CN110467734A - A kind of method of the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel - Google Patents
A kind of method of the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel Download PDFInfo
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- CN110467734A CN110467734A CN201910810657.7A CN201910810657A CN110467734A CN 110467734 A CN110467734 A CN 110467734A CN 201910810657 A CN201910810657 A CN 201910810657A CN 110467734 A CN110467734 A CN 110467734A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The invention discloses a kind of methods of the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel.Carry out in the steps below: extraction solid residue is hydrolyzed to plant tissue using Eucommia seed peel as raw material, with biological enzyme in a., obtains the thick glue of Cortex Eucommiae；B. depth, fine degradation are carried out to the thick glue of Cortex Eucommiae using biological enzyme, to remove remaining cell wall on the thick glue of Cortex Eucommiae；C. wettability surfactant is added after cell wall removal；D. ultrasound is carried out after wettability surfactant is added, remaining Cortex Eucommiae plant tissue fragment is removed from gutta-percha and falls off；E, the thick glue of Cortex Eucommiae after ultrasound, removing cell wall is heated and is stirred in 65~85 DEG C of water-bath, disperse gutta-percha loosely, with unfolding in aqueous solution, to release the remaining Cortex Eucommiae plant tissue fragment for sweeping along in micelle, removing to fall off.Eucommia ulmoides refined glue produced by the present invention is cotton-shaped in natural loose silk, any organic solvent and chemicals is free of, using wide model without limitation.
Description
Technical field
The present invention relates to eucommia ulmoides refined glue preparation method, especially a kind of thick glue solution purifying preparation Cortex Eucommiae essence of Cortex Eucommiae seed peel
The method of glue.
Background technique
Shut out swollen glue, be called in the world gutta-percha (Gutta-Percha Chinese Gutta-Percha) or
Ba Lata (Balata) is the isomer of natural Hevea rubber, is trans-polyisoprene.Wherein in Eucommia ulmoides Oliv. leaves
Gutta-percha abundance be the 2 ~ 4% of dry weight, be 8 ~ 12% in mellow fruit, be 6 ~ 10% in stem skin, in root skin for 10 ~
12%, and up to 12 ~ 18% in seed peel, it is the most economical that gutta-percha is produced using seed peel as raw material.The preparation method of gutta-percha is main at present
Be by biological enzyme degrading plant tissue targeted specifically, it is remaining after dissolution wherein has high bioactivity drug natural products
Solid residue is rich in ecosystem natural gutta-percha silk.But the content only up to 80% or so of Folium glue wire that this method obtains, up to not
To the use purity of industrial glue, thus referred to as thick glue.The collodion silk wound in thick glue sweeps along the complete plant that is not degraded largely
Object clast has not only seriously affected the purity of gutta-percha, but also the stress of product stress is often formed in gutta percha product
Centrostigma, reduce the tear-proof of rubber, wear-resisting, shock resistance, puncture-resistant, it is resistance to bend around etc. key performance.In addition, current biological
The development period of zymotechnic is still not perfect, and the biological enzyme type found is limited, it has not been found that can be by the plant in residue
The degradable biological enzyme of object clast tissue, to limit biological enzymolysis technology depth degradation Cortex Eucommiae plant tissue, therefore
The degradation technique for only relying on biological enzyme can not obtain the ecosystem eucommia ulmoides refined glue that purity reaches 98% or more.
In order to meet industrial purity requirement, the purification process of the thick glue of Cortex Eucommiae is main molten using organic solvent at present
Solution is soluble in the characteristic of low polar organic solvent using organic matter gutta-percha, is dissolved in chloroform, toluene, industrial naptha, petroleum
It after ether, n-hexane, hexamethylene equal solvent, is separated with insoluble plant tissue, obtained high-purity gutta-percha.
But gutta-percha belongs to a kind of bio-rubber polymer, it is by monomer isoprene organic molecule in plant
Macromolecule polyalcohol made of aggregated enzymatic polymerization in tissue.Macroscopical gutta-percha polymer material is long by numerous single polymers
Chain is assembled naturally, is divided into tertiary structure: 1., polymer monomer constituent be primary structure, be also short-range structure, 2.,
The monomer on-link mode (OLM) of single macromolecular chain is secondary structure or long-range structure；3., numerous single high score polymer molecules concentrate
Structure together is tertiary structure or the high molecular aggregated structure of glue.
Organic solvent dissolution method is the process of organic solvent dissolution gutta-percha, is physical and chemical process, though Du will not be changed
The firsts and seconds structure of secondary glue, still, natural three-level aggregated structure but great variety and lose original physics and change
Feature is learned, in the block structure of combination wrapped around one another.Corresponding, natural gutta-percha macromolecule is that independence is single, divides each other
Scattered Filamentous loose structure, and gutta-percha is semi-hard rubber does not have viscosity, between collodion silk mutually independent characteristic and all by
The eucommia ulmoides refined glue that the method for the present invention obtains completely retains, and is more advantageous to the natural inherent characteristic and function using gutta-percha script
Energy.
