CN106188435A - Elastin laminin composite, Preparation Method And The Use - Google Patents

Elastin laminin composite, Preparation Method And The Use Download PDF

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CN106188435A
CN106188435A CN201610567455.0A CN201610567455A CN106188435A CN 106188435 A CN106188435 A CN 106188435A CN 201610567455 A CN201610567455 A CN 201610567455A CN 106188435 A CN106188435 A CN 106188435A
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egc
ppy
composite
brilliant glue
glue
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CN106188435B (en
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邢孟秋
商海涛
魏泓
蒋坤
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Wuhan Hualianke Biotechnology Co ltd
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Qianhai Shenzhen Jin Zhuo Biotechnology Co Ltd
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
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    • C08J3/00—Processes of treating or compounding macromolecular substances
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Abstract

The present invention relates to a kind of elastin laminin composite, Preparation Method And The Use.In particular it relates to a kind of elastin laminin composite crystal glue (elastin laminin gelatin CNT, EGC).Moreover, it relates to a kind of brilliant glue composite, it comprises polypyrrole (PPY) aggregation or the PPY contiguous network being carried on EGC.Moreover, it relates to their preparation method and purposes.

Description

Elastin laminin composite, Preparation Method And The Use
This application claims Chinese patent application excellent of Application No. 201610395996.X submitted on June 3rd, 2016 First weigh.
Technical field
The present invention relates to a kind of new elastin laminin composite, Preparation Method And The Use.
Background technology
Hydrogel has in tissue engineering and biological electronics and is widely used[1].At present, the extensive concern to them Concentrate on high-performance and New function, such as the stimulation-response performance of Drug controlled release[2], for biological electronics or life The conductivity of thing sensor[3], for conductivity and the elasticity of heart tissue engineering[4,5], presser sensor conductivity and for electricity The spontaneous recovery of sub-skin[6], for the substrate of oil/water separation[7], for the magnetic response of biological brake[8].Although having excellent biography The function water gel of the property led or magnetic response performance is widely used, but still has some in some fields by flexible, elastic and response The restriction that sensitivity deficiency causes, such as high flexibility electronic equipment, organic pressure sensitive sensors and response executor.They faces Face the similar challenge highly conductive property or magnetic response character and high flexibility and elasticity combined.
It was recently reported that some syringes-injectable macropore flexible netted electronic equipment, reflect the bioelectronics of manufacture The prospect without operation transplantation of equipment[9], but the most do not report syringe-injectable huge electronic equipment of prefabricated 3D.Although report Some macropore crystalline substance glue such as such as alginate, gelatin, chitosan and hyalomitome acid crystals glue have high flexibility and syringe-can note Penetrating property, they the most do not have conductivity[10,11], because introducing such as CNT (CNT) and polypyrrole (PPY) etc. there is conduction Property rigid components reduce their flexibility by strengthening the hardness of hydrogel simultaneously[12]。
In pressure sensitive sensors field, develop several method, such as hollow-spheroid compression resistance film sensing Device[13], nanowires of gold compression resistance film sensors[14], polydimethylsiloxane (PDMS)/CNT (CNT) nanometer sheet sensing Device[15]With nano wire matrix membrane sensor[16], but these technology run into Similar Problems: complicated manufacturing process, high cost and having The conductivity of limit.Additionally, they are the 2D film for electricity dermal application rather than the huge pressure sensing of 3D for some environment Device.Report some conductivity hydrogels, but the good elasticity of compression/resistance and pressure-responsive are not conducted by these hydrogels Property combines[17,18]。
Additionally, report the magnetic hydrogel that can respond quickly to external magnetic field, it delivers medicine/thin by remote boot server Born of the same parents, it is at about 38A/m2Magnetic field gradient under can reach about 70% deformation[19].Also manufacture and good conductivity and magnetic have been rung 3D Graphene/ferrum oxide the aeroge that should combine is for soft executor or the potential application of micro switch, and it is at 1.2T magnetic There is under field intensity 52.3% radial strain[20].But, the modest magnetic field of as little as 0.2T to 3T is more can be used for common facing Bed environment, andLow-field MRI be commonly applied to MRI[21], the most in actual applications remote boot server need more flexible and Sensitive magnetic response hydrogel.
Good with high flexibility and elasticity to conductivity or magnetic responsiveness can be combined thus it still remains a need a kind of New composite.
Summary of the invention
A first aspect of the present invention provides a kind of elastin laminin composite crystal glue (EGC), it include elastin laminin, gelatin and CNT.Wherein, " brilliant glue " refers to the continuous gel-type vehicle with the macropore being interconnected.
In one embodiment of the invention, elastin laminin composite crystal glue include 30-60 weight portion elastin laminin, The gelatin of 30-80 weight portion and the CNT of 10-80 weight portion.In one embodiment, elastin laminin and the ratio of gelatin It is 30/70 to 70/30, such as 30/70 to 50/50.This elastin laminin is selected from Elastin peptide, tropoelastin or digestion bullet Property albumen.In one embodiment, elastin laminin and gelatin are by methacrylated modification.In one embodiment, Methacrylated reagent is methacrylic anhydride.In one embodiment, this elastin laminin is methacrylate grafting Elastin laminin.In one embodiment, this gelatin is methacrylate grafted gelatin.In one embodiment, described EGC also includes stabilizer, the stabilizer of such as 30-80 weight portion.This stabilizer can be amphipathic copolymer, such as polyoxy second Alkene-polyoxypropylene polyoxyethylene (PEO-PPO-PEO) three amphipathic copolymer of block, such as F-127-DA.An embodiment In, this stabilizer passes through acryliated modification.In one embodiment, acrylated reagent is acryloyl chloride.In the present invention An embodiment in, elastin laminin composite crystal glue includes the elastin laminin of 15 weight portions, the gelatin of 35 weight portions, 17.5 weights The CNT of amount part and the stabilizer of 17.5 weight portions.
The SEM morphology of EGC hydrogel demonstrate similar to cellular macroporous structure (Fig. 1 (e1)) and have 60～ The pore-size distribution of 130 μm and the interconnectivity higher than 99%, it can allow deformation and Quick drainage, and by CNT (5mg/ ML, ultimate density) it is embedded in the mesh grid of substrate layer (as from Fig. 1 (e2)).Described ultimate density refers to prepare water-setting During glue, CNT finally accounts for the concentration of hydrogel.
Present invention also offers a kind of method preparing EGC, described method includes:
A elastin laminin, gelatin, CNT and stabilizer are mixed by () in aqueous；
B () adds polymerization initiator at low temperatures in said mixture, make mixture cross-link；
C () makes products therefrom solidification in step (b) at low temperatures, to form EGC.
In one embodiment of the invention, in the step (a) of the inventive method, by the elasticity of 30-60 weight portion The stabilizer of albumen, the gelatin of 30-80 weight portion, the CNT of 10-80 weight portion and 30-80 weight portion mixes in aqueous Close.In one embodiment, elastin laminin and gelatin are by methacrylated modification.In one embodiment, methyl Acrylated reagent is methacrylic anhydride.In one embodiment, this elastin laminin is methacrylate grafted elastomeric Albumen.In one embodiment, this gelatin is methacrylate grafted gelatin.In one embodiment, this stabilizer Being amphipathic copolymer, the amphipathic copolymer of such as PEO-PPO-PEO tri-block, such as F-127-DA.In one embodiment, Described stabilizer passes through acryliated modification.In one embodiment, described polymerization initiator includes Ammonium persulfate. (APS), For example, APS and tetramethylethylenediamine (TEMED).In one embodiment, the solidification of step (c) continues 1-24h, such as 16h。
In one embodiment, step (a) is to carry out at low temperatures, such as, carry out at a temperature of 0-15 DEG C.One In individual embodiment, step (b) is carried out at 0-15 DEG C.In one embodiment, step (c) is carried out at-30-0 DEG C, excellent Select-20 DEG C.
A second aspect of the present invention provides a kind of brilliant glue composite, and it includes EGC and is carried on polypyrrole thereon (PPY).In one embodiment, the weight ratio of EGC Yu PPY is about 1:0.15-0.7.
