CN107190418B - The fiber membrane device and preparation method thereof of adsorbable-desorption protein based on 3D printing PLA material - Google Patents
The fiber membrane device and preparation method thereof of adsorbable-desorption protein based on 3D printing PLA material Download PDFInfo
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- CN107190418B CN107190418B CN201710567398.0A CN201710567398A CN107190418B CN 107190418 B CN107190418 B CN 107190418B CN 201710567398 A CN201710567398 A CN 201710567398A CN 107190418 B CN107190418 B CN 107190418B
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/44—Materials comprising a mixture of organic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
Abstract
The present invention relates to the fiber membrane devices and preparation method thereof of adsorbable-desorption protein based on 3D printing PLA material.Nano-cellulose/cellulose diacetate composite nano fiber is made by electrostatic spinning in nano-cellulose/cellulose diacetate composite spinning liquid, and it is accumulated on using PLA supporter made from 3D printing technique simultaneously, nano-cellulose/cellulose diacetate composite nano-fiber membrane is formed to get fiber membrane device provided by the invention is arrived.The present invention not only optimizes the formula of spinning solution, but also introduce substrate support of the PLA supporter as fiber membrane device, effective support is provided under high pressure drop, high-throughput separation condition for the device, the recycling of tunica fibrosa can be improved, guarantee the separative efficiency to protein.The film device is high to bovine serum albumin(BSA) adsorbance, and after circulation absorption-separating process five times, desorption rate can still keep 80% or more, can be widely applied to protein purification separation.
Description
Technical field
The present invention relates to the separating and purifying technology fields of protein, more particularly to based on 3D printing PLA material it is adsorbable-
The fiber membrane device and preparation method thereof of protein is desorbed.
Background technique
In recent years, 3D printing technique is as brand-new material material molding technology, referred to as " the system with industrial revolution meaning
Make technology ".3D printing technique is based primarily upon three-dimensional mathematical model, using the material of different shape (powdered, droplet-like, threadiness)
By the cumulative method of point-by-point or layer-by-layer integral, the 3D solid of different contour structures is ultimately formed.Just because of 3D printing technique
Has the characteristics that flexible manufacturing, which can be applied to preparation tool by the product of Free Printing unique outlook, internal structure complexity
There are the assembly unit in the separation membrane device of highly selective energy, the development for not only simplifying product manufacture process, shortening product
Period can also be provided personalized service, improves efficiency and reduce cost.
" electrostatic spinning technique " refers to that Polymer Solution drop under the effect of high-pressure electrostatic power, overcomes own face tension to be formed
Taylor cone, and then be sufficiently tensile, in moment, splitting is thousands of nanofibers, ultimately forms a kind of superfine fibre film
Method.There is very high specific surface area, wider pore diameter range using the made fiber film material of the technology, it is abundant poroid
Structure, the hole connectivity of height, and it is easy to surface modification.Based on the above feature, which is widely portable to
Isolation and purification field, such as adsorbed film, ion-exchange chromatography, microfiltration membranes, nanofiltration membrane, reverse osmosis membrane and electrodialysis.
Cellulose diacetate is that cellulose carries out esterification under the action of catalyst, and then product is hydrolyzed instead
It answers, reduces a kind of cellulose derivative that its acetyl content obtains；Cellulose acetate molecular structure itself is to protein without spy
Opposite sex absorption, effective selection often through the realization of chemical graft affinity ligand to large biological molecule, but will increase process flow,
Processing cost is improved, greatly limits it in the expansion for isolating and purifying application field.The present invention is set by simple, quick solvent
It changes method and is effectively combined TEMPO method nano-cellulose with cellulose diacetate, both evenly dispersed in the substrate Nanowire
Dimension element also imparts the chemical group that raw material have affinity to protein.Film device is provided using 3D printing technique
Substrate support realizes that nano-cellulose/cellulose diacetate compound system nanofiber is melted into film using electrostatic spinning technique,
The size and distribution of Optimum Regulation composite cellulosic membrane improve membrane material protein adsorbance, and are easy to elute, and meet in albumen
Matter isolates and purifies the application requirement of aspect.
Summary of the invention
(1) technical problems to be solved
The purpose of the invention is to the Nanowire for containing a large amount of affinity groups (carboxyl) is introduced in cellulose diacetate
Dimension element provides substrate support by 3D printing PLA material for electrostatic spinning nano fiber, expands composite material and answer what is isolated and purified
With to provide the fiber membrane device and preparation method of a kind of adsorbable-desorption protein based on 3D printing PLA material.