The pure glue of Cortex Eucommiae made from organic solvent method has a drawback: its gutta-percha prepared is blocky (condensed state of reuniting
It is blocky), change the original pattern of gutta-percha.In addition, the gutta-percha of this method preparation may contain residual organic solvents, it can only
As the raw material of industry, so that the use scope of gutta-percha is very limited.
Summary of the invention
The object of the present invention is to provide a kind of methods of the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel.This
Loose cotton-shaped (see Fig. 5) that eucommia ulmoides refined glue obtained is in natural ecosystem is invented, any organic solvent and chemical substance is free of, makes
With wide model without limitation.
Technical solution of the present invention: a kind of method of the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel, by following
Step carries out:
A. using Eucommia seed peel as raw material, extraction Cortex Eucommiae natural medicinal ingredients is hydrolyzed to plant tissue with biological enzyme and are consolidated
The thick glue of body residue, as Cortex Eucommiae；
B. depth, fine degradation are carried out to the thick glue of Cortex Eucommiae using biological enzyme, to remove remaining cell wall on the thick glue of Cortex Eucommiae；
C. wettability surfactant is added after cell wall removal；
D. ultrasound is carried out after wettability surfactant is added, removes remaining Cortex Eucommiae plant tissue fragment from gutta-percha de-
It falls；
E, the thick glue of Cortex Eucommiae after ultrasound, removing cell wall is heated and is stirred in 65~85 DEG C of water-bath, make gutta-percha it is loose,
Disperse with unfolding in aqueous solution, sweeps along remaining Cortex Eucommiae plant tissue fragment in collodion silk group, removing falls off to release.
In step a described in the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel above-mentioned, the water
Xie Weiquan enzymatic hydrolysis, specifically: raw material is sent into enzyme digestion reaction tank, cutinase, lipase, protease, half fiber are successively used
Plain enzyme, cellulase, pectase, dextranase, zytase is tieed up raw material is hydrolyzed.
In the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel above-mentioned, when full enzymatic hydrolysis, by upper one
Secondary enzymatic hydrolysis --- the canebreak and thick gutta-percha mixture that reaction pot bottom is deposited to after eluriating continue enzyme next time
Solution --- it eluriates, successively repeatedly replaces enzyme, the different tissues ingredient for each repetitive structure of raw material of repeatedly degrading collects solid
Residue obtains the thick glue of the Cortex Eucommiae containing plant tissue clast.
In step b described in the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel above-mentioned, the thick glue of Cortex Eucommiae
Degradation removal cell wall carries out in small-sized enzyme digestion reaction tank.
In step b described in the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel above-mentioned, described makes
Depth, fine degradation are carried out to the thick glue of Cortex Eucommiae with biological enzyme, are specially directed to using the plain enzyme of dimension, hemicellulase and pectase
Property, depth, precisely successively carry out cell wall enzymatic hydrolysis in turn, temperature is 45 DEG C~55 DEG C when enzymatic hydrolysis.
In step c described in the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel above-mentioned, described is wet
Lubricant nature surfactant is that molecule has amphiphilic surfactant.
In step c described in the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel above-mentioned, described is wet
Lubricant nature surfactant is nonionic polyoxyethylene fatty alcohol ether wetting agent or 12 alkylsurfuric acid sodium water solutions.
In step d described in the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel above-mentioned, ultrasonic treatment
Time is 14h ~ 22h, ultrasonic frequency >=50KHz used.
In step d described in the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel above-mentioned, ultrasonic treatment
Time is 15 ~ 20h, and ultrasonic frequency used is 59kHz.
In step e described in the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel above-mentioned, heating water bath
Temperature be 80 DEG C.
Technical solution of the present invention in order to obtain, inventor have carried out following several research:
1. digesting the thick glue of Cortex Eucommiae
After the Eucommia kernel-taking of collection, remaining samara skin is also seed peel, is hydrolyzed with holoenzyme method, and raw material is sent into enzyme
It solves in reactor, the rotating machinery that enzymolysis reactor is made of inner barrel and outer barrel；It is eluriated repeatedly with clear water, it is broken to remove plant
Bits；At the same time, cutinase, lipase, protease, hemicellulase, cellulase, pectase, dextranase, wood are successively used
Plant tissue is hydrolyzed in dextranase；Digested in first time --- after elutriation, be deposited to the canebreak of solution bottom with it is residual
The solid matter stayed in inner cylinder is separated, and the solid matter in inner cylinder is to contain more undegraded Cortex Eucommiae plant tissue slightly to shut out
Secondary glue continues second of enzymatic hydrolysis for the plant residue for continuing to remain in product gutta-percha --- it eluriates, repeatedly more
The enzyme of different function is changed, the different tissues ingredient for each repetitive structure of repeatedly degrading destroys the plant tissue of every aspect, then
It is secondary to eluriate, separate residue, the thick glue of Cortex Eucommiae seed peel (i.e. the thick glue of Cortex Eucommiae) that gel content is 80% or so is obtained, it is spare, see Fig. 2.