In one embodiment, it is loaded with scattered polypyrrole aggregation (EGC-PPY-FD) at EGC.An enforcement In scheme, scattered polypyrrole aggregation is evenly dispersed on described brilliant glue.This scattered polypyrrole aggregation can be by fast Speed crosslinking deposits and is deposited on EGC by polypyrrole aggregation.In one embodiment, Quick cross-linking deposition is by by molten Pyrrole monomer in liquid absorbs on EGC, and causes pyrrole monomer polymerization quick in situ to be formed at by Ammonium persulfate. (APS) On EGC, the polypyrrole aggregation (EGC-PPY-FD) being supported on EGC with formation.In one embodiment, at EGC-PPY- In FD, the weight ratio of EGC Yu PPY is about 1:0.15-0.30, such as 1:0.23-0.29, such as 1:0.26.
In another embodiment, the network structure of described EGC forms continuous print polypyrrole network structure.Specifically For, rigidity PPY composition forms the second network (EGC-PPY-SA) on soft support.Now, define there is soft-hard co-continuous The brilliant glue composite of network structure.In one embodiment, this composite is by Quick cross-linking, the most aging The network structure of described brilliant glue forms continuous print polypyrrole network structure and is formed.In one embodiment, described Composite is by being absorbed on EGC by pyrrole monomer, and adds Fe (NO3)3Cause pyrroles to cross-link, make residue not subsequently The pyrrole monomer of polymerization is by Fe (NO3)3Slowly oxidation polymerization is to form contiguous network structure in the network structure of described brilliant glue. In one embodiment, the concentration of the pyrrole monomer in solution is 3mg/mL-18mg/mL, such as 6.7mg/mL-13.4mg/ ML, such as 13.4mg/mL.In one embodiment, in EGC-PPY-SA, the weight ratio of EGC Yu PPY is about 1:0.32- 0.70, such as 1:0.32-0.50, such as 1:0.38.
In one embodiment, the pore-size distribution of the EGC-PPY-FD formed is 50～140 μm, and it is similar to EGC Pore-size distribution, and the pore-size distribution of EGC-PPY-SA is 20～60 μm.
The scattered PPY aggregation of EGC load shows highly flexible and syringe-injectable character and medium biography The property led.On the other hand, when rigidity PPY composition forms the second network on soft support, there is soft-hard co-continuous network structure Brilliant glue show simultaneously can bear up to 97.5% compression strain outstanding high resiliency and under 90% strain up to 50.1 ± 2.9S/ The prominent conductivity of cm and good presser sensor conductivity.
Present invention also offers the method preparing EGC-PPY-FD, it includes being soaked in pyrroles's aqueous solution EGC, and adds Enter polymerization initiator (such as APS), so that pyrrole monomer polymerization, and in-situ deposition is on the supporting structure of EGC, to form EGC- PPY-FD.In one embodiment, this reaction is carried out at low temperatures, such as, carry out at 0-15 DEG C.A reality Executing in scheme, the concentration of the pyrrole monomer in solution is 3mg/mL-18mg/mL, such as 6.7mg/mL-13.4mg/mL, as 6.7mg/mL。
Present invention also offers the method preparing EGC-PPY-SA, it includes being soaked in pyrroles's aqueous solution EGC, and adds Enter Fe (NO3)3Cause pyrroles to cross-link, make the unpolymerized pyrrole monomer of residue by Fe (NO subsequently3)3Slowly oxidation polymerization with Contiguous network structure is formed in the network structure of EGC.Generally, Fe (NO is added3)3Causing pyrroles to cross-link is at low temperatures, such as Carry out at 0-15 DEG C.Aging (such as Fe (NO3)3Slowly oxidation) can at room temperature continue 4 hours to 3 days, preferably 8 hours to 3 My god, and preferably 8 hours, 16 hours, 1 day, 2 days and 3 days.
A third aspect of the present invention provides a kind of brilliant glue composite (EGC-IONP), and it includes EGC and is carried on EGC On Iron oxide magnetic nanoparticles (IONP).In one embodiment, EGC-IONP comprises the elastic egg of 30-60 weight portion In vain, the gelatin of 30-80 weight portion, the CNT of 10-80 weight portion, the Iron oxide magnetic nanoparticles of 30-120 weight portion and The stabilizer of 30-80 weight portion.In one embodiment, EGC-IONP comprises the elastin laminin of 50 weight portions, 50 weight portions Gelatin, the CNT of 20 weight portions and the Iron oxide magnetic nanoparticles of 120 weight portions.In this application, iron oxide magnetic nano Granule is commercially available, it would however also be possible to employ prepared by technology commonly used in the art.In one embodiment, it also includes poly-pyrrole Cough up, the polypyrrole of e.g., from about 30-80 weight portion.In one embodiment, this PPY uses and sinks with Quick cross-linking like above Amass and be deposited in EGC-IONP (EGC-IONP-PPY-FD).
Present invention also offers a kind of method preparing EGC-IONP, described method includes:
A elastin laminin, gelatin, CNT, Iron oxide magnetic nanoparticles and stabilizer are mixed by () in aqueous；
B () adds polymerization initiator at low temperatures in said mixture, make mixture cross-link；
C () makes products therefrom solidification in step (b) at low temperatures, to form described composite.
In the step (a) of the method, can be by the elastin laminin of 30-60 weight portion, the gelatin of 30-80 weight portion, 10-80 The stabilizer of the CNT of weight portion, the Iron oxide magnetic nanoparticles of 30-120 weight portion and 30-80 weight portion is water-soluble Liquid mixes.In one embodiment, elastin laminin and gelatin are by methacrylated modification.An embodiment In, methacrylated reagent is methacrylic anhydride.In one embodiment, this elastin laminin is that methacrylate connects Branch elastin laminin.In one embodiment, this gelatin is methacrylate grafted gelatin.In one embodiment, should Stabilizer is amphipathic copolymer, and the amphipathic copolymer of such as PEO-PPO-PEO tri-block, such as F-127-DA.An enforcement In scheme, described stabilizer passes through acryliated modification.In one embodiment, described polymerization initiator includes Ammonium persulfate. (APS), such as APS and TEMED.In one embodiment, the solidification of step (c) continues 1-24h, such as 16h.
In one embodiment, step (a) and step (b) are carried out respectively at 0-15 DEG C.In one embodiment, Step (c) is carried out at-30-0 DEG C, preferably-20 DEG C.
Present invention also offers a kind of method preparing EGC-IONP-PPY-FD, its by PPY by described above quickly Crosslinking deposits and is deposited in EGC-IONP, to form EGC-IONP-PPY-FD.
The invention still further relates to EGC, EGC-PPY-FD, EGC-PPY-SA, EGC-IONP and EGC-IONP-PPY-FD for The purposes of oil/water separation, the manufacture of artificial heart, biosensor, teleoperator or biological brake etc..
The invention still further relates to a kind of supercompression electric conductivity and magnetic response gel robot, it includes main body and is connected to it On three to eight side arms composition.In one embodiment, this teleoperator is artificial Octopus robot.An enforcement In scheme, described material of main part is EGC-IONP composite, such as EGC-IONP-PPY-FD.In one embodiment, described Main body can be polyurethane sponge.Or, described main body can be magnetic hydrogel, such as EGC-IONP composite.An enforcement In scheme, described artificial Octopus robot can use magnetic field be controlled and operate.
The invention still further relates to a kind of biological brake, this biology brake includes EGC-IONP composite.A reality Executing in scheme, this biology brake is made up of EGC-IONP composite.In one embodiment, this biology brake conduct Circuit changing switch.In one embodiment, when magnetic field application thereon time, this biology brake is transformed into from open mode Closure state, or it is transformed into open mode from closure state.
The invention still further relates to a kind of oil/water isolation medium, it includes EGC-PPY composite as above.At one In embodiment, described oil/water isolation medium is EGC-PPY-FD.The invention still further relates to a kind of chromatograph separated for oil/water Post, wherein the oil/water isolation medium in chromatographic column includes EGC-PPY composite as above.
