CN100364620C - Artificial blood vessel collagen pre-coagulation coating - Google Patents
Artificial blood vessel collagen pre-coagulation coating Download PDFInfo
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- CN100364620C CN100364620C CNB2006101122139A CN200610112213A CN100364620C CN 100364620 C CN100364620 C CN 100364620C CN B2006101122139 A CNB2006101122139 A CN B2006101122139A CN 200610112213 A CN200610112213 A CN 200610112213A CN 100364620 C CN100364620 C CN 100364620C
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Abstract
The invention discloses a pre-coating method of artificial vessel collagen, which comprises the following steps: synthesizing vessel prosthese through woven or knitted elastic porous pipe structure, coating the collagen liquid with elasticizer for at least three times, setting the collagen in the base bottom evenly, drying to fix the collagen through heat-hinging method.
Description
Affiliated technical field
The present invention relates to a kind ofly to can be used to replace, the pre-coagulation coating method of the artificial blood vessel prosthese of bypass graft or the arbitrary part of shunting human blood circulatory system, especially use and be mixed with the collagen solution coating artificial blood vessel prosthese of plasticizer, exempt pre-blood coagulation method of operating in the operation process thereby make it not leak blood.
Background technology
Using the lesion vessels of artificial blood vessel prosthetic replacement human body is a sophisticated surgical technic.Artificial blood vessel has many different types, and can be made of different materials.Artificial blood vessel prosthese that can implant into body normally is made of biocompatible materials, can keep the tubular-shaped structures of opening and allow the unblocked operation of blood flow wherein after blood vessel prosthesis is implanted simultaneously.Blood vessel prosthesis can be made of the biocompatible fibres material, as terylene or politef, by knitting or woven forming, can be monolayer or double-decker.
The basal layer of artificial blood vessel is to be made of porous fibre wall, porous structure is extremely important, because this can make artificial blood vessel keep enough sealings to be avoided severe loss of blood in operation process to blood, keep enough holes to allow fibroblast and smooth muscle cell intyrusive simultaneously, make receptor tissue wrap up the healing blood vessel prosthesis.Synthetic artificial blood vessel prosthese is at U.S.Pat.Nos.3,805,301 and No.4, and 047,252 is described as the extendible elastic tubular structure of polyester knitting.These blood vessel prosthesis possess enough holes and allow receptor tissue's intyrusive.But this type artificial blood vessel needs pre-blood coagulation operation when implanting.After implanting, blood vessel after pre-the coagulating just no longer leaks the intyrusive that blood does not hinder autologous tissue simultaneously yet.Yet the pre-step of coagulating is saved valuable operating time thereby surgical operation especially wishes during emergency operation to default when implanting artificial blood vessel.
In order to exempt pre-blood coagulation operation in the artificial blood vessel prosthese operation process, keep enough holes to be convenient to the intyrusive and the parcel healing artificial blood vessel of receptor tissue again.Many experiments when research improves artificial blood vessel and implants to the sealing of blood, common way uses the degradable biological material (as fibrin, albumin, gelatin or collagen (R.A.Jonas, F.J.Schoen, R.J.Levy and A.R.Castaneda, " Biologicalsealants and knitted Dacron:Porosity and histological comparisons ofvascular graft materials with and without collagen and fibrin gluepretreatments; " Ann.Thorac.Surg., 41,657-663 (1986); K.Kottke-Marchant, J.M.Anderson, Y.Umemura, and R.E.Marchant, " Effectof albumin coating on the in vitro blood compatibility of Dacron arterialprostheses, " Biomaterials, 10,147-155, (1989); R.Guidoin, D.Marceau, and J.Couture, " Collagen coating as biological sealants for textilearterial prostheses; " Biomaterials, 10,156-165, (1989))) coating dipping porous crack artificial blood vessel prosthese uses fixedly coating material of glutaraldehyde or formaldehyde crosslinking then.Artificial blood vessel after the coating dipping is also crosslinked no longer leaks blood (United States Patent 4,747,848, UnitedStates Patent 5108424) when implant into body.But there is experiment to show, use glutaraldehyde, after the blood vessel prosthesis of formaldehyde chemical crosslinking is implanted, the blood vessel prosthesis outer wall of pressing close to receptor tissue constantly discharges these chemical cross-linking agents, even dosage is very low, also can cause recipient cell toxic reaction and foreign body reaction and influence surrounding tissue blood vessel prosthesis intyrusive and biological healing (Speer DP, Chyapil M, Eskelson CD, Ulreich J, " Biologicaleffects of residual glutaraldehyde in glutaraldehyde-tanned collagenbiomaterials. " J Biomed Mater Res, 14,753-64, (1980)).
