CN110496110A - A kind of nano-cellulose-pectin micro-capsule and the preparation method and application thereof - Google Patents
A kind of nano-cellulose-pectin micro-capsule and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of nano-cellulose-pectin micro-capsules and the preparation method and application thereof.Preparation method of the invention includes the following steps: that citrus nano-cellulose and oxidant are carried out oxidation reaction by (1), then carries out cation modifying with modifying agent and reacts, obtains cation nanometer cellulose；(2) pectous dextran solution is configured, solution A is denoted as；And the polyglycol solution of cation nano-cellulose is configured, it is denoted as B solution；(3) following steps 1 are used) or 2) prepare to get nano-cellulose-pectin micro-capsule is arrived；1) grade micro-capsule is prepared using instillation: the drop of solution A being instilled into B solution, millimetre-sized nano-cellulose-pectin micro-capsule is obtained after reaction；2) instrument is granulated using microcapsules and prepares micron order micro-capsule: solution A drop is sprayed into B solution, then react in microcapsules granulation instrument to get micron-sized nano-cellulose-pectin micro-capsule is arrived.Bio-compatible of the present invention is good, biological safety is high.
Description
Technical field
The present invention relates to a kind of nano-cellulose-pectin micro-capsules and the preparation method and application thereof, belong to micro-capsule technology of preparing
Field.
Background technique
Micro-capsule is a kind of carrier material with core-shell structure, and encapsulated substance can be made to exempt to be protected from environmental, kept
Stablize, under proper condition, being encapsulated substance can release again, can achieve controlled-release effect, this technology can be used for protecting
Active material, fixed cell, immobilised enzymes and controlled release drug are protected, is had extensively in biology, medicine, agricultural etc. various aspects
Application prospect.Conventional wrapper technology such as lotion, solid microcapsules, organic reagent therein and is formed by heavy wall micro-capsule meeting
Making the final bioactivity of the materials such as cell, the enzyme of encapsulating reduces.
Aqueous two-phase system is that two kinds of incompatible polymers are constituted, when two kinds of polymer (such as PEG and Dex) is appropriate
Concentration or when being mixed together at a specific temperature will spontaneous split-phase, generate sharp interface and form aqueous two-phase system
System.In recent years it is suggested using the polyelectrolyte with opposite charges in aqueous two-phase Interface composites to prepare the technology of micro-capsule
(Compartments via Polyelectrolyte Complexation in an Aqueous Two Phase
System.ACS Applied Materials&Interfaces,8(38),25603-25611.)(Zhang,L.,Cai,L.,
Lienemann,P.S.,Rossow,T.,Polenz,I.,Vallmajo-Martin,Q.,Ehrbar,M.,Na,H.,Mooney,
D.J.,&Weitz,D.A.(2016).One-Step Microfluidic Fabrication of Polyelectrolyte
Microcapsules in Aqueous Conditions for Protein Release.Angewandte Chemie
International Edition, 55 (43), 13470-13474.), this technology is entirely water during preparing micro-capsule
Phase can avoid organic reagent and damage to bioactive substances such as cell, enzymes.But the micro-capsule shell that two kinds of polyelectrolyte are formed
The disadvantages of there are bad mechanical strength, apertures greatly, easy swelling, causes it to contain object easy to leak when being used as pharmaceutical carrier.It grinds the country
The person of studying carefully is based on PEG/Dex aqueous two-phase, with CaCl2, sodium alginate, urea, urease be raw material prepare with calcium carbonate/seaweed
The micro-capsule of sour calcium double-layer structure, solid calcium carbonate layer assign the higher mechanical strength of micro-capsule (CN109701461A).But it is this
Method must use urease, and aqueous two-phase used takes a long time to wait aqueous two-phase split-phase, either operating condition,
Production cost or production time are all unfavorable for expanded production.In addition to this, in view of the bright prospects of this technology, it is necessary to
Cheap micro-capsule raw material are developed, to meet industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of nano-cellulose-pectin micro-capsule and the preparation method and application thereof, the present invention with
Discarded orange peel is the nano-cellulose and pectin of initial micro-capsule, and based on polyethylene glycol/glucan aqueous two-phase bio-compatible
Prepare micro-capsule in interface；The present invention prepares form size using the raw material (nano-cellulose, pectin) of natural botanical source can
The micro-capsule of regulation, product has higher biological safety, while also providing newly for the development and utilization of vegetalitas agricultural byproduct
Approach；Micro-capsule prepared by the present invention have stability it is high, it is non-breakable, be not easy to be swollen, the characteristic of not easy to leak, Neng Gouwei
The particle that hypotonic leakage is constructed in biological medicine, food service industry, cosmetic industry and enzyme engineering field contains object or drug particles
Transport system.