Accompanying drawing explanation
Fig. 1 is showing the most elastic, shape memory character and the figure of their form of EGC-PPY crystalline substance glue.(a1) Bear the EGC before compression (30) (elastin laminin/gelatin=30/70)-PPY-SA；(a2) EGC (the 30)-PPY-of compression is born SA；(a3) the quick resilience of EGC (the 30)-PPY-SA after compression is cancelled.(b1) drain water EGC (30)-PPY-SA without extensive Multiple deformation；(b2) EGC (the 30)-PPY-SA draining water is immersed in the water again；(b3) EGC (30)-PPY-SA recovers shape. (c1) EGC (the 30)-PPY-FD hydrogel of deformation is taken out；(c2) EGC (30)-PPY-FD hydrogel；(c3) EGC deformed (30) the shape memory sexual behaviour that-PPY-FD hydrogel slowly recovers in water.(d1) there is the EGC of " U " or " M " shape (30)-PPY-SA hydrogel；(d2) EGC (the 30)-PPY-SA hydrogel after deformation；(d3) before returning to deformation in water EGC (the 30)-PPY-SA hydrogel of " U " or " M " shape.(e1) SEM image (amplification 95 times) of EGC (30) hydrogel； (e2) demonstrate that CNT is embedded in the SEM image (amplification 23000 times) of EGC (30) hydrogel of substrate layer.(f1) by quickly The SEM image (amplification 190 times) of the EGC hydrogel (EGC (30)-PPY-FD) of the PPY coating of crosslinking；(f2) it is display PPY Aggregates of nanoparticles dispersed and distributed SEM image (amplification 11000) on EGC (30) hydrogel.(g1) by the oldest The SEM image (amplification 800 times) of the EGC hydrogel (EGC (30)-PPY-SA) of the PPY coating changed, (g2) shows PPY nanometer Granule is the image (amplification 13000 times) of the PPY network that the development of formation of deposits is good on support.(h1) 10 times are followed Ring, under 80% compression strain, the shape memory strain fixed rate of EGC (30)-PPY-SA is with the change of cycle-index；(h2) The shape recovery ratio of EGC (30)-PPY-SA is with the change of cycle-index.
Fig. 2 is showing the figure of the engineering properties of EGC crystalline substance glue.A (), under the speed of 20mm/min, has 80% strain EGC (30), EGC (30)-PPY-FD, EGC (30)-PPY-SA, elastin laminin, gelatin and the compression stress of gelatin-CNT hydrogel Strain curve.B () strains 80% under, elastin laminin/gelatin mass fraction on the impact of their mechanical strength (note: Before reaching 80% strain, EGC (0) partial rupture).(c) under the compression speed of 20mm/min and (d) 200mm/min, for The load-deformation curve of EGC (the 30)-PPY-SA hydrogel under the strain of 100 circulations 80%.E () is under 2mm/min, right In 5 circulations, the stress-strain cycle curve of EGC (the 30)-PPY-SA hydrogel under 97.5% Large strain.F () is at 24h Afterwards, under 2mm/min speed, for 5 circulations, second compression-off-load fortune of same sample under the Large strain of 97.5% OK.G () is respectively subjected to the photo of EGC (the 30)-PPY-SA of the compression strain of 0% and 97.5%.
Fig. 3 is the figure of the rheological property of brilliant glue.(a)EG(30)、(b)EGC(30)、(c)EGC(30)-PPY-FD、(d) EGC (50), (e) EGC (50)-PPY-FD and (f) EGC (30)-PPY-SA hydrogel.(g1)-(g3) is that tool is figurate The injectable behavior of EGC (50)-PPY-FD conductivity hydrogel.
Fig. 4 is the conductive figure of presser sensor. (a1)-(a3) shows and gradually deforms along with EGC (30)-PPY-SA, The presser sensor behavior that the light intensity of LED gradually steps up.B the circuit of (): (a1)-(a3) illustrates.(c1) EGC (30) deformed- PPY-SA hydrogel is as " ON/OFF " contactor；(c2) display is by adding DD water restorable EGC (30)-PPY-SA Hydrogel switch is by circuit communication, and LED is luminous；(c3) display only uses DD water that LED can not be made luminous.(d): (c1)-(c3) Circuit illustrate.(e) EGC (30), EG (50)-PPY-FD, the conductivity of EGC (50)-PPY-FD and EGC (30)-PPY-SA, logical Cross what 4 probe numeral conductivity testers (n=3 (positive direction) and n=3 (negative direction)) detected.(f) EGC (30)-PPY-SA's Apparent resistance cyclic test spectrogram (50% strain, 20mm/min).The conductivity of (g) EGC (30)-PPY-SA-compression strain spectrum Figure, is detected by 4 probe numeral conductivity testers (n=3 (positive direction) and n=3 (negative direction)).
Fig. 5 is the figure of the separation of O/w emulsion.The separation of (a) plant O/w emulsion.Emulsion before (b) separation The optical microscope image of the emulsion after optical microscope image and (c) separation.Statistical analysis (the n=of (d) droplet size 4992).E () vegetable oil does not flows in EGC (the 30)-PPY-FD hydrogel of compression, but water flows in the hydrogel of compression immediately.
Fig. 6 is the magnetic response behavior of the brilliant glue comprising IONP.A () strains 80% under, IONP ultimate density is to EGC (50) impact of-IONP compressive strength.B (), under 20mm/min speed, is circulated for 10 times, and the stress of EGC (50)-IONP- Cyclic Strain curve (20mg/mL).The high flexibility of (c) EGC (50)-IONP and compressibility.(d) under the magnetic field of weak applying, by The artificial Octopus robot that EGC (50)-IONP makes.The e long-range conductivity of EGC (50)-IONP-PPY-FD that () is controlled by magnetic field Biological brake.
Fig. 7 is the schematic diagram preparing Multifunctional elastic albumen crystalline substance glue.Including high flexibility, injectable, shape memory, biography EGC-PPY-FD, EGC-PPY-SA and EGC-IONP-PPY crystalline substance glue of the property led, presser sensor, oil-water separation and magnetic response character Manufacture.
Fig. 8 is the diagram of the high resiliency mechanism of EGC-PPY-SA crystalline substance glue under compressive stress.
Fig. 9 is that 0.5mg pyrroles is as outer target methacrylated gelatin (gelatin-MA, 12mg)1H H NMR spectroscopy.Base In gelatin-MA and the concentration of pyrroles, rubbing of methacrylate can be calculated by comparing the peak intensity at 5.4ppm and 5.65ppm You measure, and belong to the proton of methacrylate, and the peak intensity at 6.2ppm and 6.9ppm is from pyrroles's external standard.Methyl in gelatin The value of calculation of acrylate amount is 0.02285mol every 100g gelatin.
Figure 10 is the methacrylated elastin laminin (elastin laminin-MA, 18.8mg) of 0.5mg pyrroles1H NMR Spectrum.Based on elastin laminin-MA and the concentration of pyrroles, methyl-prop can be calculated by comparing the peak intensity at 5.4ppm and 5.65ppm The mole of olefin(e) acid ester, belongs to the proton of methacrylate, and the peak intensity at 6.2ppm and 6.9ppm is from pyrroles's external standard. In gelatin, the value of calculation of methacrylate amount is 0.02285mol every 100g gelatin.
Figure 11 is F-127 diacrylate1H H NMR spectroscopy.
Figure 12 is to pass through CDCl3From Fe (NO3)3The pyrroles's of the residual of the slow aging reaction extraction caused1H H NMR spectroscopy (DMSO is external standard, 0.29mg/mL).Wherein, can be according to the residual concentration of following equation calculating pyrroles:
The mole of the pyrroles of residual
=(intensity6.84ppm+ intensity6.27ppm)/4 × (intensity2.6ppm/ 6) × (0.00029/78.13) × 67.09,
Wherein, 78.13 is the mole of DMSO.And 67.09 be the mole of pyrroles.
Aliquot volume based on the reaction solution for extraction and the CDCl characterized for NMR3Aliquot volume, Ke Yiji Calculating reaction conversion ratio is 96%.
Figure 13 is to pass through CDCl3From the pyrroles's of the residual of pyrroles's fast deposition reaction, extraction of APS initiation1H H NMR spectroscopy (DMSO is external standard, 0.29mg/mL).
Figure 14 is the figure of the statistical analysis in brilliant glue aperture.The brilliant glue of (a) EGC (30), average pore size, 90 ± 14 μm, (b) EGC (30)-PPY-FD, average pore size, 98 ± 19 μm, (c) EGC (30)-PPY-SA, average pore size, 39 ± 8 μm.
