CN102068323A - Cardiac or vascular patch with anticoagulant effect - Google Patents
Cardiac or vascular patch with anticoagulant effect Download PDFInfo
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- CN102068323A CN102068323A CN2011100242558A CN201110024255A CN102068323A CN 102068323 A CN102068323 A CN 102068323A CN 2011100242558 A CN2011100242558 A CN 2011100242558A CN 201110024255 A CN201110024255 A CN 201110024255A CN 102068323 A CN102068323 A CN 102068323A
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Abstract
The invention discloses a cardiac or vascular patch with an anticoagulant effect. The surface of a substrate of the patch is modified on the surface of the woven polyamide (PA), polyethylene terephthalate (PET) or polytetrafluoroethylene (PTFE) substrate for artificial blood vessels by a coprecipitation method, and nanometer polyurethane (PU) microspheres of which the surfaces are modified by phosphorylation and which have the diameters of between 100 and 300nm into the surface of the substrate of the patch through a binder, namely polyurethane (PU), wherein the concentration of the nanometer PU microspheres is between 0.3 and 1.0mg/cm<2>. The cardiac or vascular patch has remarkable anticoagulant effect when keeping excellent mechanical properties, flexible performance and bending performance of the substrate of the patch.
Description
Technical field
The present invention relates to a kind of medical material heart or vascular patch, especially relate to a kind of heart or vascular patch with anticoagulant effect.
Background technology
Heart or vascular patch are the medical materials of often using in the operations such as congenital heart disease.The heart sticking patch is the repairing operation that is used for repairing ventricle diseases such as the interventricular septal defect of heart and locular wall reparation, also usually be applied to simultaneously the repairing operation of atrium diseases such as atrial septal defect, can cut randomly according to damaged situation, the stitching pad as various operations after the also normal cutting of product uses.Vascular patch is the fistula mouth that is used for repairing the blood vessel that causes owing to reasons such as hemangioma, angiostenosiss, and vascular patch generally all requires to be easy to characteristics such as stitching, hemostasis, and the utilization of trunks such as general aorta is more.Though the human body self material is such the perform the operation optimal heart, vascular patch material, it is very limited to originate, and can't satisfy the needs of medical operating substantially.
The at present heart that uses in the medical operating, the PA(polyamide that the vascular patch material mostly is braiding greatly), the PET(polyethylene terephthalate), the PTFE(politef) etc. the artificial blood vessel material.Though these materials have favorable mechanical performance and flexibility, but material itself does not have anticoagulation function, therefore material is before endotheliocyte forms, must use anticoagulation medicines such as heparin to surgical patient, and the use of these medicines can cause patient body to be wound bleed after, thereby blood coagulation difficulty threat to life.
And at present the anticoagulation modification of polymeric material is adopted mostly matrix material is carried out surface physics, grafting modification material, or anticoagulant medicine is blended into obtains in the polymer.These method of modifying relatively are applicable to lamellar or bulk material, but can't be used for the braided material that the heart, vascular patch use always and carry out modification; And as with said method the employed fibrous material of braided material is carried out modification, then can cause the decline significantly of polymeric fibre material mechanical performance, and can't satisfy the heart, vascular patch needs the mechanical property of materials.And lamellar or bulk material are because the defective on its softness and the buckling performance also can't be formed to heart or vascular patch.
Summary of the invention
The purpose of this invention is to provide a kind of heart or vascular patch with anticoagulant effect, overcome the defective that the anticoagulation method of modifying of existing polymeric material causes heart or vascular patch braided material mechanical performance to descend significantly, solved the technical problem that grafting method and blending method are difficult to braided material is carried out the anticoagulation modification, the inventive method is carried out the anticoagulation modification to artificial blood vessel with braided material, obtains anticoagulant effect when keeping its excellent mechanical performance, softness and buckling performance.
The technical scheme that realizes the object of the invention is as follows: a kind of heart or vascular patch with anticoagulant effect, comprise the sticking patch base material, it is characterized in that: on the surface of sticking patch base material, adopt coprecipitation that the sticking patch substrate surface is modified, by binding agent polyurethane (PU), through nano-polyurethane (PU) the microsphere embedding sticking patch substrate surface of surface phosphoric acid modification.
Described sticking patch base material is the effective braiding of artificial blood PA, PET or PTFE material.
The nano-polyurethane of described surface phosphoric acid modification (PU) microsphere is nanometer PU microsphere is soaked with phosphate buffer solution and to make.Described nanometer PU microsphere is that diameter is the medical grade nanometer PU microsphere of the emulsion method preparation of 100-300nm.