A kind of extracting method of citrus nano-cellulose provided by the invention, include the following steps: 1) by citrus peel meal with
Aqueous slkali hybrid reaction takes residue after filtering；
2) following processing at least once is carried out: by the residue and NaClO obtained in step 1)2Acetate buffer solution add
Heat treatment, takes filter residue after filtering, and obtaining filter residue is citrus fruit fibres element；
3) citrus fruit fibres element obtained in step 2) is hydrolyzed, water centrifuging and taking suspension is added, the suspension exists
Dialysis obtains the suspension of citrus nano-cellulose in water, removes water and obtains citrus nano-cellulose.
In above-mentioned extracting method, the aqueous slkali is NaOH solution；The concentration of the aqueous slkali can be 10~100g/L,
Concretely 20g/L；
The quality of the citrus peel meal and the volume ratio of the aqueous slkali can be 100g:0.5~5L, concretely 100g:
1L；
The temperature of reaction described in step 1) can be 70~100 DEG C, and the time can be 1~5h, concretely 100 DEG C of heating
2h；
Number of processing is 1~4 time in step 2)；
The residue and the NaClO2Acetate buffer solution in NaClO2Mass ratio can be 20~1:1；
The temperature that reaction is heated described in step 2) is 50~100 DEG C, and the time is 1~10h, concretely 80 DEG C of heating
2h。
Further include the steps that drying at 30~80 DEG C by the filter residue in above-mentioned extracting method, in step 2), specifically
It can be 50 DEG C；
H is used in step 3)2SO4Solution carries out the hydrolysis；The citrus fruit fibres element hydrolysis and the H2SO4Solution
Mass ratio can be 1:20~50；
The temperature of hydrolysis described in step 3) can be 30~60 DEG C, and the time can be 0.1~5h, concretely 50 DEG C of hydrolysis
1h；The revolving speed of the centrifugation can be 5000~15000rpm, concretely 10000rpm；It is described to dialyse to neutrality.
The above-mentioned extracting method of the present invention, specifically comprises the following steps:
It weighs 100g citrus peel meal and 1L 20g/L NaOH solution and 100 DEG C of heating 2h removing soluble fibres therein is added
And hemicellulose, and residue filter is retained；1L NaClO is added in filter residue2Acetate buffer solution, in 80 DEG C of heat treatment 2h,
It is repeated twice this process, to obtain citrus fruit fibres element except delignification, finally residue filter is gone out and is retained in 50 DEG C of drying standby
With；The citrus fruit fibres element for weighing 10g drying is added to 300g 60% (w/w) H2SO4In, 1h is hydrolyzed in 50 DEG C of stirrings, has been hydrolyzed
10 times of termination hydrolysis are diluted at rear addition deionized water, the repeated centrifugation at 10000rpm is until can not be centrifuged to form suspension
Liquid retains suspension and dialyses in deionized water to neutrality, is denoted as citrus nano-cellulose.
The present invention also provides the citrus nano-celluloses that above-mentioned method is prepared.
The nano-cellulose based on aqueous two-phase-pectin micro-capsule preparation method that the present invention also provides a kind of, including it is as follows
Step: (1) carrying out oxidation reaction for above-mentioned citrus nano-cellulose and oxidant, and cationization is then carried out with modifying agent and is changed
Property reaction, obtain cation nanometer cellulose；
(2) pectous dextran solution is configured, solution A is denoted as；And it configures poly- containing the cation nanometer cellulose
Ethylene glycol solution is denoted as B solution；
(3) following steps 1 are used) or 2) prepare to get nano-cellulose-pectin micro-capsule is arrived；
1) it prepares grade micro-capsule using instillation: the drop of the solution A being instilled into the B solution, after reaction to obtain the final product
To millimetre-sized nano-cellulose-pectin micro-capsule；
2) instrument is granulated using microcapsules and prepares micron order micro-capsule: the solution A drop being sprayed into the B solution, then
It is reacted in microcapsules granulation instrument to get micron-sized nano-cellulose-pectin micro-capsule is arrived.
In above-mentioned method, the condition of oxidation reaction described in step (1) is as follows: the oxidant is NaIO4Solution is dense
Degree can be 0.01~1M；Temperature can be 20~80 DEG C, be protected from light 1-3h；
The condition of the cation modifying reaction is as follows: the modifying agent is that gill draws special reagent, and concentration can be 0.01
~1M；PH value can be 4~5, and temperature can be 20~80 DEG C, and the time can be 1~3h；
It further include and removing solvent for reaction system deionized water dialysis 3~7 days after cation modifying reaction
Be concentrated be settled to mass percentage concentration can for 0.5~2%, concretely 1%.