Figure 15 is GC (30), the performance map of EGC (30)-PPY-FD and EGC (30)-PPY-SA.Wherein (a) is water content, B () is expansion rate (volume prepared by sample is 360 μ l).Note: do not consider PPY weight when calculating expansion rate.
Figure 16 is that the frequency with the different slowly EGC crystalline substance glue of aging technique time sweeps collection rheology spectrum.(a)EGC(30)- 0h, (b) EGC (30)-PPY-SA-8h, (c) EGC (30)-PPY-SA-16h, (d) EGC (30)-PPY-SA-1d, (e) EGC (30)-PPY-SA-2d and (f) EGC (30)-PPY-SA-3d crystalline substance glue.
Figure 17 is under speed 20mm/min, the image of gelatin-CNT and EGC after bearing 80% strain.
Figure 18 is the compression-unloading cyclic stress-strain curve of EGC (30)-PPY-SA.(a) 50% strain, 20mm/ Min, (b) 50% strain, 200mm/min, (c) 70% strain, 20mm/min, (d) 70% strain, 200mm/min, (e) 80% Strain, 200mm/min and (f) 80% strain, 20mm/min.
Figure 19 is the figure of the engineering properties of matched group PEG-diacrylate-elastin laminin-CNT EGC crystalline substance glue.In speed There is under 20mm/min PEG, PEG-CNT (5mg/mL) of 80% strain, PEG-EL (30)-CNT (5mg/mL), PEG-EL (30) the compression stress strain curve of-CNT-PPY-FD and PEG-EL (30)-CNT-PPY-SA crystalline substance glue.
Figure 20 is for 100 circulations, and the compression of PEG-EL (30)-CNT-PPY-SA-unloading Rotation permutations is bent Line, 80% strain, 20mm/min.
Figure 21 is the oleophobic property under water of the EGC-PPY using the different soluble organic solvent of water (density > 1.0).(a) chlorine Imitative, (b) dichloromethane and (c) Carbon bisulfide.(by different colours dyeing organic solvent).
Detailed description of the invention
In order to realize high flexibility and the elastic target combined with excellent conductive or magnetic response behavior, applicant Find that using the high flexibility of the function nano composition with high capacity amount and elastic support is effective ways.Water solublity elastin laminin (such as Elastin peptide, tropoelastin or digestion elastin laminin) is good high resiliency support material standed for, but it lacks machine Tool intensity[22].But, it is rarely employed elastin laminin crystalline substance glue, because its bad mechanical strength and pass through ice in freezing gel The brilliant big pore morphology produced that formed even reduce further mechanical strength[10,23,24]。
Applicant has been surprisingly found that use high water soluble Elastin peptide crystalline substance glue (EGC crystalline substance glue) and has obtained super flexible Support, it is strengthened further by compound with the CNT of gelatin, excellence and biocompatibility gelatinous mass and high loading[25].Soft Property Elastin peptide and gelatin chain can form the network of rigidity CNT microcell and flexibility/flexible polymer coil bridge to obtain with rigidity CNT Obtain high resiliency[26].Additionally, the CNT of hydrogel middle and high concentration can form network to improve the conductivity in support[4,27]。
Then, it is supported on high conductance polypyrrole nano components on EGC support to obtain excellent conductivity, wherein PPY morphology plays pivotal role to the macroscopic property of brilliant glue[28].When EGC loads scattered PPY aggregation, brilliant glue shows Highly flexible and syringe-injectable character and medium conductivity.When rigidity PPY composition forms the second network on soft support Time, the brilliant glue with soft-hard co-continuous network structure shows the outstanding high resiliency that can bear paramount 97.5% compression strain simultaneously Prominent conductivity and good presser sensor conductivity with paramount 50.1 ± 2.9S/cm under 90% strain.
Applicant prepares EGC-IONP and EGC-IONP-PPY with by high flexibility, sensitivity, conduction also by same procedure Property combine with magnetic response character, display as long-range and soft executor or machine human potential.It has been found that EGC- PPY hydrogel is the ideal chromatography post separated for " oil-water "[24]。
In this application, (elastin laminin-MA hydrolyzes from cattle paxwax can to pass through methacrylated Elastin peptide The most methacrylated), the brilliant gel of methacrylated gelatin (gelatin-MA) and many walls CNT prepare EGC hydrogel.Logical Cross F-127-DA polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO) three block amphipathic copolymer to be disperseed by CNT Time in water, hydrophobic PPO block will be assembled and had the non covalent hydrophobic interaction with CNT and hydrophilic PEO chain molten Extending in liquid and with gelatin-MA and elastin laminin-MA covalent bonding to form hydrogel, it will increase CNT and water-setting gum base The affinity of matter.Evaluate the affinity of CNT and hydrogel matrix by 48h immersion test in distilled water (DD water) and pass through UV-vis measures, its display > 99.9%CNT is stable in hydrogel[27].Therefore, by the hydrophobic PPO bag serving as physical crosslinking agent The CNT microcell enclosed can form the elastomeric network (CNT preparation process) with soft elastin laminin/gelatin/PEO polymer line bridge.? PPY coating on frame deposits (EGC-PPY-FD) or (2) Quick cross-linking, the most aging (EGC-by (1) Quick cross-linking PPY-SA).In the technique of EGC-PPY-FD, the pyrrole monomer absorbed in EGC hydrogel is caused, assembles, is settled out also And quick in situ absorbs on EGC support to form scattered PPY aggregation.Quick cross-linking deposition can be carried out at low temperatures, Such as carry out at 0-15 DEG C.In EGC-PPY-SA technique, by insufficient amount of Fe (NO3)3Causing pyrroles, its residue is not gathered The monomer closed is for by (NO3)3Slowly oxidation polymerization allows PPY to form contiguous network structure and slow process on support With the more intermolecular hydrogen bondings between gelatin/elastin substrate interact[29,30].In EGC-PPY-SA technique, quickly Crosslinking can be carried out at low temperatures, such as, carry out at 0-15 DEG C, aging can at room temperature carry out.
Embodiment
Method
Experimental section
Material: water solublity Elastin peptide (Elastin Products Company, CB573, molecular weight be 1000 to 60000Da.These peptides comprise cross-linking amino acids desmosine and isodensmosine, and repeat peptide Val-Gly-Val-Ala-Pro- Gly), gelatin (type A, Sigma Aldrich).Every other chemicals be purchased from Sigma Aldrich, and directly use and It is not further purified.
Embodiment 1: the synthesis of methacrylate grafted gelatin (gelatin-MA).
According to document disclosed above[25], by being combined with primary amine group, methacrylic acid ester group is introduced to gelatin Skeleton.Say briefly, at 50 DEG C, the type A gelatin of 2g is dissolved in 20mL PBS (1 ×), then by the methyl of 2mL Acrylic anhydride (MA) adds to gelatin solution and stirs 1hr at 50 DEG C together.After reacting, the PBS of 100mL is fallen Enter with dilute solution in reactor, and at 40 DEG C, use 10kDa MWCO Dialysis tubing DD H2O is by gelatin solution dialysis 5 My god.Finally, reclaiming white porosity foam by lyophilization at-45 DEG C, yield is 85%.
Embodiment 2: the synthesis of methacrylate grafted elastomeric albumen (elastin laminin-MA).
The preparation of methacrylate grafted elastomeric albumen (elastin laminin-MA) is similar to the program of foregoing description, but Whole reaction occurs in ice bath.Briefly, in ice bath, the elastin laminin of 2g is dissolved in 20mL PBS (1 ×) In, then the methacrylic anhydride (MA) of 2mL added to elastin laminin solution and in ice bath, stir 8hr together.Instead Ying Hou, at 4 DEG C, uses 1000Da MWCO Dialysis tubing DD H2Solution is dialysed 48h, and lyophilizing at-45 DEG C, yield by O It is 40%.
The synthesis of embodiment 3:F-127-diacrylate.
By using the acrylated F-127 of acryloyl chloride (PEG-b-poly-(propylene glycol)-b-PEG) to close Become F-127-diacrylate.Briefly, in ice bath, by the triethylamine of F-127 and 0.061g of 2.54g (0.2mmol) (0.6mmol) it is dissolved in 20mL anhydrous methylene chloride and advertises degassing 20min by nitrogen.Then, under nitrogen protection, will 0.05mL acryloyl chloride (0.6mmol) is slowly injected in solution.By solution stirring 24hr, and reaction temperature is risen to naturally room Temperature.After the reaction, remove solvent by rotary evaporation, and dialyse 3 days by having the Dialysis tubing DD water of the MWCO of 3.5kDa By product purification, and reclaimed by lyophilization.Reclaiming white solid, yield is 2.06g (81%).