Summary of the invention
For overcoming above-mentioned difficulties, the present invention adopts the method for heat cross-linking to come crosslinked fixedly collagen protein after adopting degradable biological materials collagen solution coatings artificial blood vessel prosthese, avoided using the method for chemical crosslinking, eliminated recipient cell toxic reaction and antixenic generation thereby reach.This artificial blood vessel is coated with stain liquid is crosslinked by the fibrous material of tool biocompatibility porous crack tubulose synthetic vessel prosthese that constitutes and the collagen protein that is mixed with plasticizer and forms, and exempts pre-blood coagulation operation in the operation process thereby make the artificial blood vessel prosthese not leak blood.The porous crack basal layer of this tubular blood vessel prosthese can be to be made of terylene, can be knitting or woven forming.
Obtain highly purified collagen fabric dispersion liquid from the refinement of cattle heel string and by the method for saltouing.The high-purity collagen protein that is mixed with plasticizer is coated with stain liquid evenly is covered in the inner face of synthetic vessel prosthese basal layer, make the artificial blood vessel structure be full of elasticity and possess handling preferably and the extending longitudinally ability.At least use collagen protein to be coated with stain liquid coating 3 times, will be after the drying by the crosslinked fixedly collagen protein of the method for heat cross-linking.
In order to keep the artificial blood vessel prosthese under dry status, to keep enough softnesses and tool elasticity, before using collagen solution coating artificial blood vessel prosthese, must mix the plasticizer of glycerol, sorbitol or other tool biocompatibility.Collagen protein 1-5% in the mixed coating material, plasticizer concentration 6-20% (weight ratio).The ethanol that adds 10-25% simultaneously promotes the evaporation of moisture.
It is to make the seepage rate of vascular stroma of original multi-pore structure reduce to zero approximately that the artificial blood vessel of synthetic knitting or woven type uses being coated with of collagen protein and plasticizer to obtain most important characteristic after the stain liquid coating according to method of the present invention.The not terylene blood vessel of 20 synthetic woven types of coating is got in experiment in contrast at random, and average seepage rate is: 381.4 ± 12.3ml/min*cm
2, reduce to zero according to seepage rate after the coating of the present invention.
Thus, purpose of the present invention is the method that blood synthetic vascular prosthesis prosthese is not leaked in a kind of preparation.
Further purpose of the present invention provides and a kind ofly prepares collagen coating synthetic vessel prosthese and make it not leak the method for blood.
Other purpose and benefit of the present invention will be manifested in the explanation of following example clearly.
Relation between the feature that the present invention comprises, character and relative theory and operating procedure and each step will be set forth one by one in the details in the following instantiation, and scope of the present invention will illustrate in the claims.
Description of drawings
For a better understanding of the present invention, must be with reference to Figure of description and explanation
Fig. 1 is the transverse section that is coated with the linear artificial blood vessel prosthese part of stain liquid coating according to the collagen protein of method preparation of the present invention;
Fig. 2 is the part transverse section that is coated with the Y-shaped artificial blood vessel prosthese of stain liquid coating according to the collagen protein of method preparation of the present invention;
Fig. 3 represents that the seepage rate of artificial blood vessel prosthese is along with progressively reducing according to method utilization collagen coating increased frequency of the present invention.
The specific embodiment
According to the synthetic vascular prosthesis prosthese 01 of the present invention preparation as shown in Figure 1: comprise tubular structure main body 02, it is the Fiber Composite Material by the tool biocompatibility, especially polyethylene terephthalate, the multi-pore structure body that constitutes as polyester knitting or the woven substrate that forms 04.Just like U.S.Pat.No.4, the two-layer matte in the outside in description substrate 04 tool in 047,252.Except that terylene, tubular structure main body 02 also can be by knitting or woven the forming of other tool biocompatible fibres material, allows the intyrusive of organizing of receptor to keep open luminal structure to allow that blood flow is smooth and easy to be passed through simultaneously as long as make it possess mushy structure.Be covered with collagen protein at substrate 04 tube chamber inner face and be coated with stain liquid coating 06, collagen protein is coated with stain liquid coating 06 and need uses the mixing of collagen protein and plasticizer to be coated with stain liquid coating 3 times at least and fixedly form by the method for heat cross-linking is crosslinked.
