CN107057127A - A kind of preparation method of pH responsive nanos cellulose antibacterial controlled release membranes - Google Patents
A kind of preparation method of pH responsive nanos cellulose antibacterial controlled release membranes Download PDFInfo
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Abstract
A kind of preparation method of pH responsive nanos cellulose antibacterial controlled release membranes, it is characterised in that：First, by preparing pH response microcapsules, the i.e. compound of polyacrylic acid and lysozyme, then this microcapsules is added in nano-cellulose solution, by solution curtain coating on glass plate, oven drying film forming.By being into film base material from nano-cellulose, the film has good mechanical property relative to other carbohydrates and protein-based film, the combination of its anti-microbial property and pH responses can control the release of active material under different pH environment, the shelf life of food can preferably be extended, tool has been widely used.
Description
Technical field
The invention belongs to high polymer material technology of preparing, more particularly to a kind of pH- responsive nanos cellulose antibacterial controlled release
The preparation method of film.
Background technology
Microorganism is to cause one of putrid and deteriorated key factor during food storage, uses antibacterial film mostly at present
Packaged food, to reach the effect of Shelf-life.But antiseptic is directly appended in film or is coated on film surface,
Due to the quick release of antibacterial substance, do not continue fungistatic effect well.There is researcher multiple by embedding, multilayer
The method such as conjunction, modified, is made antimicrobial sustained-release film, although antibacterial substance can be discharged slowly, but can not
According to the change of environmental factor, intelligently control release speed.
Microcapsules technology is the technology of micro substance parcel in the polymer, is specifically referred to a certain purpose thing（Core
Or interior phase）Got up with the high-molecular compound cladding completely of various natural or synthesis, and to original chemical property of purpose thing
Do not damage at all, the function of then making purpose thing increasingly by some outside stimulus or slow releasing function shows in outside again
Come.And pH- responses microcapsules can be changed due to the conformation of the polyelectrolyte under different pH environment, so as to influence micro- glue
The diffusional permeability of capsule, the controlled-release effect of environment pH changes can be responded by being so achieved that.And it can be lived by composite antibacterial
Property material, is prepared into while having the pH- response microcapsules of anti-microbial property.
Zeta potential is the important indicator for characterizing colloidal solution dispersion stability, and the significance of Zeta potential is
Its numerical value is related to the stability of colloidal dispersion system, and Zeta potential is to mutually exclusive between particle or attraction intensity
Measurement.Its absolute value（It is positive or negative）Higher, system is more stable, that is, dissolves or disperse that aggregation can be resisted, conversely, Zeta potential
（It is positive or negative）It is lower, more tend to condense or condense, i.e., attraction has exceeded repulsive force, disperse destroyed and occur to condense or poly-
Collection.One of its main application is exactly to study the interaction of colloid and electrolyte.
Lysozyme (LZM) is a kind of nontoxic, protein for having no side effect, has certain bacteriolysis again, therefore available
Make natural food antiseptic.Its antimicrobial spectrum is wider, is not only limited to G- bacterium, also has inhibition to part G+ bacterium.Lysozyme
Below the isoelectric point in the range of wide pH, molecule is positively charged.It can be ionized as a polyion after polyelectrolyte dissolving
With many small ions with polyion opposite charge, claim counter ion.There are the electric charge of many fixations, such as poly- third on point chain of polyion
Olefin(e) acid (PAA) is negatively charged, referred to as polyanion, and its counter ion is then positively charged to be gathered in surrounding and form electrostatic field, its electricity
Lotus density can change with environment pH change.By this special function, can control polyacrylic acid and lysozyme it
Between Zeta potential change so that the active force between changing them, reach the purpose of control load level and bacteriolyze enzyme r e lease.
Native cellulose is to be distributed most wide high polymer material in nature, is carried out functionalization or modified can be used for
The fields such as textile, sorbing material, catalyst carrier and bio-medical material, because receiving significant attention.Nano-cellulose
（NCC）Not only basic structure and performance with cellulose, and the characteristic with nano particle, such as higher Young's modulus,
Huge specific surface area, high reactivity and strong adsorption capacity, has broad application prospects.Although also having research with receiving
Rice cellulose prepares antibacterial film, but using nano-cellulose as base material, the controlled release being combined with pH- response microcapsules technologies
There is not been reported for film.