NMR characterizes.Bruker Avance 300MHz NMR spectrometer owns1H NMR tests, and by relaxation Postpone (relaxation delay, d1) and be set to 2 seconds.With the concentration of 10mg/mL, sample is dissolved in D2O.A large amount of pyrroles are added Add in the NMR solution of gelatin-MA and elastin laminin-MA as external standard for quantitatively grafting on gelatin or elastin laminin The amount of methacrylate.All NMR data see accompanying drawing.
The preparation of embodiment 4:EGC.
Previously prepared at DD H2The 50mg/mL stock solution of the gelatin-MA in O and the 50mg/mL storage of elastin laminin-MA Standby solution, and store in refrigerator before use.By 100mg multi-walled carbon nano-tubes (MWCNT), 100mg F-127-DA and 10mL DD H2O adds by probe sonication ripple homogenizer supersound process 4h to 50mL plastic tube and in ice bath, and locates before use Manage other 1h.In typical preparation, in ice bath, by the elastin laminin-MA (50mg/mL) of 30 μ l, the gelatin-MA of 70 μ l (50mg/mL), the DD H of 75 μ l2The CNT solution of O and 175 μ l is sufficiently mixed.Then, the 10%TEMED aqueous solution of 5 μ l is added With 200mg/mL Ammonium persulfate. (APS) aqueous solution of 5 μ l in succession mixing in ice bath, and with pipettor, solution is aspirated to tool (reverse 1.5mL EP tank or 96-orifice plate) good seal in the mould of body, and in order to store 16hr at being solidificated in-20 DEG C.Then, DD water is used to wash hydrogel (being expressed as EGC (30), elastin laminin/gelatin=30/70) several times thoroughly to remove desalination.With shifting Liquid device draw 90 solution produced above for μ l to 1.5mL EP pipe and at-20 DEG C solidification prepare injectable sample.Preparation has 720 μ l sample solutions of the compression-unloading cyclic test for 97.5% strain of same concentrations and ratio.
According to three groups of lyophilizing samples (3 × 360 each group of μ l), the actual weight of EGC crystalline substance glue (from 360 μ l solution) is 7.1±0.1mg.By UV-vis spectrum (Ultrospec 4300pro, UV/ visible spectrophotometer) detection CNT and water-setting The affinity of gel matrix.Use DD water by the sample cyclic washing of selection several times to remove any salt and impurity from reaction.So After, respectively those samples (volume: 360 μ l) are immersed in 48h in 2mL DD water, and water keeps colourless after 48h, collects it 1mL aliquot sample be used for UV visible light analysis, use CNT dilute solution (1mg/mL, 0.1mg/mL, 0.01mg/mL and 0.001mg/mL) as standard.After 48h, it is retained in hydrogel more than 99.9%CNT.
Identical method is used to be prepared for the EGC crystalline substance glue (EGC (50)) of elastin laminin/gelatin=50/50.
The preparation of embodiment 5:EGC-PPY-FD.
EGC (30) hydrogel (7.1mg) of preparation in embodiment 4 is immersed in 6.7mg/mL (0.1mol/L) pyrrole of 4mL Cough up in aqueous solution, and pour 1mL APS (89.6mg/mL, 0.4mmol) aqueous solution in chromium solution (actual pyrrole in ice bath Coughing up concentration is 0.08mol/L).After 30min, reaction is stopped and using DD water thorough washings gel.According to three groups of lyophilizing Sample (3 × 360 each group of μ l), the actual weight (from 360 μ l solution) of EGC-PPY-FD crystalline substance glue is 9.0 ± 0.2mg.Water-setting PPY load capacity on glue is 5.2 ± 0.4mg/mL.
The preparation of embodiment 6:EGC-PPY-SA.
EGC (30) hydrogel (7.1mg) of preparation in embodiment 4 is immersed in 13.4mg/mL (0.2mol/L) pyrrole of 2mL Cough up in aqueous solution, and by the Fe (NO of equivalent in ice bath3)3Aqueous solution (0.2mol/L, 80.8mg/mL) is poured in chromium solution. Solution is sufficiently mixed and hydrogel is compressed and discharges several times so that chromium solution absorbs to the support of hydrogel.By solution At room temperature store 3d, and EGC-PPY hydrogel is removed, and use DD H2O thoroughly washs.The sample tool used in Figure 16 There is different soak times, including 8h, 16h, 1d, 2d and 3d.According to three groups of lyophilizing samples (3 × 360 each group of μ l), EGC- The actual weight (from 360 μ l solution) of the brilliant glue of PPY-SA (3d) is 9.8 ± 0.4mg.PPY load capacity on hydrogel is 7.4 ±1.2mg/mL.PPY and the affinity of hydrogel matrix is evaluated by the same procedure for CNT, and after 48h > 99.9%PPY is retained in substrate.
The preparation of embodiment 7:IONP nano-particle.
By FeCl in round-bottomed flask3(0.81g, 5mmol) and FeCl2·4H2O (0.5g, 2.5mmol) is dissolved in 10mL DD Seal in water and by rubber spacer cap.By nitrogen, solution is advertised 20min thoroughly to remove air.At another flask In, by same procedure, 20mL 2M ammonia aqueous solution is deaerated, and at room temperature stir under 750rpm high stir speed (S.S.).So After, under nitrogen protection, by 10mL syringe, iron salt solutions is transferred in ammonia spirit.After 1h, reaction is stopped also Collect black solid by bar magnet, use water by its cyclic washing thoroughly to remove ammonia and salt.Moist, by black gains It is transferred in 50mL centrifuge tube and adds DD water to obtain 5mL aqueous mixture altogether, and adding 0.2g F-127-diacrylate Ester.In ice bath, by probe sonication ripple homogenizer by mixture supersound process 2h, then 0.1mL aliquot sample is transferred to It is dried overnight in EP pipe and under vacuum drying oven.Dry weight based on product, calculates the concentration (yield: 0.64g) of IONP.Will be another Outer 0.44g F-127-diacrylate adds to pipe and adds extra 0.33mL DD water to reach 120mg/mL's IONP/F-127 concentration.Before use, by other for solution supersound process 10h in ice bath.
Embodiment 8:EGC-IONP and the preparation of EGC-IONP-PPY-FD.
The preparation of EGC-IONP is similar with EGC crystalline substance glue.In typical preparation, in ice bath, by the elastic egg of 100 μ l The IONP of-MA (50mg/mL), the gelatin-MA (50mg/mL) of 100 μ l, the CNT solution (10mg/mL) of 200 μ l and 200 μ l is molten in vain Liquid (60mg/mL) is sufficiently mixed, and then, adds 10%TEMED aqueous solution and the 200mg/mL Ammonium persulfate. of 10 μ l of 10 μ l (APS) aqueous solution in succession mixing in ice bath, and with pipettor, solution is drawn to 1mL syringe cylinder and good seal, for 16hr is stored at being solidificated in-20 DEG C.Can with different scales but same ratio prepares sample.Then, use DD water by hydrogel Washing is several times thoroughly to remove desalination.Hydrogel is immersed in 13.6mg/mL (0.2mol/L) pyrroles's aqueous solution, and in ice bath Pouring in solution by 2mL APS (44.8mg/mL) aqueous solution, the time is 20min, uses DD water thoroughly to wash the EGC of acquisition (50)-IONP-PPY-FD crystalline substance glue.4 EGC (50)-IONP hydrogels (about 2cm length) are adhered to a piece of by superglue Polyurethane sponge prepares artificial Octopus robot.In Fig. 6 (a), by using 90mg/mL and 120mg/mL IONP aqueous solution Prepare the IONP crystalline substance glue of 30mg/mL and 40mg/mL ultimate density, by the F-127-diacrylate of same concentrations, it is steady Fixed.IONP and the affinity of hydrogel matrix is evaluated by the same procedure for CNT, and after 48h > 99.9%IONP guarantor Stay in substrate.
The method being described as follows according to the sample of the present invention made above is analyzed.And retouch referring to the drawings State beneficial effects of the present invention.