2. ultrasonic cleaning is analyzed
Can not achieve based on biological enzyme technology level " the full bio-enzyme degradation of Cortex Eucommiae plant thoroughly removes Cortex Eucommiae plant tissue, with
The status of the Folium glue wire of free high-purity out ", inventor are considered as either physically or chemically being aided with preparation high-purity Cortex Eucommiae
Glue.And in contrast, physical method is with more the advantage for keeping the original natural Wuli-Shili-Renli system approach of gutta-percha.
For these reasons, the present invention is final to determine to use ultrasonic cleaning side after carrying out a variety of physical method tests
Method.Ultrasonic wave is a kind of physical method, and characteristic is can be absorbed and decay, and is decayed related with the property of propagation medium.In
It is absorbed less when can largely be absorbed in air, and propagated in a liquid.Based on this, present invention ultrasound purifying gutta-percha exists
It is carried out in batches in aqueous solution.
The purifying of gutta-percha is the process for the plant tissue fragment that gutta-percha surface was removed, cleaned to ultrasonic wave, is based on super
The cavitation of sound wave in aqueous solution.Ultrasonic wave tearing water clusters form a large amount of vacuum cavity microbubbles, when hydrone
When tearing ultrasonic cavitation generation in the gap aqueous layer between gutta-percha and plant tissue fragment, shape in the water layer of gap
At a large amount of cavity microbubbles (see Fig. 1).The microbubble of high-frequency vibration drives gutta-percha and phytoclasts to be forced to high-frequency vibration, and shuts out
Secondary glue and plant tissue fragment have different eigentones because of base substance difference itself, cause difference frequency vibration each other
Removing.Meanwhile vacuum cavity microvesicle is penetrated because the tearing and huge interior extruding force that expand and be closed implosion generation form the micro- of high speed
The shock wave that stream, bubble closure moment generate, makes to generate 10 around bubble12~1013The pressure of pa and localized hyperthermia destroy and plant
Object fragment of tissue removes plant tissue fragment from Folium glue wire, purifies collodion silk surface.It is huge caused by ultrasonic cavitation
Pressure and vibration cause the vibrating fatigue of clast, destroy insoluble plant clast, so that them is ruptured differentiation in aqueous solution, weaken
Adhesive force of the canebreak to gutta-percha surface, thus refuted from, fall off.In addition, the vibration of gas type bubbles is also to Cortex Eucommiae
Scrub clean is done in collodion silk surface.Ultrasonic frequency is lower, and tearing hydrone ability is stronger, generates cavitation in a liquid and more holds
Easily, it measures more.But low-frequency ultrasonic waves can not only have destruction to canebreak, can also Folium glue wire be caused to be corroded and be broken.And
Ultra-high frequency ultrasonic wave then high directivity, bubble is tiny, and cavitation ability is weak, is suitable for fine, soft gutta-percha cleaning.With super
The raising of acoustic frequency, bubble is tiny, quantity increases, and is conducive to the gap penetrated between collodion silk and clast, and blasting impact power weakens,
Protect Folium glue wire not broken.Accordingly, it is considered to which the removing using high-frequency ultrasonic as remaining fine particle fragment is cleaned.
To sum up, preferably even up to a hundred with 50kHz or more since the gap between Folium glue wire and plant tissue fragment is smaller
KHz high-frequency ultrasonic is cleaned, and can be substantially reduced erosion and destruction of the ultrasonic wave to Folium glue wire in this way, is allowed to intact
The natural gutta-percha silk pattern of ground holding ecosystem.Therefore, final choice of the present invention: >=50kHz (optimal is 59kHz) is as super
The working frequency of sound wave.Meanwhile cleaning temperature, when being maintained at 50 DEG C~85 DEG C (optimal is 80 DEG C), cleaning effect is best.
Hydrone be concentrated mainly on by the cavitation of sound wave pull region of stress concentration and supersonic boundary surface reflection it is close
Collect region, and the region appears precisely at the contact interface layer that gutta-percha, plant tissue fragment are formed with hydrone respectively, especially
It is between gutta-percha and plant tissue fragment in the water molecule layer in gap, referring to Fig. 1.
3. gap between Folium glue wire and phytoclasts
Once having the gap water layer between gutta-percha and plant tissue fragment, ultrasonic wave will be between gutta-percha and plant tissue clast
Hydrone is torn between gap in water body and forms a large amount of vacuum microbubbles, the vibration of bubble expands, causes fragment removing, falls off.By
This as it can be seen that between Folium glue wire and plant tissue fragment gap presence, be to improve one of gutta-percha efficiency pass of ultrasound purifying
Key factor.