In above-mentioned method, the concentration expressed in percentage by weight of pectin is 0.1~2% in the solution A, the weight percent of glucan
Concentration is 10~25%, and the average molecular mass of the glucan is 10~100kDa, concretely 70kDa；
The concentration expressed in percentage by weight of cationic nano-cellulose is 0.05~5% in the B solution, the weight hundred of polyethylene glycol
Dividing concentration can be 8~20%, and 0.5~10kDa of molecular weight, the pH value of the B solution is 2~7.
It further include carrying out the pectin to take off the ester modified step for obtaining degreasing pectin before step (2) in above-mentioned method
Suddenly.
In above-mentioned method, the pectin extracts to obtain using orange peel, is denoted as citrus pectin, and citrus can be made full use of useless
Gurry；
The pectin carries out taking off ester modified processing as follows: by pectin dissolution soluble in water, pH value is adjusted to 8~
11,1~25min of de-ester reaction is carried out to get degreasing modification pectin is arrived.
In the present invention, the pectin extracts in accordance with the following steps: orange peel is dried in an oven, beats powder with pulverizer,
It sieves with 100 mesh sieve, obtains citrus peel meal；Citrus peel meal is added in the hydrochloric acid solution of pH=2, is heated to 95 DEG C, is extracted, is extracted
After the completion with four layers of filtered through gauze, filtrate is centrifuged, collects supernatant, equivalent dehydrated alcohol is added with precipitated pectin, through overnight
After precipitating, pectin precipitating is filtered out with four layers of gauze, and done the best with hand and squeeze out the solvent in precipitating, finally dried, with crushing
Machine beats powder, obtains citrus pectin.
In the present invention, the pectin carries out taking off ester modified step specific as follows: weighing 10g citrus pectin, 700mL is added
Deionization is water-soluble, is stirred overnight dissolution, and citrus pectin solution ph is adjusted to 8~11 with 0.1M NaOH, and de-ester reaction 1~
25min；It post-processes as follows: being adjusted to neutrality with 0.1M HCl, equivalent dehydrated alcohol is added and is settled out the citrus pectin of de- ester, passes through
After overnight precipitation, pectin precipitating is filtered out with four layers of gauze, and done the best with hand and squeeze out the solvent in precipitating, finally at 50 DEG C
It is dried in baking oven, beats powder with pulverizer, obtain described taking off ester modified pectin.
In above-mentioned method, step (3) -1) in, the volume ratio of the solution A and the B solution is 1:10~100, institute
The time for stating reaction is 1~60min；
Step (3) -2) in, the volume ratio of the solution A and the B solution is 1:10~50, and the time of the reaction is 1
~20min；
The condition setting that the microcapsules are granulated instrument is as follows: solution A is added in syringe, and the syringe is fixed on described
Microcapsules are granulated on the syringe pump of instrument, and the injector head soft silicone tube is connected with the spray head that the microcapsules are granulated instrument,
The spray head aperture is 80~1000 μm, and the spray head is located on B solution liquid level at 5~100cm, and the liquid of the B solution is high
Degree can be 1~20cm, and vibration frequency can be 1200Hz, and voltage can be 1000V, adjust syringe pump parameter feed speed can for 1~
2.4mL/min。
In the present invention, it is specific as follows that (1) using instillation prepares grade micro-capsule step: being drawn with the liquid-transfering gun of 200 μ L
Drop close to B solution, is gently instilled B solution, after 5min by pushing liquid-transfering gun that solution A formed drop by 10 μ L solution As
Form grade nano-cellulose-pectin micro-capsule；
(2) instrument is granulated using microcapsules to prepare micron order micro-capsule step specific as follows: taking solution A that commercially available 50mL is added and inject
In device, syringe is fixed on syringe pump, and injector head soft silicone tube is connected with spray head, spray head pore size can for 80~
1000 μm, spray head is located on B solution liquid level at about 10cm, and the liquid height of B solution is about 3cm, and microcapsules are granulated instrument vibration frequency
Rate can be 1200Hz, and voltage can be 1000V, and adjusting syringe pump parameter feed speed is 1-2.4mL/min, make the solution A to be formed
Drop sprays into B solution, and micro-capsule is formed after 5min.
Invention further provides above-mentioned methods, and the nano-cellulose-pectin micro-capsule is prepared.