Described is 0.3-1.0mg/cm through the nanometer PU of phosphorylation modification microsphere in the concentration of sticking patch base material
2
Described phosphorylation modified Nano PU microsphere is bondd by the binding agent PU molecule that is deposited in the sticking patch substrate surface.
Described binding agent PU is medical grade PU.
The sticking patch substrate surface is modified and is undertaken by coprecipitation, coprecipitation is as binding agent with PU solution, nanometer PU microsphere after the surface phosphoric acid modification is placed PU solution ultra-sonic dispersion, make the suspension of surface phosphoric acid modified Nano PU microsphere in PU solution, described suspension is poured in the container of placing the sticking patch base material, centrifugalize, phosphorylation modified Nano PU microsphere is bondd by the PU molecule that precipitates at the sticking patch substrate surface, finishes the modification of sticking patch substrate surface.
The inventive method selects the nanometer PU microsphere of biocompatibility as carrier, carries out surface modification with phosphate buffer solution, obtains anticoagulant effect; By the nanometer PU microsphere embedding sticking patch substrate surface of coprecipitation with the surface phosphoric acid modification, thereby make heart or vascular patch, in the mechanical performance, softness and the buckling performance that keep sticking patch base material excellence, obtain anticoagulant effect with anticoagulant effect.
Described heart or vascular patch with anticoagulant effect can be prepared by following method:
(1) nanometer PU microsphere is placed phosphate buffer solution soak 12～36h, realize its surface phosphoric acidization;
(2) the nanometer PU microsphere after the surface phosphoric acid modification is placed PU alcoholic solution ultra-sonic dispersion, make the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution;
(3) suspension that step (2) is obtained is poured in the container of placing the sticking patch base material, and centrifugalize 5～15 min take out the sticking patch base material, get final product after the drying.
Described nanometer PU microsphere is that diameter is the medical grade nanometer PU microsphere of the emulsion method preparation of 100-300nm.
The ionic strength of described phosphate buffer solution is 0.05～0.3M, and pH value is 7.
Described PU solution is the alcoholic solution of medical grade PU, and the concentration of PU is 0.1 mg/ mL.
Fig. 1 is the TEM photo of the nanometer PU microsphere of surface phosphoric acid modification, from photo as can be seen the surface of nano-polyurethane (microsphere inner dark part) by phosphate buffer solution institute modification (microsphere surface light-colored part).
Fig. 2 is the surfaces A TR-FTIR spectrogram of heart of the present invention or vascular patch, as seen from the figure, has stronger N-H to absorb near 3400 wave numbers, illustrates that nanometer PU microsphere has carried out finishing to the heart, vascular patch.
Show through multiple calcium experimental result that according to heart of the present invention or vascular patch modification can make the recalcification time of original sticking patch base material improve 105%-452% through nanometer PU microsphere surface.This experimental result shows, can effectively improve the blood compatibility of the heart, vascular patch through the surface modification of nanometer PU microsphere.
Adopt mtt assay that the cytotoxicity of heart of the present invention or vascular patch is tested, the test result of 24h shows that the toxicity of this heart, vascular patch is 0 grade (being totally nontoxic), can be used safely in the organism.
Heart or vascular patch with anticoagulant effect of the present invention, with the nanometer PU microsphere of surface phosphoric acid modification as carrier, obtain anticoagulant effect, by coprecipitation nanometer PU microsphere is embedded the vascular patch substrate surface again, thereby make heart or vascular patch with anticoagulant effect.According to heart of the present invention or vascular patch, overcome the defective that grafting method commonly used at present and blending method are difficult to braided material is carried out the anticoagulation modification, in the mechanical performance, softness and the buckling performance that keep sticking patch base material excellence, obtained anticoagulant effect.Heart prepared in accordance with the present invention or vascular patch, has significant anticoagulant effect, when using described patching material to undergo surgery, needn't use anticoagulation medicines such as heparin simultaneously, thereby avoid patient to perform the operation the back in case after being subjected to wound and bleeding, because the effect of anticoagulation medicine, cause blood to condense, jeopardize the problem of patient's life.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with the specific embodiment, but is limited by claim.
Description of drawings
Fig. 1 is the nanometer PU microsphere TEM photo of surface phosphoric acid modification;
Fig. 2 is the ATR-FTIR spectrogram on heart of the present invention or vascular patch surface.