Fig. 2 demonstrates the artificial blood vessel prosthese 12 that a Y-shaped collagen protein is coated with stain liquid coating, and blood vessel prosthesis 12 comprises main tubular structure 14 and two branch tubular bodies 16.Main tubular structure 14 and branch tubular body 16 are made of polyester knitting or the woven substrate that forms 18, and substrate 18 inboard mattes are covered with collagen protein and are coated with stain liquid coating 20, use collagen protein to be coated with stain liquid coating 3 times at least.
According to the artificial blood vessel prosthese substrate of multi-pore structure of the present invention by terylene by knitting or woven forming.Usually arrive 3000ml/min*cm by the knitting artificial blood vessel prosthese seepage rate scope that forms of terylene substrate 2000
2Between (water of clean filtering is under the 120mmHg condition), and by the woven seepage rate that forms of terylene 300 to 400ml/min*cm
2Between (water of clean filtering is under the 120mmHg condition).The proteic method of crosslinked with collagen is that the mixing with collagen protein and plasticizer is coated with stain liquid and evenly is coated with in the artificial blood vessel prosthese substrate, removes the excess coating material and place dry back crosslinked fixing by the method for heat cross-linking.Be coated with the seepage rate (unit/ml/min*cm of the artificial blood vessel of stain liquid coating according to the collagen protein of the present invention's preparation
2) approach zero.
Following example will illustrate collagen protein extraction and purification and process of being coated with stain liquid coating artificial blood vessel prosthese according to invention preparation collagen protein from the cattle heel string.The purpose of illustrative example is to set forth patent rather than limit its scope.
Example 1: the extraction of collagen liquid
The fresh bovine heel string is removed fat, fascia, under-10 ℃, be refrigerated to sclerosis, take out the remaining fascia that back reuse scalpel is rejected cattle heel string surface, be cut into the thin slice of 1mm * 1mm, weigh after the utilization distilled water washes repeatedly along the direction of cattle heel string fiber.With 0.1% (mass fraction) NaCO
3Solution soaking 2 hours with distilled water rinsing 5 times, with stainless steel cloth elimination aqueous solution, is dried, and puts into container, add respectively contain pepsin (with cattle heel string quality proportioning be 1: 10) 0.3% (mass fraction) acetic acid solution (pH=2-3) an amount of.Temperature control slowly stirs 3-5d between 0-4 ℃, uses High speed refrigerated centrifuge centrifugal with 200r/min then, gets supernatant and adds 1% (mass fraction) H
2O
2Solution leaves standstill 4h behind the mixing.Regulate pH value to 5 with 7% citric acid three sodium solution, filter precipitation, in rest solution, add sodium chloride, slowly stir, saltout.4 ℃ of standing over night, take out precipitation next day, soak 24h with Tris (pH=7) buffer down at 4 ℃, again precipitation is packed in the bag filter, be respectively 1%, 0.5%, 0.2% the acetic acid solution 1d that respectively dialyses with mass fraction, reuse distill water dialysis 3d changes dialysis solution every day 3 times, obtain the starchy high-purity collagen liquid of white smooth homogenizing at last, 4 ℃ of preservations.
Example 2: coating artificial blood vessel prosthese
The collagen protein mixing that will contain 2% collagen protein (extracting according to example 1) concentration from the cattle heel string is coated with stain liquid and fills with in the syringe of 50ml, this collagen protein mixing is coated with stain liquid and contains 12% glycerol simultaneously, 20% ethanol and distilled water, about 31,000 centipoises of viscosity.Syringe links to each other with synthetic woven artificial blood vessel one end, and the collagen protein mixing is coated with stain liquid and is pushed injection artificial blood vessel tube chamber and makes coating liquid evenly coat lumen wall, and unnecessary collagen protein mixing is coated with stain liquid and removes from the artificial blood vessel other end.Under the artificial blood vessel room temperature after the coating dry 1/2 hour, the coating drying is repeatable operation 3 times at least.
After the 3rd coating, make artificial blood vessel place vacuum drying oven crosslinked, temperature is controlled at 90-110 ℃, crosslinked 16-20 hour.