(2) technical solution
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
The preparation method of the fiber membrane device of adsorbable-desorption protein based on 3D printing PLA material, by nanofiber
Nano-cellulose/cellulose diacetate composite nano fiber is made by electrostatic spinning in element/cellulose diacetate composite spinning liquid,
And accumulated on using PLA supporter made from 3D printing technique simultaneously, form that nano-cellulose/cellulose diacetate is compound to be received
Rice tunica fibrosa, to obtain the film device.
Using PLA supporter made from 3D printing technique is fiber membrane device under high pressure drop, high-throughput separation condition
Effectively support is provided, the recycling of tunica fibrosa can be improved, guarantees the separative efficiency to protein.
The acetyl content of cellulose diacetate in composite spinning liquid is lower, has more hydroxy radical contents, hydrophily
More preferably, it can be effectively improved the water flux of fiber film material, improve Separation of Proteins efficiency.
It is made up using the composite spinning liquid comprising nano-cellulose and cellulose diacetate of electrostatic spinning technique compound
Nano fibrous membrane, can not only regulate and control scale and the distribution of fiber membrane fiber, but also significantly improve raw material to protein
Adsorption capacity.
PLA mentioned in the present invention refers to polylactic acid.
Technological parameter can be arranged as follows in electrostatic spinning technique: voltage be 20~23kV, syringe needle and receiver board away from
From 14~16cm, injection speed is 2~3mL/h, and syringe needle internal diameter is 0.80~0.82mm.Equipment used is electrostatic spinning machine,
Including HV generator, two pass micro-injection pump and conductive receiver plate.When operation, composite spinning liquid is poured into syringe
In, syringe needle internal diameter is 0.80~0.82mm, which is fixed on two pass micro-injection pump, injection speed control 2~
3mL/h, syringe needle and 14~16cm of receiver board distance adjust high pressure generator, so that voltage is maintained at 20~23kV, syringe needle drop is fast
Speed forms taylor cone, forms that nano-cellulose/cellulose diacetate is compound receives on the conductive receiver plate containing honeycomb PLA body
Rice tunica fibrosa.
Preferably, the preparation method of the PLA supporter includes:
PLA wire rod is added in FDM (i.e. Fused Deposition Modeling) printer, it will be in electrostatic spinning machine
Conductive receiver plate be fixed to the platform of the printer, designed according to digital-to-analogue structure, printed on the conductive receiver plate
The PLA supporter of honeycomb.
The supporter of honeycomb provides higher support for composite cellulosic membrane, is particularly suitable for high pressure drop, high-throughput
Separation of Proteins condition, not only can be improved the recycling performance of composite cellulosic membrane, and also ensure the separation to protein
Efficiency.
In order to guarantee that the print quality of honeycomb PLA supporter, the present invention have carried out strictly printed material used
Limit, the diameter of PLA wire rod used is limited to 1.75~1.80mm, for example, can be 1.75mm, 1.76mm, 1.77mm,
1.78mm, 1.79mm, 1.80mm, or be any subrange of above range, herein without enumerating.Use this thickness
Printed material is easy to be sprayed by spray head, will not blockage phenomenon.In addition, the present invention is also by PAL wire rod through 80~85 DEG C of dryings
Handle 3.5~4h, it is ensured that PLA wire rod is thoroughly dried, moisture-free, it is ensured that the intensity of supporter.
Preferably, the parameter setting of the FDM printer is as follows: extrusion nozzle 0.4~0.5mm of diameter, nozzle temperature 192
~196 DEG C, 30~40 DEG C of platform temperature, 0.2~0.3mm of lift height, filling rate 100%.
Structure and printed material used in conjunction with the product of the invention to be printed, inventor pass through many experiments, finally
Obtain optimal print conditions.In printing, FDM printer is arranged according to above-mentioned parameter, it is good that precision height, intensity can be obtained
PLA supporter.