The content of the invention
The present invention is proposed for there is no the nano-cellulose controlled release membranes that pH- response microcapsules technologies are combined at present
A kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes.The technical scheme is that first preparing pH- responses
This microcapsules, is then added in nano-cellulose solution, passes through by the compound of property microcapsules, i.e. polyacrylic acid and lysozyme
Solution curtain coating is on glass plate, oven drying film forming, and its specific step is included：
(1) preparation of pH- responses microcapsules：
100 ~ 400mg polyacrylic acid and 800mg lysozyme accurately are weighed, 20ml is dissolved in respectively, pH is 7.0 10mMol
In buffer solution of sodium phosphate, the mass ratio of polyacrylic acid and lysozyme is 0.2 ~ 0.4；After two kinds of solution are mixed, magnetic force is used
Agitator is mixed 4 minutes under 400rpm rotating speeds, and suspension is placed to 4 hours precipitations to complete particle at room temperature；Use
Centrifuge, by centrifuging 10 minutes, collects compound under 6000rpm rotating speeds；Finally by compound in 35 °C of drying box
Place 24 hours to remove unnecessary surface liquid, the compound being dried to obtain i.e. pH- responses microcapsules, collect microcapsules with
It is standby.
(2) preparation of nano-cellulose solution：
5 ~ 15% sodium hydroxide solutions of 10 ~ 20% urea liquids and 25ml that 25ml is accurately pipetted with 20ml pipettes are placed in
In 100ml beakers, it is sufficiently stirred for after 5 minutes being put in mixed solution into -18 °C of freezer compartment of refrigerator with glass bar, is kept for 2 ~ 5 points
Clock, then takes out；The microcrystalline cellulose that 1.5 ~ 2g is accurately weighed using electronic balance is added in mixed solution, uses strong stirring
Machine obtained the solution of clear with rotating speed 3000rpm stirring and dissolvings 20 minutes；By solution be added drop-wise to mass fraction for 5% it is dilute
In sulfuric acid, stirred using glass bar, neutrality is reached to final ph；Wash, filter through distilled water again, obtaining one layer of nanofiber
Filter cake, filter cake is dissolved in 100ml distilled water, it is ultrasonically treated after to obtain the milky aqueous solution, i.e. nano-cellulose molten
Liquid.
(3) preparation of nano-cellulose film：
The nano-cellulose solution prepared is placed on magnetic stirring apparatus, magnetic agitation rotating speed is 50rpm, while using liquid relief
Rifle is accurately drawn 0.5ml glycerine and is slowly added dropwise as plasticizer to Solutions Center, by the pH- response microcapsules prepared
200mg is slowly added into nano-cellulose solution, is continued magnetic agitation and is obtained composite solution after 5 hours；Last solution curtain coating
In 20cmOn 30cm glass plate, 30 °C of oven drying film forming.
Polyacrylic acid molecular weight is 10 ~ 500KDa in step (1).
Polyacrylic acid molecular weight is 10KDa in step (1), and the mass ratio of polyacrylic acid and lysozyme is 0.4.
Polyacrylic acid molecular weight is 500KDa in step (1), and the mass ratio of polyacrylic acid and lysozyme is 0.2.
The microcapsule diameter prepared in step (1) is 50 ~ 800nm.
Polyacrylic acid molecular weight is 10KDa in step (1), and the mass ratio of polyacrylic acid and lysozyme is 0.4, preparation it is micro-
Capsule diameter is 527nm.
Polyacrylic acid molecular weight is 500KDa in step (1), and the mass ratio of polyacrylic acid and lysozyme is 0.2, preparation
Microcapsule diameter is 436nm.
Its a diameter of 50 ~ 100nm of the nano-cellulose of preparation in step (2).
Easily controllable, the prepared pH- response microcapsules of filming technology of the present invention do not occur fracture phenomena.