Example 3: blood penetration rate comparative measurements before and after the artificial blood vessel prosthese coating
The artificial blood vessel that does not leak the collagen coating of blood according to the method preparation of example 2 detects as follows, to randomly draw 5 diameters be the synthetic woven blood vessel after the 12cm coating for 8mm length and link to each other with blood reservior, under the pressure of 120mmHg, the blood of heparinization is passed through in blood vessel, collect the blood and the metering (unit: ml/min*cm of seepage
2).The blood penetration rate of 5 artificial blood vessels of testing result is respectively: 0.03,0.04,0.03,0.0 and 0.02, and the average blood permeability is 0.024ml/min*cm
2, approach zero.
For with the woven blood vessel of coating not relatively, choose not that the artificial blood vessel of coating repeats above-mentioned experiment, recording the average blood permeability is 27.8ml/min*cm
2
Example 4: seepage rate comparative measurements before and after the artificial blood vessel prosthese coating
Artificial blood vessel seepage rate after collagen protein is coated with stain liquid coating 3 times is reduced to below 1%.Seepage rate experiment (the R.Guidoin of standard, M.King, D.Marceau, and A.Cardou, " Textile arterial prostheses:Is water permeability equivalent to porosity? " J.Biomed.Mater.Res., 21,65-87 (1987)) measure as follows.The water column pressure that is equivalent to 120mmHg is by the circular hole of 2.44cm2 area, and the sample of artificial blood vessel prosthese is fixed in 1min on the circular hole, collects and also measures water amount of seepage.Each sample is measured respectively for several times, the following expression of measurement result:
Seepage rate (porosity)=ml/min*cm
2Synthetic woven blood vessel's seepage rate is 400ml/min*cm
2Change as follows through the seepage rate after the different number of times coatings:
| Be coated with hierachy | Seepage rate | |
| 0 1 2 3 4 5 6 | 400 92 47 2.5 1 0.3 0 |
All describe purification according to example 1 from the cattle heel string at the collagen protein that the coating each time of above-mentioned experiment is used, coating process is all described operation according to example 2.The result as shown in Figure 3.Based on this, preparing a collagen coating artificial blood vessel needs 3 coating collagen mixed liquid of protein at least, even 5 times and between each coating, need treat its drying, last crosslinked fixedly collagen protein is in artificial blood vessel substrate.
Compare with the artificial blood vessel of coating not, the artificial blood vessel of collagen coating has not only reduced seepage rate, and has reduced the thrombosis generation.Following example proof is compared collagen protein and is coated with the generation that stain liquid coating artificial blood vessel prosthese has significantly reduced thrombosis with matched group.
Example 5: thrombosis compares (experiment in vitro) before and after the artificial blood vessel prosthese coating
Adopt experiment in vitro (Imai Y, Nose Y. " A new method for evaluation ofantithrombogenicity of materials. " J Biomed Mater Res 6 (3): 165-72, (1972)) estimates the thrombosis ability of artificial blood vessel prosthese before and after the coating.CaCl with the citron acidemia mixing 0.1mmol/L of 0.25ml
225 μ l inject the artificial blood vessel prosthese lumen wall according to the collagen coating of example 2 preparations, and the artificial blood vessel prosthese lumen wall that the above-mentioned blood of same volume injects coating not in contrast.The 5ml distilled water of naming a person for a particular job in the time of 5,10 and 15 minutes respectively is poured over and stops Hirschfeld-Klinger reaction on the experiment sample, and the situation of the formation of each blood vessel prosthesis specimen observation thrombosis.The result shows that two groups of sample thrombosiss have the difference of apparent Russia work.Data are semi-quantitative parameters results that experiment obtains in the following form.
| The collagen coating group | Blank group | ||
| Blood soaks the speed of blood vessel prosthesis substrate | Hurry up | Slowly | |
| Each time point thrombosis | |
0 + ++ | ++ +++ ++++ |
Shown in form, the collagen coating group does not have fibrin clot at the 5min time point and forms, and forms at 15min time point collagen coating group fibrin clot equally significantly to be less than matched group.The artificial blood vessel prosthese of coating almost is not hydrophobic when contacting with blood, needs 11 to 15 seconds blood just to soak the fiber of woven artificial blood vessel, and that blood soaks the artificial blood vessel substrate of collagen coating is balanced and rapidly.
Based on above-mentioned experimental result, under the situation of external no blood, the terylene blood vessel prosthesis blood of collagen coating soaks rapidly, and no thrombosis forms in 5 minutes.Show thrombosis at same time point matched group blood vessel prosthesis.Thrombosis quantity time point collagen coating group blood vessel prosthesis formation in 10 and 15 minutes obviously is less than the blank group.