Gap between Folium glue wire and plant tissue fragment in order to obtain, inventor are broken with plant tissue to Folium glue wire
Structure between piece has made intensive studies, and research is found: no matter how complicated plant tissue is, and how close package gutta-percha is, is shutting out
There is one layer of Gutta_containing cell walls always between secondary glue and plant tissue.If removing cell wall, just naturally in gutta-percha and
Gap is reserved between plant tissue fragment.
Cell wall is made of intercellular layer, primary wall and secondary wall three parts, dominant chemical constituent be cellulose,
Hemicellulose and pectin polysaccharide quasi polymer, relationship is successively each other present in tissue physiology's structure:
Gutta-percha ┃ Gutta_containing cell wall ┃ plant tissue
By gutta-percha in the arrangement order of the physiological structure in plant tissue it can be found that being contained between gutta-percha and plant tissue
Cellula adhesiae wall separates, and wall thickness is up to 12~15 μm.Cellulose accounts for 40~50% in cell wall composition, and there are also 10~30% hemicelluloses
With 20~30% lignin, if with cellulase and hemicellulase and pectase targetedly degrade precisely remove cellulose
Cell wall, the disappearance of cell wall just leave at least 12 μm of seam of the hydrone that can be penetrated between gutta-percha and plant tissue
Gap thickness also just tears hydrone generation vacuum microbubble for ultrasonic wave and provides gap water molecule layer, is conducive to ultrasonic cavitation
The effect removing plant tissue fragment of effect purifies gutta-percha.
4, the depth of gutta-percha cellulose cell wall, precisely enzymatic hydrolysis
Plant cell wall main component is cellulose and pectin.Cell wall is made of intercellular layer, primary wall and secondary wall three parts:
(1) intercellular layer also known as mesoglea.For one layer of pectin plasma membrane common to two flanking cells, pectin is by flanking cell adhesion
Together.
(2) primary wall is present in after cell division and is located on the inside of intercellular layer, be initially secreted by protoplast formed it is thin
Cell wall.Its main constituents is cellulose, hemicellulose, and in structure and there are structural proteins.
(3) secondary wall, be continue on the inside of primary wall after plant cell stops growing accumulation be located at plasma membrane and primary wall it
Between cell wall layer.Its main component is also cellulose, and often with the presence of a certain amount of lignin.
Nascent 1~3 μm of wall thickness, 5~10 μm of secondary wall thickness, then cell wall thickness is up to 13 microns.It is raw with pectin is mixed with
The cellulose bio-enzyme degradation cell wall of object enzyme, it is soluble in water and disappear that cell wall is hydrolyzed into oligosaccharide even monosaccharide, vacates 6
~13 μm of gaps, the layer slot for filling water are the water layer with condition of equivalent thickness for a large amount of micro- gas of ultrasonic cavitation effect generation
Bubble.
Cellulase hydrolysis reaction and general enzyme degradation reaction are different, and it is more that most important difference, which is cellulase not,
The multi-enzyme system of combined enzyme agent but multienzyme composition, and the structure of substrate is also extremely complex.
The biological enzyme of multicomponent enzyme metabolic response is polymerized together together, forms the combination of quaternary structure, this combination
Referred to as multienzyme complex.If multienzyme complex disintegrates, the catalytic activity of each enzyme disappears.First enzymatic in the complex
The product of reaction is the substrate of second enzyme, is so carried out continuously, until final product generates.And multi-enzyme system, then because rising
There is complicated multipath metabolism in the metabolism of beginning substrate, each approach has respective metabolic enzyme, by these enzymes it is common participate according to
The secondary metabolic response for completing respective approach.The metabolism of a variety of enzyme systems is different from multienzyme complex, they are in structure without each other
Association but and not formed complex, therefore referred to as multi-enzyme system.The metabolic degradation of cellulase is exactly that multiple enzymes participate in the more of completion
Enzyme system is mainly made of circumscribed 1,4 beta-glucanase, Endo-β-glucanase and beta-glucosidase etc., and there are also very high vigor
Zytase participates in.They are separated from each other the generation that will not influence mutual activity and final product.
The mechanism of degradation of enzyme:
Cellulase can make cellulose generate D-Glucose, cellobiose and oligosaccharides.Three steps of the degradation of enzyme point are completed:
1., approach effect and directionality effect
The enzyme digestion reaction first step, enzyme must and Binding Capacity in itself activated centre.Degradation of substrates speed and it is combined substrate
Quantity it is directly proportional.So enzyme approaches substrate first and is combined with substrate orientation.
2., tension force effect
The zygotic induction macromolecular enzyme of substrate three, quaternary structure conformation change, to substrate generate tension force effect, make substrate
Distortion, the key that binding site is applied occur fracture and are degraded.
3., acid-base catalysis effect
The activated centre of enzyme has the R(functional group of certain amino acid residues), these groups are often good proton donor
Or receptor, the acidic-group of these broad sense or the basic group of broad sense are that the strength that many chemical reactions occur is urged in aqueous solution
Agent.