By the present invention in that preparing the micro- glue of pH- responses in varing proportions with the polyacrylic acid and lysozyme of different molecular weight
Capsule, the complexing power of polyacrylic acid strengthens with the increase of its molecular weight and proportion, significantly limit lysozyme
Release, but with environment pH change, the charge density around polyacrylic acid is also changed, and show it is strong just
Electric charge, the lysozyme repulsive force increase with again with positive charge, adds the release diffusivity of lysozyme, so as to reach control
Effect is released, makes film that there is pH sensitiveness.Therefore, the film can apply to carry out quick response, control with environment pH change
The rate of release of Substance processed, reaches permanently effective antibacterial effect.
The present invention is into film base material from nano-cellulose, relative to existing carbohydrate film or protein-based film,
With more preferable mechanical property, it is actual to be more widely applied.
Embodiment
To make the operating process of the invention realized be easy to understand with creation characteristic, with reference to embodiment,
The present invention is expanded on further.
It is an object of the invention to provide a kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes.It is wrapped
The preparation of the microcapsules of response containing pH- and nano-cellulose film-forming process.The step is as follows：
(1) preparation of pH- responses microcapsules：
100mg ~ 400mg polyacrylic acid (10KDa or 500KDa) and 800mg lysozyme accurately are weighed, is dissolved in respectively
20ml, pH is in 7.0 10mMol buffer solution of sodium phosphate, the mass ratio of polyacrylic acid and lysozyme are 0.2 ~ 0.4；By two kinds
After solution mixing, mixed 4 minutes, suspension is placed at room temperature 4 hours under 400rpm rotating speeds using magnetic stirring apparatus；Make
With centrifuge under 6000rpm rotating speeds, by centrifuging 10 minutes, compound is collected；The last drying box by compound at 35 °C
Middle to place 24 hours, the compound being dried to obtain i.e. pH- responses microcapsules collect microcapsules with standby；
(2) preparation of nano-cellulose solution：
5 ~ 15% sodium hydroxide solutions of 10 ~ 20% urea liquids and 25ml that 25ml is accurately pipetted with 20ml pipettes are placed in
In 100ml beakers, it is sufficiently stirred for after 5 minutes being put in mixed solution into -18 °C of freezer compartment of refrigerator with glass bar, is kept for 2 ~ 5 points
Clock, then takes out；The microcrystalline cellulose that 1.5 ~ 2g is accurately weighed using electronic balance is added in mixed solution, uses strong stirring
Machine obtained the solution of clear with rotating speed 3000rpm stirring and dissolvings 20 minutes；It is 5% that the solution is added drop-wise into mass fraction
In dilute sulfuric acid, stirred using glass bar, neutrality is reached to final ph；Wash, filter through distilled water again, obtaining one layer of Nanowire
Tie up filter cake, filter cake is dissolved in 100ml distilled water, it is ultrasonically treated after obtain the milky aqueous solution, i.e. nano-cellulose
Solution；
(3) preparation of nano-cellulose film：
The nano-cellulose solution prepared is placed on magnetic stirring apparatus, magnetic agitation rotating speed is 50rpm, while using liquid relief
Rifle is accurately drawn 0.5ml glycerine and is slowly added dropwise as plasticizer to Solutions Center, by the pH- response microcapsules prepared
200mg is slowly added into nano-cellulose solution, is continued magnetic agitation and is obtained composite solution after 5 hours；Last solution curtain coating
In 20cmOn 30cm glass plate, 30 °C of oven drying film forming.
Testing index and its assay method of the present invention are as follows：
1. tensile property is determined
Film, which is cut into, during test is about 35mm, a width of 5mm sample, and assay method is according to GB1040-79《Plastic tensile is tested
Method》, using LRX-PLUS type electronic material testing machines, setting test speed is 1mm/s, by formula（1）Calculate tensile strength.
(1)
In formula, Ts is that tensile strength/MPa, P is the thickness that width that maximum pull/N, b is film sample/mm, d is film sample
Degree/mm.