PPY fast deposition ease up slow aging deposition conversion ratio.
By using DMSO as outer target1After H NMR detection reaction, the pyrroles of residual calculates conversion ratio.Owing to pyrroles exists Water has limited dissolubility, but uses a large amount of organic solvents of such as ether, chloroform solvable.Can be extracted by organic solvent Unreacted pyrroles characterizes for NMR.For slow aging reaction, respectively by the pyrroles of 6.9 μ l (6.7mg) in two EP pipes With 40.4mg Fe (NO3)3It is dissolved in 0.5mL D2O, and in ice bath, two solution are mixed 4h the most altogether Store 3d.Transparent for 0.5mL supernatant is transferred to another EP pipe, and uses 0.3mL chloroform-d (CDCl3) wash 5 times with extraction Take unreacted pyrroles.Take out 750 μ L aliquot sample and with as outer target 10 μ l DMSO/CDCl3Solution (22mg DMSO/ 1mL CDCl3) mix to implement1H NMR characterizes.Fast deposition is reacted, ice bath will contain the pyrroles of 6.9 μ l (6.7mg) 1mL D2O and 250 μ l APS/D2O solution (89.6mg/mL) mixing 30min.Black PPY aggregation suspends in the solution, logical Cross the syringe filtering aaerosol solution being equipped with 0.45 μm PDFE filter disc.The clear solution of 0.5mL is transferred to another EP pipe And by 0.3mL CDCl3Extract 5 times.Take out 750 μ L aliquot sample and with as outer target 10 μ l DMSO/CDCl3Solution (22mg DMSO/1mL CDCl3) mix to implement1H NMR characterizes.
SEM characterizes.
First by hydrogel sample lyophilizing, the thin layer with sputtering coating gold it is then loaded on metal sample container for table Levy.In JEOL-5900 scanning electron microscope, embodiment characterizes, and uses the running voltage of 20eV.By image J software The aperture information of statistical analysis crystalline substance glue.
Compression test and cyclic test.
According to such scheme, prepare the water with disk geometry (4～5mm height, 8mm diameter) the most in a mold Gel sample.Under the speed of 20mm/min, implement compression test until 80% compression strain.Be equipped with a pair compression plate and The universal tensile testing machine (Instron 5965) of 500N load elements is upper implements compression cyclic test.Before the test, in compression Drip on platform a water, and the hydrogel sample selected is respectively subjected to the compression strain of 50%, 70% or 80%, then exists Discharge to 0% under the constant rate of speed of 20mm/min or 200mm/min, repeated 100 times with detection compression performance and hydrogel Recovery.The cyclic test of the maximum strain for having 97.5%, it is (mutually same that height of specimen is respectively 9.8mm with 9.1mm Product, but have some permanent deformations), and compression speed is 2mm/min.
Shape memory sexual behaviour.
EGC (the 30)-PPY-SA hydrogel with the initial length of 10mm is used for measuring.The initial gage length table of sample It is shown as L1.By sample compression to 80% strain under speed 20mm/min, and the gauge length compressed is L2.Sample is kept 1min under this strain, and the water extruded thoroughly absorbs on napkin, then makes sample not have any load time to be 5min, Measure fixing gauge length as L3.Then, sample is immersed in water and is used for again being hydrated 5min, and measure recovery Gauge length is as L4.Those gauge lengths are measured, by little for data round numbers to three by the clearance distance of two compression plates Number (mm) (automatically measures L by instrument2, and by using exact position knob regulation clearance distance manual measurement L1、L3And L4, And actual minimum step is 0.003～0.005mm).Shape memory fixed rate and recovery rate is calculated according to following equation.
Maximum compression strains: εm=(L1–L2)/L1× 100%
Fixing strain: εu=(L1–L3)/L1× 100%
Overstrain: εp=(L1–L3)/L1× 100%
Strain fixed rate: Rf=εu/εm× 100%
Strain recovery rate: Rr=(εm-εp)/εm× 100%
Rheological charactristics.
At 25 DEG C, the steel parallel-plate of 8mm diameter geometry is used to find to carry out all stream on compound rheological instrument at TA Become and learn oscillation experiment.In vibration-frequency experimentation, sample is made to bear the shearing accelerating to 200rad/s from 0.1rad/s slowly Speed, has the constant strain of 0.5%.
Conductivity measurement.
Under the current range of 0.1 μ A to 100mA, by having the ST-2258C numeral of linear probe (2.0mm interval) The sheet resistance of 4-test instrument probe (Suzhou Jingge Electrical Co., Ltd.) detection hydrogel sample.In inspection Before survey, it is necessary to by all samples cyclic washing to remove the initiator of residual.Conductivity can be calculated by equation σ=1/ ρ.? Detect each sample under the compression strain of 70%, and calculate the average result of three values of detection under positive current and at negative current The average result of three data of lower acquisition.Detect under the different compression strains of 10%, 30%, 50%, 70% and 90% with The data of 4g meter.
The resistance detection of pressure correlation.
The platform of indoor construction detects pressure-responsive conductivity, including Instron compression test platform, high sensitivity Digital multimeter and related software, conduction copper cash and insulating tape.Discharge, directly by sample compression and under speed 20mm/min To the maximum strain of 50%.
Plant O/w emulsion separates.
96 orifice plates using the diameter with about 6.5mm prepare sample as mould, and program is same as described above.At dress After carrying PPY, crystalline substance glue laminated is reduced in 1mL syringe cylinder (outlet diameter is 2mm).By mixing 0.5mL vegetable oil and 9.5mL DD water prepares O/w emulsion, and supersound process 10mins together.Aperture by image J software statistics credit crystallize glue Information.By 5 separation detection flows on phase isomorphous glue, each 0.8mL emulsion flows through brilliant glue (2mm diameter exit), and Before reuse, the brilliant glue of washing in the vessel comprising DD water.
Material EGC, EGC-PPY-FD, EGC-PPY-SA, EGC-IONP, the EGC-related in description referring to the drawings IONP-PPY-FD all uses the concrete grammar described in above example to prepare, and is prepared as according to the particular content of experiment Corresponding shape.Wherein EGC (30) and EGC (50) represents material elastase/gelatin=30/70 or 50/50 respectively.
With reference to Fig. 1
In order to obtain shape memory character, hydrogel should have (i) macropore spongy architecture to allow water freely to flow Enter/flow out, the favorable elasticity that highly polar and (iii) that (ii) absorbs for water recovers for shape[31].In the present invention, by Highly polar in the macroporous structure of EGC-PPY-FD and EGC-PPY-SA and PPY, two kinds of EGC-PPY hydrogels show good bullet Property and shape memory sexual behaviour.The SEM form of EGC hydrogel demonstrate similar to honeycomb sample macroporous structure (Fig. 1 (e1)) and Having the pore-size distribution of 60～130 μm and the interconnectivity higher than 99%, it can allow deformation and Quick drainage, and will CNT (5mg/mL, ultimate density) is embedded in substrate layer, such as the mesh grid from Fig. 1 (e2).After the coating of PPY, EGC (30)-PPY-FD and EGC (30)-PPY-SA both of which keeps the macroporous structure similar with EGC (30) (Fig. 1 (f1) and (g1)), But the pore-size distribution of EGC (30)-PPY-FD is 50～140 μm, it is similar to EGC crystalline substance glue, and the distribution of the latter is drop dramatically to 20 ～60 μm, show EGC (30)-PPY-SA have accumulated more PPY.Fig. 1 (f2) and (g2) show that PPY nano-particle gathers respectively The PPY network that in the dispersed and distributed of collective or support, the development of formation of deposits is good.Develop the formation of good PPY network by flowing Change frequency of oscillation is swept collection experiment (rheology oscillation-frequency sweeping experiment) and is entered one Step confirms.Additionally, along with the increase of the slow ageing time of PPY, storage modulus substantially increases, and slow deposition two days it After, storage modulus G in frequency range ' often higher than loss modulus G " and do not intersect, show the biggest at high shear rates The dynamic mechanical properties of scale allosteric rearrangement and EGC (30)-PPY is arranged by PPY rigidity network, and forms soft-hard doubly-linked Continuous structure (Figure 16).