It can be seen that approaching effect in enzymatic reaction step and consequential orientation effect being the starting first of enzymatic hydrolysis
Step.However, gutta-percha Gutta_containing cell is by other plant tissues due to the complexity of plant tissue and the compactness of institutional framework
It is tightly wrapped, has blocked approach of the enzyme to substrate, though aqueous solution has apparent infiltration expansion to plant tissue, but
Molecular weight also cannot be approached and be located on cellulose cell wall in the huge cellulase of 5000~400000 dalton.
So the bio-enzyme degradation of the accurately cell wall of depth, it can only be to be obtained by enzyme degrading plant tissue twice
The thick glue of Cortex Eucommiae seed peel be object, degrade, the cell wall that eliminates on the thick glue of Cortex Eucommiae of most of organization structure of the plant it is directly sudden and violent
Dew in aqueous solution, cellulase, hemicellulase can directly approach by medium aqueous solution be exposed to outside cellulose it is thin
Cell wall reaches accurate degradation.
Another major reason digested to cell wall is that cell wall and gutta-percha surface binding force are strong, is difficult clear
Washout is gone, and referring to Fig. 3, the brown spot in Fig. 3 on white gutta-percha is Gutta_containing cell fragment.From figure 3, it can be seen that without
The thick glue of the Cortex Eucommiae that cellulase depth finely digests is separated even across ultrasound with wetting surfactant, still visible a small amount of
Remaining chloasma fragment on gutta-percha, this isabelline fragment is exactly cellulose cell wall.
5, the hydrophilic of gutta-percha discongests dispersion purifying
After cell wall is digested, about 12 μm of gap is vacated between gutta-percha and plant tissue clast, gap space is molten immediately
Liquid is full to form water layer.Wetting surfactant is added before ultrasound, improves gutta-percha wettability of the surface, more conducively water
Molecule infiltration is removed into above-mentioned gap, is cleaned.
Phytoclasts be it is hydrophilic, can disperse in aqueous solution, and the Folium glue wire of alkane chain is hydrophobic organic point
Subchain, with very strong hydrophobicity and hampering be entangled with pockets of gutta-percha it is loose, unlock, can not release in micelle and sweep along
Clast and fragment.Therefore, the state that winding is entangled in conglomeration only is opened when the hydrophilic dispersion in aqueous solution of gutta-percha long filament,
Unfold and freely scatter, the clast fragment being stripped can just escape Folium glue wire tangle and fetter freely be dispersed in it is water-soluble
In liquid.
Gutta-percha by ultrasonic cleaning cannot be come spread apart in aqueous solution due to the effect of surface tension, removing,
The phytoclasts to fall off cannot still escape into aqueous solution.And wettability surfactant is added, nonionic is specifically added
Type polyoxyethylene aliphatic alcohol ether wetting agent or 12 alkylsurfuric acid sodium water solutions, so that the decline of both glue and water interfacial surface tension,
The two kinds of substances to repel each other become affine each other because of contact interface；Especially there is adding for the surfactant of strong wetting action
Enter, the affine of Folium glue wire and hydrone can be effectively improved, reduce gutta-percha disperse in aqueous solution can, enhance gutta-percha
Free dispersity in aqueous solution.Surfactant molecule has unique amphipathic: one end is hydrophilic polar group,
Such as-OH ,-COOH ,-SO3H ,-NH2, has hydrophily；The other end be oleophylic non-polar group, such as R-(alkyl), Ar-(virtue
Base), the above hydrocarbon chain of general 8 carbon atoms of nonpolar hydrocarbon chain shows the higher compatibility to organic chain, have it is lipophilic and
Hydrophobicity.
The interface for eliminating two-phase, just reduces surface tension and surface free energy.Active agent molecule be arranged in two-phase it
Between, it is transferred to the surface of two-phase inside ontology phase molecule.The disappearance at interface causes two alternate surface free energies to be remarkably decreased,
Cortex Eucommiae xanthan molecule can freely stretch under the conditions of constant temperature and pressure, and it is right that the per surface area that Folium glue wire is contacted with water increases institute
The function-that aqueous solution ontology is done -- surface free energy is degraded significantly, so that the Folium glue wire of curling winding can freely exist
It is extended in aqueous solution, substantially effectively unfolds dispersion in aqueous solution, to release to being stripped plant tissue fragment
Constraint.
Fig. 4 is that the thick glue of Cortex Eucommiae seed peel without ultrasound removing directly uses wettable surfaces' activity isolating plant tissues clast,
The gutta-percha of purifying.Gutta-percha in photo is still the laminated structure of seed peel, and it is broken not release the plant tissue being wherein mingled with
Piece, so purity is less than 95%.