The specific embodiment
In following examples, used nanometer PU microsphere is the medical grade nanometer PU microsphere that commercially available emulsion legal system is equipped with, and PA, PTFE, PET base material are commercially available artificial blood vessel with weaving PA, PTFE and PET material; PU is commercially available medical grade PU.
Embodiment 1
A kind of heart or vascular patch with anticoagulant effect is base material with artificial blood vessel with braiding PA, and its surface embeds the diameter 100nm nanometer PU microsphere of phosphorylation modification, and the concentration of described nanometer PU microsphere on the sticking patch base material is about 0.4mg/cm
2
Described heart or vascular patch with anticoagulant effect prepares by the following method: with the nanometer PU microsphere 1g of diameter 100nm, the ionic strength that places 200mL is 0.1M, and pH value is 7 phosphate buffer solution immersion 24h, realizes its surface phosphoric acidization; Then the nanometer PU microsphere 5mg after the surface phosphoric acid modification is placed 50mL, ultrasonic 20min disperses in the PU alcoholic solution of 0.1mg/ mL, makes the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution; At last this suspension is poured into the bottom and has placed in the big centrifuge tube of artificial blood vessel with braiding PA base material of diameter 4cm, 3000rpm centrifugalize 10min takes out braiding PA, and drying gets final product.
Embodiment 2
A kind of heart or vascular patch with anticoagulant effect is base material with artificial blood vessel with braiding PA, and its surface embeds the diameter 300nm nanometer PU microsphere of phosphorylation modification, and the concentration of described nanometer PU microsphere on the sticking patch base material is about 0.96mg/cm
2
Described heart or vascular patch with anticoagulant effect prepares by the following method: with the nanometer PU microsphere 1g of diameter 300nm, the ionic strength that places 200mL is 0.1M, and pH value is 7 phosphate buffer solution immersion 24h, realizes its surface phosphoric acidization; Then the nanometer PU microsphere 12mg after the surface phosphoric acid modification is placed 50mL, ultrasonic 20min disperses in the PU alcoholic solution of 0.1mg/ mL, makes the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution; At last this suspension is poured into the bottom and has placed in the big centrifuge tube of artificial blood vessel with braiding PA base material of diameter 4cm, 3000rpm centrifugalize 10min takes out braiding PA, and drying gets final product.
Embodiment 3
A kind of heart or vascular patch with anticoagulant effect is base material with artificial blood vessel with braiding PA, and its surface embeds the diameter 200nm nanometer PU microsphere of phosphorylation modification, and the concentration of described nanometer PU microsphere on the sticking patch base material is about 0.48mg/cm
2
Described heart or vascular patch with anticoagulant effect prepares by the following method: with the nanometer PU microsphere 1g of diameter 200nm, the ionic strength that places 200mL is 0.1M, and pH value is 7 phosphate buffer solution immersion 24h, realizes its surface phosphoric acidization; Then the nanometer PU microsphere 6mg after the surface phosphoric acid modification is placed 50mL, ultrasonic 20min disperses in the PU alcoholic solution of 0.1mg/ mL, makes the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution; At last this suspension is poured into the bottom and has placed in the big centrifuge tube of artificial blood vessel with braiding PA base material of diameter 4cm, 3000rpm centrifugalize 10min takes out braiding PA, and drying gets final product.
Embodiment 4
A kind of heart or vascular patch with anticoagulant effect is base material with artificial blood vessel with braiding PTFE, and its surface embeds the diameter 100nm nanometer PU microsphere of phosphorylation modification, and the concentration of described nanometer PU microsphere on the sticking patch base material is about 0.32mg/cm
2
Described heart or vascular patch with anticoagulant effect prepares by the following method: with the nanometer PU microsphere 1g of diameter 100nm, the ionic strength that places 200mL is 0.1M, and pH value is 7 phosphate buffer solution immersion 24h, realizes its surface phosphoric acidization; Then the nanometer PU microsphere 4mg after the surface phosphoric acid modification is placed 50mL, ultrasonic 20min disperses in the PU alcoholic solution of 0.1mg/ mL, makes the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution; At last this suspension is poured into the bottom and has placed in the big centrifuge tube of artificial blood vessel with braiding PTFE base material of diameter 4cm, 3000rpm centrifugalize 10min takes out braiding PTFE, and drying gets final product.