Additionally, with reference to (a1)-(a3) in Fig. 1, when EGC (30)-PPY-SA cylinder bears compression stress, and macropore support becomes Shape and expressed water, to discharge stress, absorb water simultaneously and recover immediately, as shown in Figure 1a when cancelling stress.Can from Fig. 1 b To find out, when removing water, EGC (the 30)-PPY-SA (using same method to prepare) of deformation loses its elasticity and protects Hold deformation, but when reusing water, recover its original geometry structure immediately, show shape memory sexual behaviour.By (1) single shaft Compression sample reaches 80% strain, and (2) water absorbs water to keep deformation by napkin, and (3) remove load 5min and (4) by sample weight Newly it is immersed in the water 5min for recovering to evaluate further the shape-memory properties of this EGC (30)-PPY-SA.Calculate 10 circulations Strain fixed rate and strain recovery rate, as described in detail at experimental section.Due to PPY rigidity network, when removing load, pressure The hydrogel of contracting somewhat recovers, and fixed rate is about 88～90%.When being again immersed in water, shape is in about 0.3 second Recover, and recovery rate is maintained at about 99% after 10 circulations, shows good shape memory (Fig. 1 (h1) and (h2) )[32].Fig. 1 c shows the similar shape memory sexual behaviour of this EGC (30)-PPY-FD, and it has slower recovery rate.Can will be somebody's turn to do EGC (30)-PPY-SA hydrogel is molded as " U " and the letter of " M ", can use water by its fast quick-recovery, as shown in Figure 1 d.
With reference to Fig. 2
In order to detect the high elastic of EGC-PPY hydrogel, compare EGC (30), EGC (30)-PPY hydrogel (EGC (30)-PPY-FD and EGC (30)-PPY-SA) and control sample, including elastin laminin, gelatin and the pressure of gelatin-CNT hydrogel Contracting performance, wherein proof resilience albumen/gelatin concentration is identical.In Fig. 2 (a), pure gelatin hydrogel has higher compressive strength, But under 75% strain, produce local mechanical fracture.By adding CNT (5mg/mL), the machinery of gelatin-CNT composite aquogel is strong Degree sharply increases, but compression stress diminishes.And Elastin peptide hydrogel only has the ultralow machine of 0.9kPa under 80% strain Tool intensity.Therefore, introduce elastin laminin and drastically reduce the mechanical strength (elastin laminin/gelatin=30/70) of EGC (30) extremely 11.4kPa, and under 80% strain, elastin laminin-base composite aquogel does not the most have any mechanical breaking, even if existing Rigidity PPY layer and CNT composition.There is scattered PPY aggregation coating or continuous P PY network, EGC (30)-PPY-FD and EGC (30)-PPY-SA shows that the compressive strength of 26.7kPa and 58.4kPa does not has any fracture under 80% strain respectively, increases by 2 Times or 5 times.In order to confirm that the elasticity increased, owing to Elastin peptide, uses PEG-diacrylate by same procedure inspection (700) matched group of gelatin is replaced.PEG crystalline substance glue shows highly flexible but has less compression stress and mixing with CNT Miscellaneous (ultimate density of 5mg/mL) produces fracture, but shows the rubber elastic behavior (Figure 19) similar to elastin laminin and PPY.Fig. 2 B () display elastin laminin peptide components reduces brilliant glue mechanical strength, and EGC (70) when there is 5mg/mL CNT to a miracle Only having the intensity of 2.0 ± 0.4kPa, the total concentration of its elastase/gelatin is 5mg/0.35mL.
In order to use fast quick-recovery and stable macropore conductivity hydrogel to evaluate high resiliency further, 100 times are followed Ring, this EGC (30)-PPY-SA crystalline substance glue bears 80% deformation respectively under the speed of 20mm/min and 200mm/min.200mm/ The hydrogel of the high compression rate requirement deformation of min can recover rapidly in 1.08s.As shown in Fig. 2 (c) and 2 (d), two should Power-strain spectrum shows similar closed curve.After 100 times circulate, for 20mm/min rate recovery loss 8.8% and right Lose 13.8% in 200mm/min rate recovery, and hydrogel still keeps good shape and elasticity, shows its stability With the potential application in heart tissue engineering.Under relatively low strain dynamic, this sample shows preferable stability and elastic performance, There is less recovery and lose (Figure 18).For 5 circulations, when EGC (the 30)-PPY-SA crystalline substance glue of same preparation is at 2mm/min Speed under bear 97.5% supertension shrinkage strain time, when for the first time circulation, it is high that compressive strength jumps to 6348.6kPa Value, as shown in Fig. 2 (e).After circulating at 5 times, under 97.5% strain, the recovery loss of compressive strength is 26.8% and sample is high Spend and be contracted to 8.6mm (12.2% deformation) from 9.8mm, but brilliant glue keeps overall shape not have any obvious fracture, shows PPY The limited local fracture of layer.The sample being immersed in water recovers to 9.1mm, has 7.1% permanent deformation, and examines after 24h Look into the second compression cyclic test of the strain with up to 97.5%.Enjoyably, the compressive strength under 97.5% strain is recovered extremely 6014.5kPa, and after 5 times circulate, the recovery loss of compressive strength is only 14.6%, as shown in Fig. 2 (f).In circulation After test, sample have other 0.5mm shrink (5.5%), but in water soak after stay less than 0.1mm permanent deformation (< 1% permanent deformation).Showing the outstanding elasticity of EGC-PPY-SA crystalline substance glue, it can use 6.35Mpa stress to provide the compression of 97.5% Strain and brilliant glue support keep good, only have the limited local fracture of rigidity PPY layer.
With reference to Fig. 3
Sweep the detection of collection method by vibration-frequency and evaluate elastin laminin-gelatin (EG (30)), EGC (EGC (30) and EGC ) and the dynamic mechanical properties of EGC-PPY (EGC (30)-PPY-SA, EGC (50)-PPY-FD and EGC (30)-PPY-FD) (50). According to Fig. 3 (a), along with the increase of shear rate, between storage modulus and loss modulus vestige, there is intersection, be reflected in high shear Long range molecular motion under speed and extensive allosteric rearrangement and show high flexibility and the injectable character of EG (30) hydrogel. Fig. 3 (b) and 3 (c) show EGC (30) support and the rheological properties of EGC (30)-PPY-FD, wherein G ' and G " substantially increase, but Despite the presence of desired rigidity CNT and PPY, still have the similar transition under high-rate of shear, show they highly flexible and can Injection behavior.Rigid components only strengthens brilliant glue, but engineering properties is still arranged by soft support.EGC (50) and EGC (50)-PPY-FD Show similar rheological behavior and be intended as EGC (30) and EGC (30)-PPY-FD, but less storage modulus.So And, for EGC (30)-PPY-SA, G ' and G " the two almost increases an order of magnitude, but G " always less than G ', show EGC (30)-PPY-SA is due to rigidity PPY networks forfeit injectable character.Correspondingly, EGC (50)-PPY-FD shows its injectable Character, as shown in Fig. 3 (g).Pin (ID 1.6mm) can be passed through injected by figurate for this tool conductivity hydrogel, and very The fast original shape recovering it.On the contrary, EGC (30)-PPY-SA can not be injected into, but has significantly higher elastic modelling quantity and tool There is the high resiliency of quick recovery properties.
With reference to Fig. 4
Fig. 4 (a) display deforms with hydrogel, and LED changes its light intensity, shows that the pressure of EGC (30)-PPY-SA is quick Sense conductivity, it can be used as potential source biomolecule sensor.In order to show conductivity and the shape memory sexual behaviour of gel further, as Shown in Fig. 4 (c), by adding DD water, EGC (the 30)-PPY of deformation recovers the original-shape to it, and when the water-setting recovered During glue bridgt circuit, LED bulb is lighted, but pure DD water individually can not illuminate bulb.In order to evaluate presser sensor conduction further Property, Fig. 4 (e) provides EGC (30), EG (50)-PPY-FD, EGC (50)-PPY-FD and EGC (30)-PPY-SA hydrogel Conductivity.Under the compression strain of 70%, CNT mesh network provides 0.004 ± 4.4 × 10 to EGC hydrogel-5The biography of S/cm The property led, but, the conductivity of EGC (the 50)-PPY-FD hydrogel comprising PPY and CNT rise two orders of magnitude reach 0.375 ± The value of 0.024S/cm.CNT network structure, EG (50)-PPY-FD is not had only to have the value of 0.00758 ± 0.00199S/cm.Companion With the formation of the good PPY network of development, under 70% strain, the conductivity of EGC (30)-PPY-SA hydrogel is increased significantly to 14.7±1.4S/cm.Owing to material has uneven cross section, conductivity is that strain is relevant, therefore for pressure correlation.Figure The real-time apparent resistance spectrum of EGC (the 30)-PPY-SA of 50% compression strain is born in 4 (f) display repeatedly, circulates its display good every time Good strain dependency and comparable resistance.The highest resistance not having strain and real time resistance is expressed as R0And R, And pass through R/R0Calculate relative resistance, its under strain is directly proportional and strains 50% with hydrogel close to 25% initial value. According to the compressive stress strain curve of EGC (30)-PPY-SA, pressure sensibility (Δ R/R0Every kPa) it is about 0.086 every kPa.