Using electrostatic spinning technique fiber is made in spinning solution by the present invention, and simultaneously by fiber accumulation on PLA supporter,
Composite cellulosic membrane is formed, the fiber membrane device of adsorbable-desorption protein is directly obtained.Spinning solution used is composite spinning
Liquid contains nano-cellulose and cellulose diacetate.Preferably, in the composite spinning liquid, the quality of the nano-cellulose
Account for the 0.60-1.50% of the cellulose diacetate quality, preferably 0.60-0.75%；With
The concentration of the cellulose diacetate is 10~13wt%.
Inventor has found in the course of the research, the nano-cellulose concentration and fiber membrane device in the composite spinning liquid
Protein adsorbance is positively correlated, and the protein of cellulose diacetate concentration and fiber membrane device in the composite spinning liquid is inhaled
Attached amount and desorption rate are negatively correlated.It is also not that the concentration of nano-cellulose is higher, two acetic acid are fine but in actual fabrication process
The lower the concentration for tieing up element the better.Nano-cellulose can be improved the protein adsorbance of film device, but when excessive concentration, Compound spinning
The spinnability of silk liquid is deteriorated；Cellulose diacetate has good hydrophily, and the water that can improve fiber film material of film device is logical
Amount improves Separation of Proteins efficiency.Based on above-mentioned consideration, the present invention exists the quality control of nano-cellulose in composite spinning liquid
The 0.5~1.50% of the cellulose diacetate quality, preferably 0.60-0.75%；
The concentration of cellulose diacetate is controlled in 10~13wt%.
Preferably, the degree of substitution with acetyl group of the cellulose diacetate is 2.3~2.5, and molecular weight is 39000~60000.
Wherein, when the degree of substitution with acetyl group of cellulose diacetate is 2.5, molecular weight is best when being 39000, because of the cellulose diacetate
Hydrophily it is best.
Preferably, the preparation method of the composite spinning liquid includes:
(1) bamboo pulp is added in TEMPO oxidation system, keeps pH to react 6.5~7.0h 10.2~10.5, is received
Rice aqueous cellulosic suspension；The first organic solvent is added dropwise to the nano-cellulose water slurry and obtains nanometer through rotary evaporation
Cellulose organic solvent suspension；
TEMPO oxidation system, that is, TEMPO/NaBr/NaClO system, wherein the content of three be respectively 0.04g, 0.4g,
10g.Bamboo pulp is added in TEMPO oxidation system and carries out oxidation reaction, product is washed, is ultrasonically treated, and obtains nanofiber
Plain water slurry.The first organic solvent, preferably dimethyl sulfoxide is added dropwise to the nano-cellulose water slurry, it is molten to carry out
Agent displacement, through rotary evaporation, obtains nano-cellulose organic solvent suspension.
The condition of rotary evaporation are as follows: vacuumize rotary evaporation 4h at 80 DEG C.
(2) cellulose diacetate is dissolved in the nano-cellulose organic solvent suspension, it is organic adds second
Solvent, then stirs 4~8h at normal temperature, and standing and defoaming obtains nano-cellulose/cellulose diacetate composite spinning liquid.
Second organic solvent is dimethyl sulfoxide and chloroform, and in the composite spinning liquid, dimethyl sulfoxide
Volume ratio with chloroform is (1~3): (1~2).
The fiber membrane device of adsorbable-desorption protein based on 3D printing PLA material, using any of the above-described kind of side of preparation
Method is made.
(3) beneficial effect
Above-mentioned technical proposal of the invention has the advantages that
1, the fiber membrane device for adsorbable-desorption protein that the invention discloses a kind of based on 3D printing PLA material and
TEMPO method nano-cellulose is dispersed in Solution of CA-Acetone system by technology of preparing using solvent displacement, excellent
Compound system formula is changed；Under novel two part solvent system, Static Spinning nanosizing film forming has not only regulated and controled composite cellulosic membrane
Fibre dimensions and distribution, also significantly improve absorption of the raw material to protein.
2, substrate support of the 3D printing technique formed honeycomb shape PLA material as fiber membrane device is used in the present invention, it will
3D printing technique be applied to preparation have it is highly selective can separation membrane device in assembly unit, for the device high pressure drop,
Effectively support is provided under high-throughput separation condition, the recycling of tunica fibrosa can be improved, guarantees that the separation to protein is imitated
Rate.