Nano-cellulose of the present invention-pectin micro-capsule is applied to biological medicine, food service industry, cosmetic industry or enzyme work
The particle that hypotonic leakage is constructed in journey field contains object or drug particles transport in system.
The invention has the following advantages that
The present invention is based on polyethylene glycol/glucan to discard the nano-cellulose and pectin that orange peel is initial micro-capsule
Prepare micro-capsule in the bio-compatible interface of aqueous two-phase；The present invention utilizes the raw material (nano-cellulose, pectin) of natural botanical source
Preparation, when pH value is acid, the microcapsule structure of formation is more uniform, and when especially pH is 3, the cyst wall of micro-capsule more thickeies, this
The mechanical strength that micro-capsule can be improved, is destroyed it not, improves the concentration of nano-cellulose in B solution, micro-capsule can be made to be formed
More thick and solid shell；When using ester modified pectin is taken off, the stabilization of cyst wall can be improvedProperty, it is ensured that the micro-capsule of high mechanical strength Cyst wall, to improve the stability of micro-capsule；The present invention is big by control dropIt is small, the micro- of the adjustable control of form can be prepared
Capsule can not only make millimetre-sized composite microcapsule, can also make micron-sized micro-capsule.Product of the present invention has higher life
Object safety, while also new approach is provided for the development and utilization of vegetalitas agricultural byproduct；The tool of micro-capsule prepared by the present invention
Have stability it is high, it is non-breakable, be not easy to be swollen, the characteristic of not easy to leak, can be biological medicine, food service industry, makeup conduct
The particle that hypotonic leakage is constructed in industry and enzyme engineering field contains object or drug particles transport system.
Detailed description of the invention
Fig. 1 is the micro-capsule microscope photo of 1-3 of embodiment of the present invention preparation.
Fig. 2 is micro-capsule microscope photo prepared by the embodiment of the present invention 4.
Fig. 3 is micro-capsule microscope photo prepared by the embodiment of the present invention 5.
Fig. 4 is the photo after micro-capsule prepared by the embodiment of the present invention 5 is soaked in deionized water for 24 hours.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1,
The extracting method of citrus nano-cellulose, specifically comprises the following steps:
It weighs 100g citrus peel meal and 1L 20g/L NaOH solution and 100 DEG C of heating 2h removing soluble fibres therein is added
And hemicellulose, and residue filter is retained；1L NaClO is added in filter residue2Acetate buffer solution, in 80 DEG C of heat treatment 2h,
It is repeated twice this process, to obtain citrus fruit fibres element except delignification, finally residue filter is gone out and is retained in 50 DEG C of drying standby
With；The citrus fruit fibres element for weighing 10g drying is added to 300g 60% (w/w) H2SO4In, 1h is hydrolyzed in 50 DEG C of stirrings, has been hydrolyzed
10 times of termination hydrolysis are diluted at rear addition deionized water, the repeated centrifugation at 10000rpm is until can not be centrifuged to form suspension
Liquid retains suspension and dialyses in deionized water to neutrality, is denoted as citrus nano-cellulose.
The extracting method of citrus pectin, includes the following steps:
Orange peel is dried in 50 DEG C of baking ovens, powder is beaten with pulverizer, sieves with 100 mesh sieve, obtain citrus peel meal.By 300g mandarin orange
Orange peel powder is added in the hydrochloric acid solution of the pH=2 of 4.5L, is heated to 95 DEG C, extracts 1h, with four layers of gauze mistake after the completion of extracting
Filtrate is centrifuged at 4000rpm 20min, collects supernatant by filter, and equivalent dehydrated alcohol is added with precipitated pectin, is sunk overnight
Behind shallow lake, pectin precipitating is filtered out with four layers of gauze, and done the best with hand and squeeze out the solvent in precipitating, finally in 50 DEG C of baking oven
Drying, beats powder with pulverizer, obtains citrus pectin.
Step 1: material modification
(1) citrus nano-cellulose cation modifying: measuring 100mL citrus nano-cellulose suspension, and NaIO is added4
Concentration is 0.1M, is protected from light 3h in 50 DEG C, and citrus nano-cellulose Surface Oxygen is dissolved dialdehyde base, is centrifuged after completion of the reaction
Retain precipitating.Precipitating is taken to be scattered in 100mL deionized water again, it is 0.2M that gill, which is added, and draws special reagent concentration, and adjustment pH is 4-
5, in 60 DEG C of reaction 3h, citrus nano-cellulose surface is made to form cation group, uses deionized water dialysis 4 after completion of the reaction
It, and be concentrated using rotary evaporation and to be settled to 1% (w/w) and be denoted as cation nanometer cellulose.