Wetting surfactant be promote gutta-percha dissolve, disperse in aqueous solution, collodion silk chain is unfolded open most has
Effect and most direct auxiliary agent.Nonionic polyoxyethylene fatty alcohol ether wetting agent or 12 sodium alkyl sulfates, are with highly hydrophilic
Polar group alcoholic extract hydroxyl group, ether oxygen base, sodium sulphate be water-wet side, and with long-chain low polar hydrophobic hydrophobic end and gutta-percha
Alkane chain is mutually affine.
Gutta-percha due to transconfiguration and there are a large amount of crystal region on strand, advise by the molecules align of crystal region
It is whole, it piles up closely, intermolecular interaction is stronger, and surfactant wetting agents molecule is difficult to penetrate into crystal phase.Therefore crystalline state polymerization
The dissolution of object is than amorphous polymer difficulty, and the combination dissolution of surfactant need to first pass through the melting of crystal phase and become non-
Crystalline state, surfactant wetting agents are easy to disperse in aqueous solution in conjunction with amorphous state gutta-percha.It follows that being higher than gutta-percha
Under conditions of melting temperature, i.e., temperature be 65~85 DEG C, it is optimal be 80 DEG C under the conditions of, it is molten that gutta-percha is capable of forming dispersion agent posture
Solution is in aqueous solution, and gutta-percha is just at this time and removing plant tissue fragment disperses to be separated from each other in aqueous solution together, loose
Folium glue wire dispersion opens the constraint of the plant tissue fragment to fall off to removing in aqueous solution, and broken with removing plant tissue
Piece disperses to be separated from each other in aqueous solution together, and on eucommia ulmoides refined glue having a specific gravity smaller than that of water is bubbled through the water column, and specific gravity is greater than the profit of water
The plant tissue fragment that rises then is sunken to the bottom, so that eucommia ulmoides refined glue be made.
The left side Fig. 5 is 400 magnification micrographs of amplification, and the right is naked eyes photo, and photo proves, after tangling conglomeration state opening
Folium glue wire surface high-cleanness and be in loose condition (of surface), the plant tissue clast and fragment being stripped can be freely from collodion silk nets
Middle escape is scattered in aqueous solution, and is separated from each other with gutta-percha and is sunken to solution bottom, and supernatant collodion silk is then Cortex Eucommiae essence
Glue is shown in the photo on the left side Fig. 5, shows as pure white gutta-percha.
Compared with prior art, inventor finally obtains Du of the invention on the basis of in summary studying and testing
The preparation method of secondary essence glue: Gutta_containing cell wall is precisely removed using the ultrasonic cavitation of ultrasonic wave, bio-enzyme degradation and increases Du
The secondary interfragmental gap of glue-plant tissue is to enhance ultrasonic cavitation, wettability surfactant enhancing gutta-percha water-soluble
The remaining plant tissue fragment for being attached to gutta-percha surface is thoroughly removed, and then is made by the principle of free dispersity in liquid
Eucommia ulmoides refined glue.This method is generally aqueous solvent method of purification, and not only process regulation is easy, and eucommia ulmoides refined glue obtained has not been changed
Original pattern of gutta-percha remains the original independence of natural gutta-percha is single, disperses each other the cotton-shaped loose structure of silk (see figure
5 naked eyes photos), mutually independent characteristic is all completely retained by smart glue between collodion silk, is more advantageous to and is utilized gutta-percha script
Natural inherent characteristic and function.Eucommia ulmoides refined glue product degree of polymerization height, tension, tear-proof made from this method, and molecular weight it is big,
Narrowly distributing is perfectly suitable for the processing of natural Cortex Eucommiae, and is free of any organic solvent and chemical substance, unlimited using wide model
System.
Detailed description of the invention
Fig. 1 is the interface dense layer cavitation schematic diagram that water molecule layer is formed in gutta-percha and plant tissue and gap；
Fig. 2 be acid protease, lipase, cellulase, dextranase, to the seed of bark of eucommia after Eucommia seed peel degradation
The thick glue of skin；
Fig. 3 is the Cortex Eucommiae that under the conditions of 80 DEG C prepared by surfactant without cellulase and the accurate degradation treatment of hemicellulose
Seed peel eucommia ulmoides refined glue；Yellowish-brown spot therein is cell wall residual fragment.