Example 6: thrombosis relatively (is tested in the body) before and after the artificial blood vessel prosthese coating
(hybrid dog) experiment is as follows in the collagen coating artificial blood vessel prosthese body.Under the general anesthesia between dog thigh arteriovenous implantable shunt pipe (use that 5cm long two is short to be conical puncture tube, be convenient to insert connect artificial blood vessel prosthese).After the blood vessel prosthesis connection is finished, slowly unclamp earlier the vascular occlusion clamp of vein end, and then slowly unclamp the blocking-up pincers of arterial end.Blood vessel prosthesis is taken off at blocking-up isocon two ends after making blood flow move 10 minutes and 30 minutes in blood vessel prosthesis.The blood that the blood vessel prosthesis intracavity is unnecessary is weighed after flowing out, and the thrombosis that the naked-eye observation lumen wall forms uses enough distilled water flushing blood vessel prosthesis (3 times) also to weigh once more then.
The terylene blood vessel of the 8mm diameter of the standard that matched group uses is being connected the pre-blood coagulation operation that moves ahead with thigh arteriovenous shunt pipe.Thrombotic vision of experiment and objective weight data evidence in the blood vessel prosthesis body so can be provided.The blood that leaks from the blood vessel prosthesis wall in the experimentation is collected equally and weighs and compares.
The artificial blood vessel of collagen coating does not have the blood seepage.And after organizing blood vessel and a strand arteriovenous shunt pipe in advance with fixed attention and being connected, in first 5 minutes, the average seepage 31ml blood of every 5cm blood vessel prosthesis.Second 5 minutes about 4-6ml.The pre-coagulation vessel follow-on test of matched group one example 30 minutes, the about 1.7ml blood of average every 5cm artificial blood vessel per minute seepage.
Collagenic coating artificial blood vessel prosthese implantable shunt pipe 10 and naked-eye observation in 30 minutes all do not have thrombosis and form.At the glossy thin fiber albumin layer of experimental group blood vessel prosthesis collagen coating surface coverage one smooth white, wash repeatedly and back wall energy in most blood vessel prosthesis is observed a successive fibrin thin film through distilled water, there is not the discovery of typical blood clot.
In pre-blood coagulation operational group 5 routine blood vessel prosthesis inwalls, there are 4 examples to observe tangible typical blood clot and form, the blood clot multidigit accounts for 1/3 to 1/2 of blood vessel prosthesis pipe week in the transverse section of blood flow direction.1 official holiday body inwall forms like fibrous albuminous coat structure in addition.May be because the blood leakage that blood vessel wall continues all has bigger blood clot to form at the every routine blood vessel prosthesis outer wall of matched group.
Based on above-mentioned experimental result, the dacron-made artificial blood vessel thrombosis of collagen coating generates and significantly is less than the pre-group of coagulating, this may be relevant with the generation of collagen protein anticoagulant minimizing thrombosis, and the purpose that is pre-blood coagulation operation simultaneously promptly is to need blood clotting to prevent the cause of blood vessel wall leakage blood.But blood clot participates in cell transition reaction hypertrophy and will be substituted by fibrocyte, is useful so minimizing dacron-made artificial blood vessel substrate blood clot forms what reduce vascular thrombosis and thromboembolism.
Substitute the artificial blood vessel prosthese of lesion vessels for implant into body, be coated with the artificial blood vessel prosthese at least 3 times of the synthetic woven tool multi-pore structure of stain liquid coating according to the mixing of method of the present invention utilization collagen protein and plasticizer, can make the blood vessel prosthesis feature obtain significantly to improve.The benefit of expection is not only and has been exempted the pre-blood coagulation operation in the operation process.Although many experiment confirm multi-pore structures to keep behind the artificial blood vessel implant into body long-term unobstructed be necessary, in operation process, must use patient's the capable pre-blood coagulation of blood to operate simultaneously and prevent to lose with a large amount of blood leakage of postoperative in the art.In fact, pre-blood coagulation is operated more consuming time and is needed certain skill and practical experience.Need emergency operation as the patient in addition or have the blood coagulation illness then to make the pre-blood coagulation difficulty that becomes maybe can't operate.