(2) micro-capsule is prepared with unmodified citrus pectin.
Step 2: polyethylene glycol/glucan aqueous two-phase of the configuration containing pectin, cation nanometer cellulose
(1) pectous dextran solution, concentration of pectin 1wt% are configured, glucan concentration is 20wt%, and molecular weight is
70kDa is denoted as solution A.
(2) polyglycol solution of cation nano-cellulose is configured, cation nanometer cellulose concentration is
0.25wt%, Polyethylene glycol 15wt%, molecular weight 6kDa, adjustment pH are 7, are denoted as B solution.
Step 3: preparing nano-cellulose-pectin micro-capsule
Grade micro-capsule is prepared using instillation.10 μ L solution As are drawn with the liquid-transfering gun of 200 μ L, by pushing liquid-transfering gun
Solution A is formed into drop, close to B solution, drop is gently instilled into B solution, forms grade nano-cellulose-pectin after 5min
Micro-capsule.
Table 1
| Nano-cellulose current potential (mV) | Nano-cellulose size (nm) | |
| Initially | -50±2 | 200-300 |
| Cation modifying | 48±3 | 200-300 |
It is observed using micro-capsule of the optical microscopy to formation, as a result as shown in Figure 1, micro-capsule being capable of shape with this condition
At, micro-capsule diameter about 1.5mm, the micro-capsule morphological inhomogeneity of formation.Illustrate cation nanometer cellulose and pectin in aqueous two-phase
Interface reacts, this is because nano-cellulose after cation modifying charge from -50 ± 2 become 48 ± 3 (tables
1), the positive charge rush on surface can be compound with the carboxyl on pectin surface, and coated hard shell is further formed on interface
Form micro-capsule.
Embodiment 2,
Micro-capsule is prepared according to the method for the embodiment of the present invention 1, difference is, configures the poly- second of cation nano-cellulose
Glycol solution pH value is adjusted to 5, obtains nano-cellulose-pectin micro-capsule.
Embodiment 3,
Micro-capsule is prepared according to the method for the embodiment of the present invention 1, difference is, configures the poly- second of cation nano-cellulose
Glycol solution pH value is adjusted to 3, obtains nano-cellulose-pectin micro-capsule.
It is observed using micro-capsule of the optical microscopy to formation, the result of the embodiment of the present invention 2 and 3 is as shown in Figure 1, work as
When pH value is acid, the microcapsule structure of formation is more uniform, and when especially pH is 3, the cyst wall of micro-capsule more thickeies, this can improve micro-
The mechanical strength of capsule, is destroyed it not.
Embodiment 4,
Step 1: material modification
(1) citrus nano-cellulose cation modifying.100mL citrus nano-cellulose suspension is measured, NaIO is added4
Concentration is 0.1M, is protected from light 3h in 50 DEG C, and citrus nano-cellulose Surface Oxygen is dissolved dialdehyde base, is centrifuged after completion of the reaction
Retain precipitating.Precipitating is taken to be scattered in 100mL deionized water again, it is 0.2M that gill, which is added, and draws special reagent concentration, and adjustment pH is 4-
5, in 60 DEG C of reaction 3h, citrus nano-cellulose surface is made to form cation group, uses deionized water dialysis 4 after completion of the reaction
It, and be concentrated using rotary evaporation and to be settled to 1% (w/w) and be denoted as cation nanometer cellulose.
(2) micro-capsule is prepared with unmodified citrus pectin.
Step 2: polyethylene glycol/glucan aqueous two-phase of the configuration containing pectin, cation nanometer cellulose
(1) pectous dextran solution, concentration of pectin 1wt% are configured, glucan concentration is 20wt%, and molecular weight is
70kDa is denoted as solution A.
(2) polyglycol solution of cation nano-cellulose is configured, cation nanometer cellulose concentration is
0.5wt%, Polyethylene glycol 15wt%, molecular weight 6kDa, adjustment pH are 3, are denoted as B solution.
Step 3: preparing nano-cellulose-pectin micro-capsule
Grade micro-capsule is prepared using instillation.10 μ L solution As are drawn with the liquid-transfering gun of 200 μ L, by pushing liquid-transfering gun
Solution A is formed into drop, close to B solution, drop is gently instilled into B solution, forms grade nano-cellulose-pectin after 5min
Micro-capsule.
It is observed using micro-capsule of the optical microscopy to formation, as a result as shown in Fig. 2, compared with the embodiment of the present invention 3,
The concentration for improving nano-cellulose in B solution can make micro-capsule form more thick and solid shell.