3, nano-cellulose/cellulose diacetate composite nano-fiber membrane that electrostatic technique spins in the present invention, fiber ruler
It spends low, is evenly distributed, poroid abundant, protein adsorbance is high, is easy to elute.After adding nano-cellulose, pure diacetate fiber
The protein adsorbance of plain nano fibrous membrane is improved by 15.27mg/g to 280mg/g or more；Circulation absorption-separating process five times,
Eluting rate is still up to 80% or more.
Detailed description of the invention
Fig. 1 is nano-cellulose made from embodiment 1/cellulose diacetate composite nano fiber element film scanning electron microscope
Figure；
Fig. 2 is nano-cellulose made from embodiment 2/cellulose diacetate composite nano fiber element film scanning electron microscope
Figure；
Fig. 3 is nano-cellulose made from embodiment 3/cellulose diacetate composite nano fiber element film scanning electron microscope
Figure；
Fig. 4 is nano-cellulose made from embodiment 4/cellulose diacetate composite nano fiber element film scanning electron microscope
Figure；
Fig. 5 is the scanning electron microscope (SEM) photograph of cellulose diacetate film made from comparative example 1.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
S11,8g bamboo pulp is added in TEMPO (0.04g), NaBr (0.4g) and NaClO (10g) oxidation system, is led to
It crosses NaOH and adjusts pH 10.2, then react 6.5h, it is 0.2% that product, which is obtained solid content by washing filtering, ultrasound centrifugation,
Nano-cellulose water slurry.
8.2g dimethyl sulfoxide is slowly added dropwise in the water slurry, is subsequently vacuumed out the rotary evaporation 4h at 80 DEG C, obtains
To nano-cellulose dimethyl sulfoxide suspension.
S12,1.64g cellulose diacetate (degree of substitution with acetyl group 2.5, molecular weight 39000) is dissolved in 8.03g nanometers
It in cellulose dimethyl sulfoxide suspension, is completely dissolved to cellulose diacetate, when solution is transparent, then 0.2g dimethyl is sub-
Sulfone and 6.1g chloroform are added dropwise in solution, then at normal temperature after magnetic agitation 4h, stop stirring, standing and defoaming obtains
To nano-cellulose/cellulose diacetate composite spinning liquid.By calculating it is found that the quality of nano-cellulose accounts for diacetate fiber
The 1% of quality amount, the concentration of cellulose diacetate are 10wt%.
S13, the PLA wire rod of diameter 1.75mm is dried 4h at 80 DEG C.Then, PLA wire rod after processing is put
Enter FDM printer guide roll, the conductive receiver plate in electrostatic spinning machine is fixed to printing machine platform, according to honeycomb threedimensional model
Data, setting slice and print parameters: extrusion nozzle diameter 0.4mm, 192 DEG C of nozzle temperature, 40 DEG C of platform temperature, lift height
0.2mm, filling rate 100% finally obtain honeycomb PLA supporter.
S14, the resulting composite spinning liquid of S12 is poured into 20mL equipped in No. 7 needle applicators, syringe needle internal diameter is
The syringe is fixed on two pass micro-injection pump by 0.80mm, and injection speed control is in 2mL/h, syringe needle and receiver board distance
14cm adjusts high pressure generator, voltage is made to be maintained at 20kV, and syringe needle drop quickly forms taylor cone, is containing honeycomb PLA material
Nano-cellulose/cellulose diacetate composite nano-fiber membrane is formed on the conductive receiver plate of material.
Then, composite membrane is soaked in deionized water for 24 hours, the tunica fibrosa dress containing honeycomb PLA supporter can be obtained
It sets.
Embodiment 2
S21,8g bamboo pulp is added in TEMPO (0.04g), NaBr (0.4g) and NaClO (10g) oxidation system, is led to
It crosses NaOH and adjusts pH 10.5, then react 6.5h, product obtains receiving for solid content 0.2% by washing filtering, ultrasound centrifugation
Rice aqueous cellulosic suspension.
5.25g dimethyl sulfoxide is slowly added dropwise into the water slurry, is subsequently vacuumed out rotary evaporation 4h at 80 DEG C, obtains
To nano-cellulose dimethyl sulfoxide suspension.
S22,2.1g cellulose diacetate (degree of substitution with acetyl group 2.3, molecular weight 60000) is dissolved in obtained by S21 and is received
It in rice cellulose dimethyl sulfoxide suspension, is completely dissolved to cellulose diacetate, when solution is transparent, then by 4.65g bis-
Methyl sulfoxide and 9.06g chloroform are added dropwise in solution, then at normal temperature after magnetic agitation 8h, stop stirring, stand
Deaeration obtains nano-cellulose/cellulose diacetate composite spinning liquid.By calculating it is found that the quality of nano-cellulose accounts for two
The 0.5% of cellulose acetate quality, the concentration of cellulose diacetate are 10wt%.