Fig. 4 is the not sonicated sheet seed of bark of eucommia hide glue of surfactant purifying；
Fig. 5 is loose, the cotton-shaped Cortex Eucommiae seed peel essence glue of ultrasound-surfactant purifying, and the left side is 400 magnification micrographs of amplification,
The right is naked eyes photo.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
A kind of method of the thick glue solution purifying preparation eucommia ulmoides refined glue of the Cortex Eucommiae seed peel of embodiment 1., carries out in the steps below:
A. using Eucommia seed peel as raw material, plant tissue is hydrolyzed with biological enzyme and extracts Cortex Eucommiae natural medicinal ingredients
The thick glue of solid residue, as Cortex Eucommiae；
B. depth, fine degradation are carried out to the thick glue of Cortex Eucommiae using biological enzyme, to remove remaining cell wall on the thick glue of Cortex Eucommiae；It is first
First, under the conditions of best pectin enzyme activition pH, 3% pectase is added under the conditions of 45 DEG C, stirring pectase biodegrade is remaining
Pectin is discongested also still by the Gutta_containing cell of pectin adhesion, and exposed cell wall is in aqueous solution；It is close using having with cellulase
The hemicellulose of pH zymologic property is activated simultaneously in identical pH citric acid-sodium citrate buffer with cellulase, is made into
Mixed enzymolysis liquid stirs enzymolysis 18h under the conditions of temperature 50 C, and point three sections of 3 × 6h are carried out, the intermediate static enzymatic hydrolysis of interval
Act on 3h.Cellulose is formed in the complicated cell wall of the common biological of cellulase and hemicellulase degradation, is fully being planted
The gap for ultrasonic cavitation is createed between object fragment of tissue and gutta-percha；By degradation constitute cell wall cellulose and
Hemicellulose can make the gap between gutta-percha and plant tissue increase 12~15 μm, tear hydrone for ultrasonic wave and generate
Microbubble provides more favorable condition, and then is more advantageous to ultrasonic cavitation removing plant tissue fragment, purifies gutta-percha；
C. wettability surfactant is added after cell wall removal, magnetic agitation is carried out after addition and is sufficiently mixed；Wettability is added
Gutta-percha wettability of the surface can be improved in surfactant, and hydrone of being more convenient for penetrates into gutta-percha tissue and neutralizes and plant group
Knit formation gap water layer among interfragmental gap；And can be improved the affine of Folium glue wire and hydrone, reduce gutta-percha
Dispersion energy in aqueous solution enhances gutta-percha free dispersity in aqueous solution；So that the Folium glue wire of curling winding
Can freely extend in aqueous solution, substantially effectively unfold dispersion in aqueous solution, thus release to be stripped plant
The constraint of object fragment of tissue；The gutta-percha density for unfolding dispersion is less than water, floats on aqueous solution surface, and moistens the plant tissue to rise
Fragment, clast sedimentation concentrate on bottom in aqueous solution, realize the purifies and separates of slagging-off, and obtain aqueous solution surface layer eucommia ulmoides refined glue.
D. ultrasound is carried out after wettability surfactant is added, removes remaining Cortex Eucommiae plant tissue fragment from gutta-percha
It falls off；The ultrasonic treatment, mainly make to pierce a large amount of micro-bubbles of water molecule layer between gutta-percha and plant tissue fragment into
Row ultrasonic cavitation, and then clean the vibration of microbubble to the repeated stock of Folium glue wire surface, and cause gutta-percha and plant
Being forced to difference frequency vibration and being stripped plant tissue fragment for object fragment of tissue, realizes the final cleaning and purifying of gutta-percha.Promote
Make the combination of gutta-percha and surfactant, dissolution and dispersion in aqueous solution, loosely, the gutta-percha unfolded, which releases, sweeps along
The plant tissue clast that removing in collodion silk group falls off.
E. the thick glue of Cortex Eucommiae after ultrasound, removing cell wall is heated simultaneously in 65~85 DEG C of (optimal is 80 DEG C) water-baths
Stirring, makes that gutta-percha is loose, disperses with unfolding in aqueous solution, and to release, to sweep along in collodion silk group, removing to fall off residual
Remaining Cortex Eucommiae plant tissue fragment.Due to the winding of filament gutta-percha, gutta-percha sweeps along the plant for being mingled with removing and the generation that falls off
Fragment of tissue, clast.Under condition of water bath heating, surfactant facilitates under Folium glue wire and hydrone interfacial surface tension
Drop, stirring promote the dissolution of gutta-percha, dispersion；Especially with the surfactant of strong wetting action, Du can be effectively improved
Affine, the enhancing gutta-percha free dispersity in aqueous solution of secondary collodion silk and hydrone.It heats in a water bath, magnetic agitation adds
The dissolution in aqueous solution of the thick glue of fast hardness Cortex Eucommiae disperses, unfolds.The gutta-percha loosely opened is swept along before releasing it to be mingled with
, through the canebreak that falls off of ultrasound removing；After release, the pure eucommia ulmoides refined glue specific gravity dispersed in aqueous solution is less than water,
Concentration floats on the surface, and impregnates plant tissue clast, debris sedimentation and the aqueous solution bottom of swelling, is separated from each other to obtain high-purity
Spend eucommia ulmoides refined glue.
In aforementioned step a, described is hydrolyzed to full enzymatic hydrolysis, specifically: raw material is sent into enzyme digestion reaction tank, according to
It is secondary with cutinase, lipase, protease, hemicellulase, cellulase, pectase, dextranase, zytase to raw material into
Row hydrolysis.