2. compound Zeta potential is determined
Use sodium acetate（0.05M, pH4.5）The compound prepared is diluted, passes through dynamic light scattering（DLS）Measure Zeta potential；With
Deionized water（pH7.0）The compound prepared is diluted, passes through dynamic light scattering（DLS）Measure Zeta potential.
3. the measure of diffusion coefficient
It is 16cm by area2Film be placed in the dissolution medium containing 40ml（PH4.5 0.05M buffer solution of sodium phosphate）Sealing
In flask, then by flask under 10 °C with 100rpm continuous oscillations, buffering is discharged into from film by HPLC quantitative analyses
LZM in solution.Control group deionized water（pH7.0）For dissolution medium.
Release dynamics measurement is combined with mathematical modeling, determines the diffusion coefficient of lysozyme in film.The model is based on
Fick second law.At any time t due to Fickian spread from film desorb lysozyme total amount it is as follows：
(2)
In formula,；For the positive root of non-zero；；；Solved during for balance
The bacteriolyze enzyme amount of suction；For the volume of dissolution medium；For the area of film；K be lysozyme in film with the ratio in solution.
4. the measure of anti-microbial property
The preparation of LB culture mediums：Peptone 1g, yeast extract 0.5g, sodium chloride 1g, distilled water 95ml, shake container until molten
Matter is dissolved, and pH to 7.4 is adjusted with 5mol/L NaOH, and 100ml, 125 DEG C of sterilizing 25min are settled to distilled water.
The preparation of solid potato culture medium：Potato 20g, peeling, is cut into block and is added in 100ml distilled water, boil
30min（Note controlling the control of firepower, can suitably moisturizing）, with filtered through gauze, add sucrose 2g in filtrate, agar 2g, pH from
So（About 6.0）, 100ml is settled to distilled water, loads triangular flask, 125 DEG C of sterilizing 25min.
The enrichment culture of Escherichia coli：Strain is connected in LB culture mediums in desinfection chamber, complete warm shaken cultivation case is set
Parameter is 38 DEG C, 100r/min, Shaking culture 16h.
Bactericidal test：The Escherichia coli of culture are seeded in the solid potato culture medium surface of sterilizing with oese,
And it is uniform in the coating of its surface.Sample thin film is broken into several a diameter of 1cm sequin and then justifies small film by card punch
Piece is layered on flat board, it is adhering closely on culture jin, is closed the lid, be put into 12 ~ 20h in 38 DEG C of constant temperature and humidity incubators,
Observation whether there is inhibition zone and recorded.
Embodiment 1:
160mg polyacrylic acid (10KDa) and 800mg lysozyme accurately are weighed, 20ml is dissolved in respectively, pH is 7.0
In 10mMol buffer solution of sodium phosphate；After two kinds of solution are mixed, 4 points are mixed under 400rpm rotating speeds using magnetic stirring apparatus
Clock, suspension is placed at room temperature 4 hours；Using centrifuge under 6000rpm rotating speeds, by centrifuging 10 minutes, collect multiple
Compound；Finally compound is placed 24 hours in 35 °C of drying box, the compound the being dried to obtain i.e. micro- glue of pH- responses
Capsule, collects microcapsules with standby；
10% sodium hydroxide solution of 15% urea liquid and 25ml that 25ml is accurately pipetted with 20ml pipettes is placed in 100ml beakers
In, it is sufficiently stirred for after 5 minutes being put in mixed solution into -18 °C of freezer compartment of refrigerator with glass bar, is kept for 2 minutes, then taken out；
The microcrystalline cellulose that 1.5g is accurately weighed using electronic balance is added in mixed solution, with machine,massing with rotating speed
3000rpm stirring and dissolvings 20 minutes, obtain the solution of clear；The solution is added drop-wise to the dilute sulfuric acid that mass fraction is 5%
In, stirred using glass bar, neutrality is reached to final ph；Wash, filter through distilled water again, obtaining one layer of nanofiber filter
Cake, filter cake is dissolved in 100ml distilled water, it is ultrasonically treated after obtain the milky aqueous solution, i.e. nano-cellulose solution；
The nano-cellulose solution prepared is placed on magnetic stirring apparatus, magnetic agitation rotating speed is 50rpm, while using liquid relief
Rifle is accurately drawn 0.5ml glycerine and is slowly added dropwise as plasticizer to Solutions Center, by the pH- response microcapsules prepared
200mg is slowly added into nano-cellulose solution, is continued magnetic agitation and is obtained composite solution after 5 hours；Last solution curtain coating
In 20cmOn 30cm glass plate, 30 °C of oven drying film forming.