In sum, the artificial blood vessel prosthese of the synthetic woven tool multi-pore structure of the mixed liquor coating of collagen protein and plasticizer has been exempted intrusion and parcel growth that the pre-blood coagulation operation in the operation process provides ideal substrate to be convenient to receptor tissue simultaneously, in addition, thus the blood vessel prosthesis thrombosis behind the collagen coating generates obviously to reduce and has reduced artificial blood vessel and implant the danger that the back thromboembolism takes place.Synthetic weaving polyester artificial vascular according to the present invention use make behind the collagen coating its soft flexible possess handling preferably.
According to the method operation of above elaboration, the object of the invention can objective effective realization thus.But do not deviating under the spirit and scope of the invention situation, above-mentioned operation concrete steps and some clause can have certain change, therefore to describe some material of related method and use be to be used for demonstration to set forth invention for above-mentioned case description and accompanying drawing, and should not be construed as the scope that the restriction invention is contained.
Claims (7)
1. method for preparing artificial blood vessel's prosthese with pre-coagulation coating, described artificial blood vessel's prosthese with coating comprises artificial blood vessel's prosthese and the coating that is coated on artificial blood vessel's prosthese, coating material evenly is coated in artificial blood vessel's prosthese inwall, apply at least three times, dry then, heat cross-linking and make a kind of blood that do not leak and exempt the pre-artificial blood vessel's prosthese that coagulates operation immediately.It is characterized in that described artificial blood vessel is dacron, coating material contains collagen protein, plasticizer glycerol and sorbitol and short evaporant ethanol.
2. the method for preparing artificial blood vessel's prosthese according to claim 1, be characterised in that the coating solution that will contain collagen protein, plasticizer and short evaporant evenly is coated on artificial blood vessel's inwall, drying is carried out heat cross-linking then, obtains described artificial blood vessel's prosthese.
3. according to right 1 or the 2 described methods that prepare artificial blood vessel's prosthese, it is characterized in that plasticizer is selected from glycerol and sorbitol, short evaporant is selected from ethanol.
4. the method for preparing artificial blood vessel's prosthese according to claim 1 and 2 is characterized in that artificial blood vessel's prosthese made by biocompatible materials, and it is the synthetic textiles with elasticity porous crack cylinder structure, is knit type or woven type.
5. the method for preparing artificial blood vessel's prosthese according to claim 1 and 2, the concentration that it is characterized in that collagen protein is 1-5%, and the concentration of plasticizer is 6-20%, and short evaporant is 10-25%, and above concentration all is weight percentage.
6. the method for preparing artificial blood vessel's prosthese according to claim 1 and 2, wherein applying coating solution is at least 3 times.
7. the method for preparing artificial blood vessel's prosthese according to claim 1 and 2, the temperature of heat cross-linking are the 90-110 degree, and the heat cross-linking time is 16-20 hour.
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| CN104027844A (en) * | 2014-04-04 | 2014-09-10 | 张志辉 | Novel method for coating artificial blood vessel with Astragalus polysaccharide |
| CN106264779A (en) * | 2016-08-05 | 2017-01-04 | 江苏百优达生命科技有限公司 | A kind of artificial blood vessel with pre-coagulation coating |
| CN106237389A (en) * | 2016-08-05 | 2016-12-21 | 江苏百优达生命科技有限公司 | A kind of composite artificial blood vessel |
| CN108175874A (en) * | 2018-01-10 | 2018-06-19 | 深圳市第二人民医院 | Compound support frame material based on electrostatic spinning yarn and hydrogel and preparation method thereof |
| CN109330740B (en) * | 2018-09-18 | 2021-04-23 | 武汉纺织大学 | Method for reducing permeability of artificial blood vessel |
| CN114432499B (en) * | 2021-12-20 | 2023-02-17 | 浙江脉通智造科技(集团)有限公司 | Artificial blood vessel and preparation method thereof |
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| WO2003039613A1 (en) * | 2001-11-06 | 2003-05-15 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Synthetic vascular prosthesis |
| CN1169494C (en) * | 2001-05-23 | 2004-10-06 | 中国科学院化学研究所 | Cell scaffold with composite structure for tissue engineering and its preparing process and application |
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| CN1169494C (en) * | 2001-05-23 | 2004-10-06 | 中国科学院化学研究所 | Cell scaffold with composite structure for tissue engineering and its preparing process and application |
| WO2003039613A1 (en) * | 2001-11-06 | 2003-05-15 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Synthetic vascular prosthesis |
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