S23, the PLA wire rod of diameter 1.75mm is dried 3.5h at 85 DEG C.Then by treated, PLA wire rod is put
Enter FDM printer guide roll, the conductive receiver plate in electrostatic spinning machine is fixed to printing machine platform, according to honeycomb threedimensional model
Data, setting slice and print parameters: extrusion nozzle diameter 0.4mm, 196 DEG C of nozzle temperature, 30 DEG C of platform temperature, lift height
0.2mm, filling rate 100% finally obtain honeycomb PLA supporter.
S24, the resulting composite spinning liquid of S22 is poured into 20mL equipped in No. 7 needle applicators, syringe needle internal diameter is
The syringe is fixed on two pass micro-injection pump by 0.82mm, and injection speed control is in 3mL/h, syringe needle and receiver board distance
16cm adjusts high pressure generator, voltage is made to be maintained at 23kV, and syringe needle drop quickly forms taylor cone, is containing honeycomb PLA material
Nano-cellulose/cellulose diacetate composite nano-fiber membrane is formed on the conductive receiver plate of material.
Then, composite membrane is soaked in deionized water for 24 hours, the tunica fibrosa dress containing honeycomb PLA supporter can be obtained
It sets.
The preparation method embodiment 1 of embodiment 3 to embodiment 5 is substantially the same, and difference is shown in Table 1.
It should be understood that 1 to 5 in table 1 respectively represents embodiment 1 to embodiment 5,6 to 9 and respectively represents following pair
Ratio 1 is to comparative example 4.
In addition, the present invention has also carried out comparative experiments.
Comparative example 1
It weighs 1.64g cellulose diacetate and 8mL dimethyl sulfoxide (density 1.10g/mL) and 4mL chloroform is molten
Agent (density 1.50g/mL) is added in 20mL conical flask, and magnetic agitation 4h under room temperature forms transparent homogeneous spinning solution.Stirring
By spinning solution standing and defoaming 8h after uniformly, 20mL is subsequently poured into equipped in No. 7 needle applicators, syringe needle internal diameter is 0.80mm, will
The syringe is fixed on two pass micro-injection pump, and setting injection speed is 2mL/h, syringe needle and receiver board distance 14cm, is adjusted
High pressure generator makes voltage be maintained at 20kV, and syringe needle drop quickly forms taylor cone, the shape on the conductive receiver plate for post aluminium foil
At cellulose diacetate nano fibrous membrane.
Then, film is soaked in deionized water for 24 hours, removes residual solvent and impurity, dries, can obtain at 60 DEG C of baking oven
Pure cellulose diacetate nano fibrous membrane.
Comparative example 2
8g bamboo pulp is added in TEMPO (0.04g), NaBr (0.4g) and NaClO (10g) oxidation system, is passed through
NaOH adjusts pH 10.2, then reacts 6.5h, and it is 0.2% that product, which is obtained solid content by washing filtering, ultrasound centrifugation,
Nano-cellulose water slurry.
8.2g dimethyl sulfoxide is slowly added dropwise in the water slurry, is subsequently vacuumed out the rotary evaporation 4h at 80 DEG C, obtains
To nano-cellulose dimethyl sulfoxide suspension.
1.64g cellulose diacetate (degree of substitution with acetyl group 2.5, molecular weight 39000) is dissolved in 8.03g nanofiber
In plain dimethyl sulfoxide suspension, be completely dissolved to cellulose diacetate, when solution is transparent, then 0.2g dimethyl sulfoxide with
6.1g chloroform is added dropwise in solution, then at normal temperature after magnetic agitation 4h, stops stirring, standing and defoaming is received
Rice cellulose/cellulose diacetate composite spinning liquid.
Composite spinning liquid is poured into 20mL equipped in No. 7 needle applicators, syringe needle internal diameter is 0.80mm, which is consolidated
Due on two pass micro-injection pump, injection speed control adjusts high pressure generator in 2mL/h, syringe needle and receiver board distance 14cm,
Voltage is set to be maintained at 20kV, syringe needle drop quickly forms taylor cone, forms Nanowire on the conductive receiver plate for posting aluminium foil
Tie up element/cellulose diacetate composite nano-fiber membrane.