When full enzymatic hydrolysis, the last time is digested -- the canebreak for reacting pot bottom and thick Cortex Eucommiae are deposited to after eluriating
Glue mixture continues to digest next time -- and it eluriates, successively repeatedly replaces enzyme, each repetitive structure of raw material of repeatedly degrading
Different tissues ingredient, collect solid residue obtain the thick glue of the Cortex Eucommiae containing plant tissue clast.
In aforementioned step b, the thick glue degradation removal cell wall of Cortex Eucommiae carries out in small-sized enzyme digestion reaction tank.
In aforementioned step b, described carries out depth, fine degradation to the thick glue of Cortex Eucommiae using biological enzyme, specially uses
Tie up plain enzyme, hemicellulase and pectase targetedly, depth, precisely successively carry out cell wall enzymatic hydrolysis in turn, temperature when enzymatic hydrolysis
It is 45 DEG C~55 DEG C；Accurate degradation of the pectase to the thick glue of Cortex Eucommiae seed peel has dispersed the pencil being sticked together by pectin containing glue
Cell exposes the cell wall on Folium glue wire surface；Cellulase and hemicellulase synergistic effect carry out residual cells wall
Precisely, efficiently degradation removes cell wall, creates gap between plant tissue clast, fragment.
In aforementioned step c, the wettability surfactant is that molecule has unique amphiphilic surfactant；
Specifically, the wettability surfactant is nonionic polyoxyethylene fatty alcohol ether wetting agent or 12 sodium alkyl sulfate water
Solution；Gap is under the action of nonionic polyoxyethylene fatty alcohol ether wettability surfactant or 12 sodium alkyl sulfate, In
Water molecule layer is formed in gap.
In aforementioned step d, sonication treatment time is 14 ~ 22h, preferably 15 ~ 20h, and optimal is 16h, ultrasound used
Wave frequency rate >=50KHz, optimal is 59kHz.
Claims (10)
1. a kind of method of the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel, which is characterized in that carry out in the steps below:
A. using Eucommia seed peel as raw material, extraction Cortex Eucommiae natural medicinal ingredients is hydrolyzed to plant tissue with biological enzyme and are consolidated
The thick glue of body residue, as Cortex Eucommiae；
B. depth, fine degradation are carried out to the thick glue of Cortex Eucommiae using biological enzyme, to remove remaining cell wall on the thick glue of Cortex Eucommiae；
C. wettability surfactant is added after cell wall removal；
D. ultrasound is carried out after wettability surfactant is added, removes remaining Cortex Eucommiae plant tissue fragment from gutta-percha de-
It falls；
E, the thick glue of Cortex Eucommiae after ultrasound, removing cell wall is heated and is stirred in 65~85 DEG C of water-bath, make gutta-percha it is loose,
Disperse with unfolding in aqueous solution, sweeps along remaining Cortex Eucommiae plant tissue fragment in collodion silk group, removing falls off to release.
2. the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel according to claim 1, which is characterized in that
In step a, described is hydrolyzed to full enzymatic hydrolysis, specifically: raw material is sent into enzyme digestion reaction tank, cutinase, rouge are successively used
Raw material is hydrolyzed in fat enzyme, protease, hemicellulase, cellulase, pectase, dextranase, zytase.
3. the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel according to claim 2, which is characterized in that
When full enzymatic hydrolysis, the last time is digested --- the canebreak and thick gutta-percha that reaction pot bottom is deposited to after eluriating mix
Object continues to digest next time --- and it eluriates, successively repeatedly replaces enzyme, the difference for each repetitive structure of raw material of repeatedly degrading
Structural constituent collects solid residue and obtains the thick glue of the Cortex Eucommiae containing plant tissue clast.
4. the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel according to claim 1, which is characterized in that
In step b, the thick glue degradation removal cell wall of Cortex Eucommiae carries out in small-sized enzyme digestion reaction tank.
5. the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel according to claim 1, which is characterized in that
In step b, described carries out depth, fine degradation to the thick glue of Cortex Eucommiae using biological enzyme, specially uses and ties up plain enzyme, hemicellulose
Enzyme and pectase targetedly, depth, precisely successively carry out cell wall enzymatic hydrolysis in turn, temperature is 45 DEG C~55 DEG C when enzymatic hydrolysis.
6. the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel according to claim 1, which is characterized in that
In step c, the wettability surfactant is that molecule has amphiphilic surfactant.
7. the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel according to claim 6, which is characterized in that
In step c, the wettability surfactant is nonionic polyoxyethylene fatty alcohol ether wetting agent or 12 sodium alkyl sulfates
Aqueous solution.
8. the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel according to claim 1, which is characterized in that
In step d, sonication treatment time is 14h ~ 22h, ultrasonic frequency >=50KHz used.
9. the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel according to claim 8, which is characterized in that
In step d, sonication treatment time is 15 ~ 20h, and ultrasonic frequency used is 59kHz.
10. the method for the thick glue solution purifying preparation eucommia ulmoides refined glue of Cortex Eucommiae seed peel according to claim 1, feature exist
In in step e, the temperature of heating water bath is 80 DEG C.
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