulates pH=2～3, magnesium ion is deviate from porphyrin ring, add ferrous ions soln, fully stir iron generation, the black precipitate of generation is iron pheophytin acid, and after-filtration, washing precipitation are clean;

C, salifying method:

The iron pheophytin acid that makes is dissolved to fully with concentrated base, adds the salify ion Zn ²⁺Postprecipitation separates, and drying can obtain cyan iron pheophytin zinc salt.