Embodiment 5
A kind of heart or vascular patch with anticoagulant effect is base material with artificial blood vessel with braiding PTFE, and its surface embeds the diameter 300nm nanometer PU microsphere of phosphorylation modification, and the concentration of described nanometer PU microsphere on the sticking patch base material is about 0.96mg/cm
2
Described heart or vascular patch with anticoagulant effect prepares by the following method: with the nanometer PU microsphere 1g of diameter 300nm, the ionic strength that places 200mL is 0.1M, and pH value is 7 phosphate buffer solution immersion 24h, realizes its surface phosphoric acidization; Then the nanometer PU microsphere 12mg after the surface phosphoric acid modification is placed 50mL, ultrasonic 20min disperses in the PU alcoholic solution of 0.1mg/ mL, makes the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution; At last this suspension is poured into the bottom and has placed in the big centrifuge tube of artificial blood vessel with braiding PTFE base material of diameter 4cm, 3000rpm centrifugalize 10min takes out braiding PTFE, and drying gets final product.
Embodiment 6
A kind of heart or vascular patch with anticoagulant effect is base material with artificial blood vessel with braiding PTFE, and its surface embeds the diameter 200nm nanometer PU microsphere of phosphorylation modification, and the concentration of described nanometer PU microsphere on the sticking patch base material is about 0.48mg/cm
2
Described heart or vascular patch with anticoagulant effect prepares by the following method: with the nanometer PU microsphere 1g of diameter 200nm, the ionic strength that places 200mL is 0.1M, and pH value is 7 phosphate buffer solution immersion 24h, realizes its surface phosphoric acidization; Then the nanometer PU microsphere 6mg after the surface phosphoric acid modification is placed 50mL, ultrasonic 20min disperses in the PU alcoholic solution of 0.1mg/ mL, makes the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution; At last this suspension is poured into the bottom and has placed in the big centrifuge tube of artificial blood vessel with braiding PTFE base material of diameter 4cm, 3000rpm centrifugalize 10min takes out braiding PTFE, and drying gets final product.
Embodiment 7
A kind of heart or vascular patch with anticoagulant effect is base material with artificial blood vessel with braiding PET, and its surface embeds the diameter 100nm nanometer PU microsphere of phosphorylation modification, and the concentration of described nanometer PU microsphere on the sticking patch base material is about 0.4mg/cm
2
Described heart or vascular patch with anticoagulant effect prepares by the following method: with the nanometer PU microsphere 1g of diameter 100nm, the ionic strength that places 200mL is 0.1M, and pH value is 7 phosphate buffer solution immersion 24h, realizes its surface phosphoric acidization; Then the nanometer PU microsphere 5mg after the surface phosphoric acid modification is placed 50mL, ultrasonic 20min disperses in the PU alcoholic solution of 0.1mg/ mL, makes the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution; At last this suspension is poured into the bottom and has placed in the big centrifuge tube of artificial blood vessel with braiding PET base material of diameter 4cm, 3000rpm centrifugalize 10min takes out braiding PET, and drying gets final product.
Embodiment 8
A kind of heart or vascular patch with anticoagulant effect is base material with artificial blood vessel with braiding PET, and its surface embeds the diameter 300nm nanometer PU microsphere of phosphorylation modification, and the concentration of described nanometer PU microsphere on the sticking patch base material is about 0.96mg/cm
2
Described heart or vascular patch with anticoagulant effect prepares by the following method: with the nanometer PU microsphere 1g of diameter 300nm, the ionic strength that places 200mL is 0.1M, and pH value is 7 phosphate buffer solution immersion 24h, realizes its surface phosphoric acidization; Then the nanometer PU microsphere 12mg after the surface phosphoric acid modification is placed 50mL, ultrasonic 20min disperses in the PU alcoholic solution of 0.1mg/ mL, makes the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution; At last this suspension is poured into the bottom and has placed in the big centrifuge tube of artificial blood vessel with braiding PET base material of diameter 4cm, 3000rpm centrifugalize 10min takes out braiding PET, and drying gets final product.
Embodiment 9
A kind of heart or vascular patch with anticoagulant effect is base material with artificial blood vessel with braiding PET, and its surface embeds the diameter 200nm nanometer PU microsphere of phosphorylation modification, and the concentration of described nanometer PU microsphere on the sticking patch base material is about 0.48mg/cm
2
Described heart or vascular patch with anticoagulant effect prepares by the following method: with the nanometer PU microsphere 1g of diameter 200nm, the ionic strength that places 200mL is 0.1M, and pH value is 7 phosphate buffer solution immersion 24h, realizes its surface phosphoric acidization; Then the nanometer PU microsphere 6mg after the surface phosphoric acid modification is placed 50mL, ultrasonic 20min disperses in the PU alcoholic solution of 0.1mg/ mL, makes the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution; At last this suspension is poured into the bottom and has placed in the big centrifuge tube of artificial blood vessel with braiding PET base material of diameter 4cm, 3000rpm centrifugalize 10min takes out braiding PET, and drying gets final product.