Excellent elasticity and stress/strain dependency resistance show that the EGC hydrogel that PPY loads can be that the huge pressure of 3D rings The good candidate of induction sensor[13].Fig. 4 g provides the conductivity vs. strain spectrum of EGC (30)-PPY-SA, itself and non-linear increasing Add, for best sample, it is thus achieved that the high conductance of 50.1 ± 2.9S/cm under 90% strain, according to we grasp optimal Knowledge, its top is between current conductivity pressurized water gel[18,33]。
With reference to Fig. 5
As document is reported, grid or the filter paper substrate of the coating of the most superoleophobic hydrogel separate for oil/water[34].This That invents has intrinsic interconnecting macroporous structure and the brilliant glue of oleophobic property PPY coating under water[29,35]Can also be used for Oil-water separation and do not have There is porous support.When plant O/w emulsion (5:95, v:v) is by being filled with the injection of EGC (the 30)-PPY-FD crystalline substance glue of compression During device, the most transparent water flows through brilliant glue, as shown in Figure 5 a.By the inspection of optical microscope, there are 1～28 μm grains after filtration The oil droplet of degree distribution is wholly absent, as shown in Fig. 5 b～5d.The oleophobic property of the brilliant glue of Fig. 5 e display, wherein vegetable oil cannot flow into pressure EGC (the 30)-PPY-FD hydrogel of contracting.Separating power is higher than 99% and flow can reach 404 ± 101L/hr m2(n= 5)。
With reference to Fig. 6
Considering high flexibility and the elasticity of compression of EGC, it can be the good candidate of magnetic response material, rings with the magnetic above reported Answering alginate-ferrum oxide tempering gel phase ratio, it has the modulus of 55～60kPa and at about 38A/m under 80% strain2 Applying magnetic field gradient under show about 70% deformation[19].EGC (50)-ferrum oxide (IONP) is prepared brilliant according to embodiment 8 Glue, wherein by the Fe of 20mg/mL (ultimate density)3O4Nano-particle is introduced to EGC (50), but its compression under 80% strain Intensity is only 5.1 ± 1.2kPa, and the brilliant glue with 40mg/mL IONP only has the value of 11.8 ± 2.4kPa, and display has The high flexibility of the IONP of high carrying capacity, as shown in Fig. 6 (a) and (b).From Fig. 6 (c), under the low-intensity magnetic field of constant bar EGC (50)-IONP (20mg/mL) magnetic hydrogel cylinder shows super flexible, and it is easily bent to 180 °, and this external 1mL injects In the constrained environment of device bucket, flexural deformation restricted and when putting in magnetic field along direction of principal axis whole hydrogel cylinder by gently Minute-pressure is reduced to the strain of about 45%.Fig. 6 (d) display high flexibility and sensitive property become the simulation controlled by the magnetic field applied Artificial Octopus robot.After coating PPY, EGC (50)-IONP-PPY-FD keeps high flexibility and flexible under magnetic field To 90 °, it may act as the long-range conductivity biology brake controlled by the magnetic field applied, as shown in Fig. 6 (e)[20,36]。
Therefore it may be concluded that water solublity elastin laminin peptidyl crystalline substance glue macropore support load there is conductive rigidity High resiliency, injectability and shape memory character can be combined by PPY or IONP with conductivity or magnetic properties.Institute There are the excellent elasticity of EGC hydrogel display that PPY coats, flexibility, conductivity that shape memory sexual behaviour is relevant with stress.Especially Ground, when EGC support loads scattered PPY, generation have the excellent flexibility of figurate conductivity hydrogel display and Injectable character, shows that it is potential as syringe-injectable biosensor or biological electronics；Along with EGC-PPY is soft-hard The formation of co-continuous network, product display high elastic modulus and the outstanding elasticity with fast quick-recovery, have under 90% strain The excellent conductive of 50.1 ± 2.9S/cm, and even can bear the compression of 97.5%, show for heart tissue engineering Learn material or the good candidate of presser sensor biosensor.Magnetic response hydrogel EGC-IONP also keeps high flexibility and shows Sensitive magnetic response behavior, and can be used as biological brake.
Those skilled in the art it is to be understood that can in any combination between each feature above-mentioned, and this group Close the most within the scope of the present application.Artisan will appreciate that without departing from appended claims of the invention institute The change made in the case of the scope and spirit of the present invention disclosed and retouching, all belong to the protection model of the claim of the present invention Within enclosing.
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Claims (13)

1. an elastin laminin composite crystal glue, it includes elastin laminin, gelatin and CNT, the most described elastin laminin and Described gelatin is by methacrylated modification.
2. elastin laminin composite crystal glue as claimed in claim 1, it also includes stabilizer.
3. a brilliant glue composite, it includes the brilliant glue described in claim 1 or 2 and is carried on polypyrrole thereon.
4. brilliant glue composite as claimed in claim 3, is wherein loaded with scattered polypyrrole aggregation on described brilliant glue.
5. brilliant glue composite as claimed in claim 3, wherein forms the poly-pyrrole of continuous print in the network structure of described brilliant glue Cough up network structure.
6. a brilliant glue composite, it includes the brilliant glue described in claim 1 and the iron oxide magnetic being carried on described brilliant glue Property nano-particle.
7. brilliant glue composite as claimed in claim 6, it is additionally included on described composite the polypyrrole of load.
8. brilliant glue composite as claimed in claim 7, is wherein loaded with scattered polypyrrole on described composite and gathers Collective.
9. the method preparing brilliant glue described in claim 1, described method includes:
A elastin laminin, gelatin, CNT and stabilizer are mixed by () in aqueous；
B () adds polymerization initiator at low temperatures in said mixture, make mixture cross-link；
C () makes products therefrom solidification in step (b) at low temperatures, to form the brilliant glue described in claim 1.
10. the method preparing brilliant glue composite described in claim 3, described method includes
(a) in accordance with the method for claim 9, to prepare the brilliant glue described in claim 1,
B described brilliant glue is soaked in pyrroles's aqueous solution by (), and add the second polymerization initiator, so that pyrrole monomer polymerization, and In-situ deposition is on the supporting structure of described brilliant glue, to form the scattered polypyrrole aggregation being carried on described brilliant glue；Or Person
(a1) in accordance with the method for claim 9, to prepare the brilliant glue described in claim 1,
(b1) described brilliant glue is soaked in pyrroles's aqueous solution, and adds Fe (NO3)3, make pyrrole monomer be polymerized, the most aging also In-situ deposition is on the supporting structure of described brilliant glue, to form continuous print polypyrrole network knot in the network structure of described brilliant glue Structure.
11. methods as claimed in claim 10, wherein the second polymerization initiator in step (b) is ammonium sulfate.
The method of 12. 1 kinds of composites prepared described in claim 6, described method includes:
A elastin laminin, gelatin, CNT, Iron oxide magnetic nanoparticles and stabilizer are mixed by () in aqueous；
B () adds polymerization initiator at low temperatures in said mixture, make mixture cross-link；
C () makes products therefrom solidification in step (b) at low temperatures, to form described composite.
13. methods as claimed in claim 12, described method also includes:
The composite of step (c) gained is soaked in pyrroles's aqueous solution, and adds the second polymerization initiator, so that pyrroles is single Body is polymerized, and in-situ deposition is on the supporting structure of described composite, is carried on the dispersion on described composite to be formed Polypyrrole aggregation.
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