Determine tensile property, anti-microbial property, the Zeta potential of PAA/LZM compounds, the release performance of film.The drawing of film
Stretch performance and be shown in Table 1, anti-microbial property and be shown in Table the 2, Zeta potential of PAA/LZM compounds and be shown in Table 3, release performance and be shown in Table 4.
Example 2:
160mg polyacrylic acid (500KDa) and 800mg lysozyme accurately are weighed, 20ml is dissolved in respectively, pH is 7.0
In 10mMol buffer solution of sodium phosphate, the mass ratio of polyacrylic acid and lysozyme is 0.2；After two kinds of solution are mixed, magnetic is used
Power agitator is mixed 4 minutes under 400rpm rotating speeds, suspension is placed at room temperature 4 hours；Using centrifuge in 6000rpm
Under rotating speed, by centrifuging 10 minutes, compound is collected；Finally compound is placed 24 hours in 35 °C of drying box, dried
Obtained compound i.e. pH- responses microcapsules, collect microcapsules with standby；
15% sodium hydroxide solution of 18% urea liquid and 25ml that 25ml is accurately pipetted with 20ml pipettes is placed in 100ml beakers
In, it is sufficiently stirred for after 5 minutes being put in mixed solution into -18 °C of freezer compartment of refrigerator with glass bar, is kept for 5 minutes, then taken out；
The microcrystalline cellulose that 2g is accurately weighed using electronic balance is added in mixed solution, with machine,massing with rotating speed 3000rpm
Stirring and dissolving 20 minutes, obtains the solution of clear；The solution is added drop-wise in the dilute sulfuric acid that mass fraction is 5%, uses glass
Glass rod is stirred, and neutrality is reached to final ph；Wash, filter through distilled water again, obtaining one layer of nanofiber filter cake, filter cake is molten
Solution in 100ml distilled water, it is ultrasonically treated after obtain the milky aqueous solution, i.e. nano-cellulose solution；
The nano-cellulose solution prepared is placed on magnetic stirring apparatus, magnetic agitation rotating speed is 50rpm, while using liquid relief
Rifle is accurately drawn 0.5ml glycerine and is slowly added dropwise as plasticizer to Solutions Center, by the pH- response microcapsules prepared
200mg is slowly added into nano-cellulose solution, is continued magnetic agitation and is obtained composite solution after 5 hours；Last solution curtain coating
In 20cmOn 30cm glass plate, 30 °C of oven drying film forming.
Determine tensile property, anti-microbial property, the Zeta potential of PAA/LZM compounds, the release performance of film.The drawing of film
Stretch performance and be shown in Table 1, anti-microbial property and be shown in Table the 2, Zeta potential of PAA/LZM compounds and be shown in Table 3, release performance and be shown in Table 4.