Claims (10)
1. a heart or vascular patch with anticoagulant effect, comprise the sticking patch base material, it is characterized in that:, adopt coprecipitation that the sticking patch substrate surface is modified on the surface of sticking patch base material, by binding agent PU, through the nanometer PU microsphere embedding sticking patch substrate surface of surface phosphoric acid modification.
2. heart or the vascular patch with anticoagulant effect according to claim 1 is characterized in that described sticking patch base material is the effective braiding of artificial blood PA, PET or PTFE material.
3. heart or the vascular patch with anticoagulant effect according to claim 1, the nanometer PU microsphere that it is characterized in that described surface phosphoric acid modification, be nanometer PU microsphere is soaked with phosphate buffer solution and to make, described nanometer PU microsphere is that diameter is the medical grade nanometer PU microsphere of the emulsion method preparation of 100-300nm.
4. heart or the vascular patch with anticoagulant effect according to claim 1 is characterized in that described is 0.3-1.0mg/cm through the concentration of the nanometer PU of phosphorylation modification microsphere on the sticking patch base material
2
5. heart or the vascular patch with anticoagulant effect according to claim 1 is characterized in that described phosphorylation modified Nano PU microsphere is bondd by the binding agent PU molecule that is deposited in the sticking patch substrate surface.
6. heart or the vascular patch with anticoagulant effect according to claim 1 is characterized in that described binding agent PU is medical grade PU.
7. heart or the vascular patch with anticoagulant effect according to claim 1 is characterized in that described heart or vascular patch are prepared by following method:
(1) nanometer PU microsphere is placed phosphate buffer solution soak 12～36h, realize its surface phosphoric acidization;
(2) the nanometer PU microsphere after the surface phosphoric acid modification is placed PU alcoholic solution ultra-sonic dispersion, make the suspension of surface phosphoric acid modified Nano PU microsphere in the PU alcoholic solution;
(3) suspension that step (2) is obtained is poured in the container of placing the sticking patch base material, and centrifugalize 5～15 min take out the sticking patch base material, get final product after the drying.
8. heart or the vascular patch with anticoagulant effect according to claim 7 is characterized in that described nanometer PU microsphere is that diameter is the medical grade nanometer PU microsphere of the emulsion method preparation of 100-300nm.
9. heart or the vascular patch with anticoagulant effect according to claim 7, the ionic strength that it is characterized in that described phosphate buffer solution is 0.05～0.3M, pH value is 7.
10. heart or the vascular patch with anticoagulant effect according to claim 7 is characterized in that described PU solution is the alcoholic solution of medical grade PU, and the concentration of PU is 0.1 mg/ mL.
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| CN201110024255.8A CN102068323B (en) | 2011-01-21 | 2011-01-21 | Cardiac or vascular patch with anticoagulant effect |
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| CN201110024255.8A CN102068323B (en) | 2011-01-21 | 2011-01-21 | Cardiac or vascular patch with anticoagulant effect |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108853587A (en) * | 2017-05-10 | 2018-11-23 | 上海交通大学 | Magnesium alloy and macromolecule silk material shuffling composite patch and application thereof |
| CN110786963A (en) * | 2019-11-25 | 2020-02-14 | 上海畅迪医疗科技有限公司 | Composite heart or blood vessel patch |
| CN113907915A (en) * | 2021-09-27 | 2022-01-11 | 浙江大学 | Suture-free blood coagulation auxiliary fixing heart patch and preparation method thereof |
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| WO1995020381A1 (en) * | 1994-01-28 | 1995-08-03 | Fidia Advanced Biopolymers S.R.L. | Coating of biomedical objects with microspheres obtained with biocompatible polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108853587A (en) * | 2017-05-10 | 2018-11-23 | 上海交通大学 | Magnesium alloy and macromolecule silk material shuffling composite patch and application thereof |
| CN110786963A (en) * | 2019-11-25 | 2020-02-14 | 上海畅迪医疗科技有限公司 | Composite heart or blood vessel patch |
| CN113907915A (en) * | 2021-09-27 | 2022-01-11 | 浙江大学 | Suture-free blood coagulation auxiliary fixing heart patch and preparation method thereof |
| CN113907915B (en) * | 2021-09-27 | 2022-07-29 | 浙江大学 | Suture-free blood coagulation auxiliary fixing heart patch and preparation method thereof |
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