Then, composite membrane is soaked in deionized water for 24 hours, can obtains that nano-cellulose/cellulose diacetate is compound to be received
Rice tunica fibrosa.
Comparative example 3
That the preparation method is the same as that of Example 1 is substantially the same for comparative example 3, the difference is that:
Composite spinning liquid includes nano-cellulose and Triafol T, wherein the concentration (nanofiber of nano-cellulose
Quality amount accounts for the percentage of Triafol T quality) it is 2wt%, the concentration of Triafol T is 10wt%.
Comparative example 4
That the preparation method is the same as that of Example 1 is substantially the same for comparative example 4, the difference is that:
In composite spinning liquid, (nano-cellulose quality accounts for the percentage of cellulose diacetate quality to the concentration of nano-cellulose
Number) it is 2wt%, the concentration of cellulose diacetate is 5wt%, and the volume ratio of dimethyl sulfoxide and chloroform is 1.5:1.
(1) protein adsorption-desorption is tested
Fiber membrane device (comparative example 1 and comparative example 2 be tunica fibrosa) immerses in 1.5mg/mL bovine serum albumin solution, vibration
Swing absorption for 24 hours, centrifugal treating 5min measures solution absorbance at UV280nm, obtains film adsorbance.
Fiber membrane device (comparative example 1 and comparative example 2 be tunica fibrosa) after adsorbed proteins is immersed the NaCl's containing 1.5M
In 0.1M Tris hydrochloric acid eluent, oscillation desorption 8h measures solution absorbance at UV280nm, obtains film desorption rate.
Test result is as shown in table 2.
Can be seen that from the test result of comparative example 1 and comparative example 2 even if without containing PLA supporter, nano-cellulose and
The protein adsorption-desorption performance of composite cellulosic membrane after both cellulose diacetates are compound is fine also superior to pure cellulose diacetate
Tie up film.This illustrates that composite spinning liquid used in the present invention can improve tunica fibrosa to the adsorption capacity of protein.
It can be seen that this hair after comparing from test result and comparative example 1, the test result of comparative example 2 of each embodiment
The test result of bright embodiment is significantly better than the test result of comparative example 1 and comparative example 2.Even multiple circulation absorption-desorption
Afterwards, the desorption rate of fiber membrane device still keeps good level.And the tunica fibrosa without containing PLA supporter is inhaled after recycling three times
After attached-desorption, elution amount is significantly reduced.This is because PLA supporter can provide under high pressure drop, high-throughput separation condition
The recycling of tunica fibrosa can be improved in effectively support, guarantees the separative efficiency to protein.
Spinning solution in comparative example 3 is nano-cellulose/Triafol T composite spinning liquid.Due to Triafol T
Hydroxy radical content be lower than cellulose diacetate, hydrophily can not show a candle to cellulose diacetate.Under low concentration, this variation is to egg
The absorption of white matter-elution property influences significant.But when concentration is higher (as shown in comparative example 3), composite fibre film device
Water flux substantially reduces, so that the protein adsorption capacity of fiber membrane device is remarkably decreased, but influences on eluting power little.
It can be seen that the content of nano-cellulose and two in composite spinning liquid from the test result of embodiment 1 and comparative example 4
The content of cellulose acetate has a certain impact to test result.When the too high levels of nano-cellulose, and cellulose diacetate
Content it is too low when, the adsorbance and recycling elution amount of fiber membrane device do not occur raised phenomenon.On the contrary, adsorbance and
Also there is a degree of reduction in recycling elution amount.This is because, the nanofiber too high levels in composite spinning liquid, so that spinning
The spinnability of silk liquid reduces, and along with the content of hydrophilic cellulose diacetate is too low, accumulation is in PLA branch after electrostatic spinning
Membrane fiber size on support body is uneven, and the water flux of tunica fibrosa substantially reduces, to reduce the albumen of fiber membrane device
Matter adsorption capacity and eluting power.
(2), structure detection
Fig. 1 to Fig. 4 is respectively that embodiment 1, embodiment 2, compound cellulose film made from embodiment 3 and embodiment 4 are swept
Electron microscope is retouched, Fig. 5 is the scanning electron microscope (SEM) photograph of cellulose acetate film made from comparative example 1.