Embodiment 5,
Step 1: material modification
(1) citrus nano-cellulose cation modifying.100mL citrus nano-cellulose suspension is measured, NaIO is added4
Concentration is 0.1M, is protected from light 3h in 50 DEG C, and citrus nano-cellulose Surface Oxygen is dissolved dialdehyde base, is centrifuged after completion of the reaction
Retain precipitating.Precipitating is taken to be scattered in 100mL deionized water again, it is 0.2M that gill, which is added, and draws special reagent concentration, and adjustment pH is 4-
5, in 60 DEG C of reaction 3h, citrus nano-cellulose surface is made to form cation group, uses deionized water dialysis 4 after completion of the reaction
It, and be concentrated using rotary evaporation and to be settled to 1% (w/w) and be denoted as cation nanometer cellulose.
(2) citrus pectin takes off ester modified.10g citrus pectin is weighed, addition 700mL deionization is water-soluble, it is stirred overnight dissolution,
Citrus pectin solution ph is adjusted to 9 with 0.1M NaOH, after de-ester reaction 25min, neutrality is adjusted to 0.1M HCl, is added
The citrus pectin of de- ester is settled out by equivalent dehydrated alcohol, after overnight precipitation, is filtered out pectin precipitating with four layers of gauze, is used in combination
Hand, which is done the best, squeezes out the solvent in precipitating, finally dries in 50 DEG C of baking oven, beats powder with pulverizer, obtains taking off ester modified fruit
Glue.
Step 2: polyethylene glycol/glucan aqueous two-phase of the configuration containing pectin, cation nanometer cellulose
(1) pectous dextran solution, concentration of pectin 0.5wt% are configured, glucan concentration is 20wt%, molecular weight
For 70kDa, it is denoted as solution A.
(2) polyglycol solution of cation nano-cellulose is configured, cation nanometer cellulose concentration is 1wt%,
Polyethylene glycol is 15wt%, molecular weight 6kDa, and adjustment pH is 3, is denoted as B solution.
Step 3: preparing nano-cellulose-pectin micro-capsule
Instrument is granulated using microcapsules and prepares micron order micro-capsule, takes solution A to be added in commercially available 50mL syringe, syringe is fixed
In on syringe pump, injector head soft silicone tube is connected with spray head, and spray head pore size is 200 μm, and spray head is located at B solution liquid
On face at about 10cm, the liquid height of B solution is about 3cm, and it is 1200Hz, voltage 1000V that microcapsules, which are granulated instrument vibration frequency,
Adjusting syringe pump parameter feed speed is 1-2.4mL/min, sprays into the solution A drop to be formed in B solution, is formed after 5min micro-
Capsule.
Table 2
| Pectin current potential (mV) | |
| Initially | -28±1 |
| It takes off ester modified | -46±1 |
It is observed using micro-capsule of the optical microscopy to formation, as a result as shown in figure 3, being carried out when being granulated instrument with microcapsules
The nozzle of 200 μm of microcapsules selection be capable of forming when preparing micro-capsule about 500 μm of the uniform micro-capsule of size and form.And micro-capsule
There is no merging, illustrate that cyst wall at this time is enough that micro-capsule is made to keep stablizing.It is exhausted by the negative electrical charge for taking off ester effect raising pectin
, can be preferably compound with modified nanometer cellulose to (result such as table 2) after value, in addition continued growing in the present embodiment sun from
The concentration of the nano-cellulose of son is to 1%, which ensure that the microcapsule wall of high mechanical strength.In addition illustrate that this method passes through control
Droplet size can not only make millimetre-sized composite microcapsule, can also make micron-sized micro-capsule.
Micro-capsule is cleaned with deionized water, and is soaked in deionized water, micro- sem observation is carried out to it afterwards for 24 hours, is tied
Fruit illustrates under the action of osmotic pressure, water can enter inside micro-capsule, this property as shown in figure 4, the slightly increase of micro-capsule size
It is vital for verifying in encapsulating living cells.Although water enters inside micro-capsule, so that microcapsule structure becomes larger, micro-capsule is remained to
Good working condition is kept, encapsulated substance is can protect and does not reveal, encapsulated substance can be protected, can be applied to biological medicine, food
Conduct industry, cosmetic industry and enzyme engineering field (table 3).
Table 3
Embodiment 6,
Step 1: material modification
(1) citrus nano-cellulose cation modifying.100mL citrus nano-cellulose suspension is measured, NaIO is added4
Concentration is 0.1M, is protected from light 3h in 50 DEG C, and citrus nano-cellulose Surface Oxygen is dissolved dialdehyde base, is centrifuged after completion of the reaction
Retain precipitating.Precipitating is taken to be scattered in 100mL deionized water again, it is 0.2M that gill, which is added, and draws special reagent concentration, and adjustment pH is 4-
5, in 60 DEG C of reaction 3h, citrus nano-cellulose surface is made to form cation group, uses deionized water dialysis 4 after completion of the reaction
It, and be concentrated using rotary evaporation and to be settled to 1% (w/w) and be denoted as cation nanometer cellulose.