Example 3:
320mg polyacrylic acid (10KDa) and 800mg lysozyme accurately are weighed, 20ml is dissolved in respectively, pH is 7.0
In 10mMol buffer solution of sodium phosphate, the mass ratio of polyacrylic acid and lysozyme is 0.4；After two kinds of solution are mixed, magnetic is used
Power agitator is mixed 4 minutes under 400rpm rotating speeds, suspension is placed at room temperature 4 hours；Using centrifuge in 6000rpm
Under rotating speed, by centrifuging 10 minutes, compound is collected；Finally compound is placed 24 hours in 35 °C of drying box, dried
Obtained compound i.e. pH- responses microcapsules, collect microcapsules with standby；
10% sodium hydroxide solution of 15% urea liquid and 25ml that 25ml is accurately pipetted with 20ml pipettes is placed in 100ml beakers
In, it is sufficiently stirred for after 5 minutes being put in mixed solution into -18 °C of freezer compartment of refrigerator with glass bar, is kept for 2 minutes, then taken out；
The microcrystalline cellulose that 1.5g is accurately weighed using electronic balance is added in mixed solution, with machine,massing with rotating speed
3000rpm stirring and dissolvings 20 minutes, obtain the solution of clear；The solution is added drop-wise to the dilute sulfuric acid that mass fraction is 5%
In, stirred using glass bar, neutrality is reached to final ph；Wash, filter through distilled water again, obtaining one layer of nanofiber filter
Cake, filter cake is dissolved in 100ml distilled water, it is ultrasonically treated after obtain the milky aqueous solution, i.e. nano-cellulose solution；
The nano-cellulose solution prepared is placed on magnetic stirring apparatus, magnetic agitation rotating speed is 50rpm, while using liquid relief
Rifle is accurately drawn 0.5ml glycerine and is slowly added dropwise as plasticizer to Solutions Center, by the pH- response microcapsules prepared
200mg is slowly added into nano-cellulose solution, is continued magnetic agitation and is obtained composite solution after 5 hours；Last solution curtain coating
In 20cmOn 30cm glass plate, 30 °C of oven drying film forming.
Determine tensile property, anti-microbial property, the Zeta potential of PAA/LZM compounds, the release performance of film.The drawing of film
Stretch performance and be shown in Table 1, anti-microbial property and be shown in Table the 2, Zeta potential of PAA/LZM compounds and be shown in Table 3, release performance and be shown in Table 4.
Example 4:
320mg polyacrylic acid (500KDa) and 800mg lysozyme accurately are weighed, 20ml is dissolved in respectively, pH is 7.0
In 10mMol buffer solution of sodium phosphate, the mass ratio of polyacrylic acid and lysozyme is 0.4；After two kinds of solution are mixed, magnetic is used
Power agitator is mixed 4 minutes under 400rpm rotating speeds, suspension is placed at room temperature 4 hours；Using centrifuge in 6000rpm
Under rotating speed, by centrifuging 10 minutes, compound is collected；Finally compound is placed 24 hours in 35 °C of drying box, dried
Obtained compound i.e. pH- responses microcapsules, collect microcapsules with standby；
15% sodium hydroxide solution of 18% urea liquid and 25ml that 25ml is accurately pipetted with 20ml pipettes is placed in 100ml beakers
In, it is sufficiently stirred for after 5 minutes being put in mixed solution into -18 °C of freezer compartment of refrigerator with glass bar, is kept for 5 minutes, then taken out；
The microcrystalline cellulose that 2g is accurately weighed using electronic balance is added in mixed solution, with machine,massing with rotating speed 3000rpm
Stirring and dissolving 20 minutes, obtains the solution of clear；The solution is added drop-wise in the dilute sulfuric acid that mass fraction is 5%, uses glass
Glass rod is stirred, and neutrality is reached to final ph；Wash, filter through distilled water again, obtaining one layer of nanofiber filter cake, filter cake is molten
Solution in 100ml distilled water, it is ultrasonically treated after obtain the milky aqueous solution, i.e. nano-cellulose solution；
The nano-cellulose solution prepared is placed on magnetic stirring apparatus, magnetic agitation rotating speed is 50rpm, while using liquid relief
Rifle is accurately drawn 0.5ml glycerine and is slowly added dropwise as plasticizer to Solutions Center, by the pH- response microcapsules prepared
200mg is slowly added into nano-cellulose solution, is continued magnetic agitation and is obtained composite solution after 5 hours；Last solution curtain coating
In 20cmOn 30cm glass plate, 30 °C of oven drying film forming.
Determine tensile property, anti-microbial property, the Zeta potential of PAA/LZM compounds, the release performance of film.The drawing of film
Stretch performance and be shown in Table 1, anti-microbial property and be shown in Table the 2, Zeta potential of PAA/LZM compounds and be shown in Table 3, release performance and be shown in Table 4.