As can be seen from Figure, under DMSO/ chloroform system, when nano-cellulose concentration is 0.5% and 1.0%
When, many nutty structures are obviously generated in composite fibre, dimensional homogeneity decline or even few fibers form pearl shape
Looks, wind between fiber and kink phenomenon is obvious.When nano-cellulose concentration is 0.6% and 0.75%, composite fibre forming
Continuous and uniformly, average fibre diameter is respectively 381 ± 116nm and 430 ± 108nm, the fibre dimensions more than 80% 200~
Within the scope of 500nm.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (11)
1. the preparation method of the fiber membrane device of adsorbable-desorption protein based on 3D printing PLA material, which is characterized in that
It is multiple that by electrostatic spinning nano-cellulose/cellulose diacetate is made in nano-cellulose/cellulose diacetate composite spinning liquid
Nanofiber is closed, and is accumulated on using PLA supporter made from 3D printing technique simultaneously, nano-cellulose/bis- acetic acid are formed
Cellulose composite nano-fiber membrane, to obtain the fiber membrane device.
2. preparation method according to claim 1, which is characterized in that the preparation method of the PLA supporter includes:
PLA wire rod is added in FDM printer, the conductive receiver plate in electrostatic spinning machine is fixed to the flat of the printer
Platform designs according to digital-to-analogue structure, the PLA supporter of honeycomb is printed on the conductive receiver plate.
3. preparation method according to claim 2, which is characterized in that the diameter of the PLA wire rod is 1.75~1.80mm,
And through 80~85 DEG C of 3.5~4h of drying process.
4. preparation method according to claim 2, which is characterized in that the parameter setting of the FDM printer is as follows: squeezing out
0.4~0.5mm of nozzle diameter, 192~196 DEG C of nozzle temperature, 30~40 DEG C of platform temperature, 0.2~0.3mm of lift height is filled out
Fill rate 100%.
5. preparation method according to claim 1, which is characterized in that in the composite spinning liquid, the nano-cellulose
Quality account for the 0.60-1.50% of the cellulose diacetate quality；With
The concentration of the cellulose diacetate is 10~13wt%.
6. preparation method according to claim 1, which is characterized in that the degree of substitution with acetyl group of the cellulose diacetate is
2.3~2.5, molecular weight is 39000~60000.
7. preparation method according to claim 5, which is characterized in that in the composite spinning liquid, the nano-cellulose
Quality account for the 0.60-0.75% of the cellulose diacetate quality.
8. preparation method according to any one of claims 1 to 7, which is characterized in that the preparation side of the composite spinning liquid
Method includes:
(1) bamboo pulp is added in TEMPO oxidation system, keeps pH to react 6.5~7.0h 10.2~10.5, obtains Nanowire
Tie up plain water slurry；The first organic solvent is added dropwise to the nano-cellulose water slurry and obtains nanofiber through rotary evaporation
Plain organic solvent suspension；
(2) cellulose diacetate is dissolved in the nano-cellulose organic solvent suspension, adds the second organic solvent,
Then 4~8h is stirred at normal temperature, and standing and defoaming obtains nano-cellulose/cellulose diacetate composite spinning liquid.
9. preparation method according to claim 8, which is characterized in that first organic solvent is dimethyl sulfoxide；
Second organic solvent is dimethyl sulfoxide and chloroform, and in the composite spinning liquid, dimethyl sulfoxide and three
The volume ratio of chloromethanes is (1~3): (1~2).
10. preparation method according to any one of claims 1 to 7, which is characterized in that the operation of the electrostatic spinning includes
Following steps:
The composite spinning liquid is poured into syringe, syringe needle internal diameter is 0.80~0.82mm, which is fixed on two pass
On micro-injection pump, injection speed control adjusts high pressure generator in 2~3mL/h, syringe needle and 14~16cm of receiver board distance,
Voltage is set to be maintained at 20~23kV, syringe needle drop quickly forms taylor cone, is formed and is received on the conductive receiver plate for have PLA supporter
Rice cellulose/cellulose diacetate composite nano-fiber membrane.
11. the fiber membrane device of adsorbable-desorption protein based on 3D printing PLA material, which is characterized in that wanted using right
Any one of 1 to 10 preparation method is asked to be made.
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