(2) citrus pectin takes off ester modified.10g citrus pectin is weighed, addition 700mL deionization is water-soluble, it is stirred overnight dissolution,
Citrus pectin solution ph is adjusted to 9 with 0.1M NaOH, after de-ester reaction 25min, neutrality is adjusted to 0.1M HCl, is added
The citrus pectin of de- ester is settled out by equivalent dehydrated alcohol, after overnight precipitation, is filtered out pectin precipitating with four layers of gauze, is used in combination
Hand, which is done the best, squeezes out the solvent in precipitating, finally dries in 50 DEG C of baking oven, beats powder with pulverizer, obtains taking off ester modified fruit
Glue.
Step 2: configuration is containing FITC-BSA (i.e. FITC mark bovine serum albumin(BSA)), pectin, cation nanometer cellulose
Polyethylene glycol/glucan aqueous two-phase
(1) dextran solution containing FITC-BSA, pectin, concentration of pectin 0.5wt% are configured, glucan concentration is
Then 20wt%, molecular weight 70kDa are added the FITC-BSA of 0.004g, are denoted as solution A.
(2) polyglycol solution of cation nano-cellulose is configured, cation nanometer cellulose concentration is 1wt%,
Polyethylene glycol is 15wt%, molecular weight 6kDa, and adjustment pH is 3, is denoted as B solution.
Step 3: preparing nano-cellulose-pectin micro-capsule
Instrument is granulated using microcapsules and prepares micron order micro-capsule, takes solution A to be added in commercially available 50mL syringe, syringe is fixed
In on syringe pump, injector head soft silicone tube is connected with spray head, and spray head pore size is 200 μm, and spray head is located at B solution liquid
On face at about 10cm, the liquid height of B solution is about 3cm, and it is 1200Hz, voltage 1000V that microcapsules, which are granulated instrument vibration frequency,
Adjusting syringe pump parameter feed speed is 1-2.4mL/min, sprays into the solution A drop to be formed in B solution, is formed after 5min micro-
Capsule.
The micro-capsule prepared is cleaned 3 times with deionized water, is soaked in deionized water, is surveyed in 48h to its fluorescence intensity
It is fixed, to determine whether FITC-BSA leaks.The result shows that FITC-BSA does not leak out micro-capsule on a large scale yet in 48h, pass through
The above results illustrate that nano-cellulose of the present invention-pectin micro-capsule micro-capsule is high, non-breakable with stability, are not easy to be swollen, be not easy
The characteristic of leakage.
The effect experiment of 4 micro-capsule of table embedding FITC-BSA
Claims (10)
1. a kind of extracting method of citrus nano-cellulose, include the following steps: citrus peel meal and aqueous slkali hybrid reaction 1),
Residue is taken after filtering；
2) following processing at least once is carried out: by the residue and NaClO obtained in step 1)2Acetate buffer solution heating at
Reason, takes filter residue after filtering, and obtaining filter residue is citrus fruit fibres element；
3) citrus fruit fibres element obtained in step 2) is hydrolyzed, water centrifuging and taking suspension is added, the suspension is in water
Dialysis obtains the suspension of citrus nano-cellulose, removes water and obtains citrus nano-cellulose.
2. according to the method described in claim 1, it is characterized by: the aqueous slkali is NaOH solution；The aqueous slkali it is dense
Degree is 10~100g/L；
The quality of the citrus peel meal and the volume ratio of the aqueous slkali are 100g:0.5~5L；
The temperature of reaction described in step 1) is 70~100 DEG C, and the time is 1~5h；
Number of processing is 1~4 time in step 2)；
The residue and the NaClO2Acetate buffer solution in NaClO2Mass ratio be 20~1:1；
The temperature that reaction is heated described in step 2) is 50~100 DEG C, and the time is 1~10h；
Further include the steps that drying at 30~80 DEG C by the filter residue in step 2)；
H is used in step 3)2SO4Solution carries out the hydrolysis；The citrus fruit fibres element hydrolysis and the H2SO4The mass ratio of solution
For 1:20~50；
The temperature of hydrolysis described in step 3) is 30~60 DEG C, and the time is 0.1~5h；The revolving speed of the centrifugation be 5000~
15000rpm；It is described to dialyse to neutrality.