As can be seen from Table 1, the tensile strength scope of the nano-cellulose film is 115.35 ~ 132.85MPa, and 4 kinds are not
The mechanical property of same type film is more or less the same, but relative to carbohydrate, protein-based film, the film has good mechanical property
Can, it is more extensive in terms of practical application.
As can be seen from Table 2, by the experiment of inhibition zone, 4 kinds of films all occur in that inhibition zone, illustrate that the film has good
Good anti-microbial property.
As can be seen from Table 3, Zeta potential of 4 kinds of films in pH7.0 deionized waters is significantly lower than in pH4.5 sodium acetates
Zeta potential, illustrate that the Zeta potential of pH- response microcapsules also changes when external environment pH changes, so as to
Enough change the intensity of repulsive force between polyacrylic acid and lysozyme.
With reference to table 3, table 4 as can be seen that due between the complexing power and polyacrylic acid and lysozyme of polyacrylic acid compared with
Low Zeta potential, release of the lysozyme in pH7.0 deionized waters is greatly restricted, with pH reduction, polypropylene
Zeta potential between acid and lysozyme gradually increases, and its repulsive force also gradually strengthens, in pH4.5 sodium acetates, in film
Lysozyme is released；Although Zeta can be improved to a certain extent by improving the ratio of polyacrylic acid and the molecular weight of polyacrylic acid
Current potential, the repulsion force between increase polyacrylic acid and lysozyme, but the complexing power of polyacrylic acid is also improved simultaneously, make
The rate of release of lysozyme in microcapsules slows down.
The tensile property of the nano-cellulose film of the different ratios of raw materials of table 1
| Title | PAA and LZM ratios | Tensile property（MPa） |
| PAA (10KDa)/LZM- nano-celluloses | 0.2 | 115.35 |
| PAA (500KDa)/LZM- nano-celluloses | 0.2 | 120.67 |
| PAA (10KDa)/LZM- nano-celluloses | 0.4 | 130.15 |
| PAA (500KDa)/LZM- nano-celluloses | 0.4 | 132.85 |
The anti-microbial property of the nano-cellulose film of the different ratios of raw materials of table 2
| Title | PAA and LZM ratios | Whether inhibition zone is occurred |
| PAA (10KDa)/LZM- nano-celluloses | 0.2 | It is |
| PAA (500KDa)/LZM- nano-celluloses | 0.2 | It is |
| PAA (10KDa)/LZM- nano-celluloses | 0.4 | It is |
| PAA (500KDa)/LZM- nano-celluloses | 0.4 | It is |
The Zeta potential of the nano-cellulose film of the different ratios of raw materials of table 3
The release performance of the nano-cellulose film of the different ratios of raw materials of table 4
It can be drawn with reference to table 1, table 3, table 4 to draw a conclusion：When polyacrylic acid molecular weight is 10KDa, polyacrylic acid and lysozyme
Mass ratio is 0.4 film prepared, is 0.2 relative to mass ratio, and it discharges diffusivity and is more or less the same, but possesses more preferable mechanics
Performance；When polyacrylic acid molecular weight is 500KDa, polyacrylic acid is 0.2 film prepared with lysozyme mass ratio, and mass ratio is
0.4, although tensile property reduces 12.18MPa, but mechanical property is totally more or less the same, and its release performance is preferably, it is main
To be 0.4 film prepared with lysozyme mass ratio due to the polyacrylic acid using 500KDa molecular weight, polyacrylic acid so that poly-
The complexing power of acrylic acid is greatly improved, and limits the rate of release of lysozyme.
A kind of pH- responsive nanos cellulose antibacterial controlled release membranes of the present invention, its have good mechanical property,
Anti-microbial property, when environment pH changes, can control the release of active material, the either aspect of performance in film in itself
Or in terms of practical application, there is good application prospect relative to general thin.