3. the citrus nano-cellulose that method of any of claims 1 or 2 is prepared.
4. a kind of preparation method of the nano-cellulose based on aqueous two-phase-pectin micro-capsule, includes the following steps: that (1) wants right
Citrus nano-cellulose described in asking 3 and oxidant carry out oxidation reaction, then carry out cation modifying with modifying agent and react,
Obtain cation nanometer cellulose；
(2) pectous dextran solution is configured, solution A is denoted as；And configure the poly- second two containing the cation nanometer cellulose
Alcoholic solution is denoted as B solution；
(3) following steps 1 are used) or 2) prepare to get nano-cellulose-pectin micro-capsule is arrived；
1) grade micro-capsule is prepared using instillation: the drop of the solution A being instilled into the B solution, milli is obtained after reaction
The nano-cellulose of meter level-pectin micro-capsule；
2) instrument is granulated using microcapsules and prepares micron order micro-capsule: the solution A drop being sprayed into the B solution, then in institute
It states microcapsules and is granulated in instrument and react to get micron-sized nano-cellulose-pectin micro-capsule is arrived.
5. according to the method described in claim 4, it is characterized by: the condition of oxidation reaction described in step (1) is as follows: described
Oxidant is NaIO4Solution, concentration are 0.01~1M；Temperature is 20~80 DEG C, is protected from light 1-3h；
The condition of the cation modifying reaction is as follows: the modifying agent is that gill draws special reagent, and concentration is 0.01~1M；pH
Value is 4~5, and temperature is 20~80 DEG C, and the time is 1~3h；
Further include after cation modifying reaction by reaction system deionized water dialysis 3~7 days, and remove solvent by its
It is 0.5%~2% that concentration, which is settled to mass percentage concentration,.
6. method according to claim 4 or 5, it is characterised in that: the concentration expressed in percentage by weight of pectin is in the solution A
0.1~2%, the concentration expressed in percentage by weight of glucan is 10~25%, the average molecular mass of the glucan is 10~
100kDa；
The concentration expressed in percentage by weight of cationic nano-cellulose is 0.05~5% in the B solution, and the weight percent of polyethylene glycol is dense
Degree is 8~20%, 0.5~10kDa of molecular weight, and the pH value of the B solution is 2~7.
7. the method according to any one of claim 4-6, it is characterised in that: further include by the fruit before step (2)
Glue carries out taking off ester modified the step of obtaining degreasing modification pectin；
The pectin carries out taking off ester modified processing specific as follows: by pectin dissolution soluble in water, pH value is adjusted to 8~
11,1~25min of de-ester reaction is carried out to get degreasing modification pectin is arrived.
8. the method according to any one of claim 4-7, it is characterised in that: step (3) -1) in, the solution A and institute
The volume ratio for stating B solution is 1:10~100, and the time of the reaction is 1~60min；
Step (3) -2) in, the volume ratio of the solution A and the B solution is 1:10~50, the time of the reaction is 1~
20min；
The condition setting that the microcapsules are granulated instrument is as follows: solution A is added in syringe, and the syringe is fixed on micro- glue
Capsule is granulated on the syringe pump of instrument, and the injector head soft silicone tube is connected with the spray head that the microcapsules are granulated instrument, described
Spray head aperture is 80~1000 μm, and the spray head is located on B solution liquid level at 5~100cm, and the liquid height of the B solution is 1
~20cm, vibration frequency 1200Hz, voltage 1000V, adjusting syringe pump parameter feed speed are 1~2.4mL/min.
9. the nano-cellulose-pectin micro-capsule is prepared in method described in any one of claim 4-8.
10. nano-cellulose described in claim 9-pectin micro-capsule is in biological medicine, food service industry, cosmetic industry or enzyme engineering
The particle that hypotonic leakage is constructed in field contains object or drug particles transport the application in system.
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Citations (2)
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|---|---|---|---|---|
| CN103205912A (en) * | 2013-03-25 | 2013-07-17 | 上海大学 | Method for using kelp residues to prepare nano-crystalline cellulose whisker hydrosol |
| CN103590277A (en) * | 2013-11-27 | 2014-02-19 | 上海大学 | Method for preparing nano-crystalline cellulose spheres by utilizing onionskins |
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2019
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205912A (en) * | 2013-03-25 | 2013-07-17 | 上海大学 | Method for using kelp residues to prepare nano-crystalline cellulose whisker hydrosol |
| CN103590277A (en) * | 2013-11-27 | 2014-02-19 | 上海大学 | Method for preparing nano-crystalline cellulose spheres by utilizing onionskins |
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