Claims (8)
1. a kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes, it is characterised in that：First prepare pH- responses
Microcapsules, are then added in nano-cellulose solution, by molten by the compound of property microcapsules, i.e. polyacrylic acid and lysozyme
Liquid is cast on glass plate, and oven drying film forming, its specific steps are included：
(1) preparation of pH- responses microcapsules：
100 ~ 400mg polyacrylic acid and 800mg lysozyme accurately are weighed, 20ml is dissolved in respectively, pH is 7.0 10mMol
In buffer solution of sodium phosphate, the mass ratio of polyacrylic acid and lysozyme is 0.2 ~ 0.4；After two kinds of solution are mixed, magnetic force is used
Agitator is mixed 4 minutes under 400rpm rotating speeds, suspension is placed at room temperature 4 hours；Turned using centrifuge in 6000rpm
Under speed, by centrifuging 10 minutes, compound is collected；Finally compound is placed 24 hours in 35 °C of drying box, dry
To compound be pH- response microcapsules, collect microcapsules with standby；
(2) preparation of nano-cellulose solution：
5 ~ 15% sodium hydroxide solutions of 10 ~ 20% urea liquids and 25ml that 25ml is accurately pipetted with 20ml pipettes are placed in
In 100ml beakers, it is sufficiently stirred for after 5 minutes being put in mixed solution into -18 °C of freezer compartment of refrigerator with glass bar, is kept for 2 ~ 5 points
Clock, then takes out；The microcrystalline cellulose that 1.5 ~ 2g is accurately weighed using electronic balance is added in mixed solution, uses strong stirring
Machine obtained the solution of clear with rotating speed 3000rpm stirring and dissolvings 20 minutes；It is 5% that the solution is added drop-wise into mass fraction
In dilute sulfuric acid, stirred using glass bar, neutrality is reached to final ph；Wash, filter through distilled water again, obtaining one layer of Nanowire
Tie up filter cake, filter cake is dissolved in 100ml distilled water, it is ultrasonically treated after obtain the milky aqueous solution, i.e. nano-cellulose
Solution；
(3) preparation of nano-cellulose film：
The nano-cellulose solution prepared is placed on magnetic stirring apparatus, magnetic agitation rotating speed is 50rpm, while using liquid relief
Rifle is accurately drawn 0.5ml glycerine and is slowly added dropwise as plasticizer to Solutions Center, by the pH- response microcapsules prepared
200mg is slowly added into nano-cellulose solution, is continued magnetic agitation and is obtained composite solution after 5 hours；Last solution curtain coating
In 20cmOn 30cm glass plate, 30 °C of oven drying film forming.
2. a kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes according to claim 1, its feature
It is：Polyacrylic acid molecular weight is 10 ~ 500KDa in step (1).
3. a kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes according to claim 1, its feature
It is：Polyacrylic acid molecular weight is 10KDa in step (1), and the mass ratio of polyacrylic acid and lysozyme is 0.4.
4. a kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes according to claim 1, its feature
It is：Polyacrylic acid molecular weight is 500KDa in step (1), and the mass ratio of polyacrylic acid and lysozyme is 0.2.
5. a kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes according to claim 1, its feature
It is：The microcapsule diameter prepared in step (1) is 50 ~ 800nm.
6. a kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes according to claim 1, its feature
It is：Polyacrylic acid molecular weight is 10KDa in step (1), and the mass ratio of polyacrylic acid and lysozyme is 0.4, micro- glue of preparation
The a diameter of 527nm of capsule.
7. a kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes according to claim 1, its feature
It is：Polyacrylic acid molecular weight is 500KDa in step (1), and the mass ratio of polyacrylic acid and lysozyme is 0.2, micro- glue of preparation
The a diameter of 436nm of capsule.
8. a kind of preparation method of pH- responsive nanos cellulose antibacterial controlled release membranes according to claim 1, its feature
It is：Its a diameter of 50 ~ 100nm of the nano-cellulose of preparation in step (2).
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| CN109126488A (en) * | 2018-08-22 | 2019-01-04 | 中南林业科技大学 | A kind of antibacterial type ultrafiltration membrane and preparation method thereof |
| CN112796039A (en) * | 2020-12-30 | 2021-05-14 | 江苏大学 | Preparation method of pH intelligent response controlled-release antibacterial packaging fiber film |
| CN115323823A (en) * | 2022-09-16 | 2022-11-11 | 广西大学 | Preparation method and application of intelligent antibacterial coating emulsion for packaging paper |
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