CN102068323B - Cardiac or vascular patch with anticoagulant effect - Google Patents
Cardiac or vascular patch with anticoagulant effect Download PDFInfo
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- CN102068323B CN102068323B CN201110024255.8A CN201110024255A CN102068323B CN 102068323 B CN102068323 B CN 102068323B CN 201110024255 A CN201110024255 A CN 201110024255A CN 102068323 B CN102068323 B CN 102068323B
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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.Heart sticking patch is for repairing the repairing operation of the ventricle diseases such as the interventricular septal defect of heart and locular wall reparation, also be usually applied to the repairing operation of the atrium diseases such as atrial septal defect simultaneously, can cut randomly according to damaged situation, product also after normal cutting the stitching pad as various operations use.Vascular patch is that vascular patch generally all requires to be easy to the features such as stitchings, hemostasis for repairing the fistula mouth of the blood vessel causing due to reasons such as hemangioma, angiostenosiss, and generally the trunk utilization such as aorta is more.Although human body self material is such the perform the operation optimal heart, vascular patch material, originates very limited, substantially cannot meet the needs of medical operating.
The heart using in medical operating at present, the PA(polyamide that vascular patch material is mostly braiding), PET(polyethylene terephthalate), PTFE(politef) etc. artificial blood vessel material.Although these materials have good mechanical performance and flexibility, but material itself does not have anticoagulation function, therefore material is before endotheliocyte forms, must use to surgical patient the anticoagulation medicines such as heparin, 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 to surface physics, grafting modification material, or anticoagulant medicine is blended into and is obtained in polymer.These method of modifying are relatively applicable to lamellar or bulk material, but cannot carry out modification for the heart, braided material that vascular patch is conventional; And as the fibrous material that braided material was used carried out to modification with said method, can cause the significantly decline of polymeric fibre material mechanical performance, and cannot meet the heart, the needs of vascular patch to the mechanical property of materials.And lamellar or bulk material are due to the defect on its softness and buckling performance, also cannot be formed to heart or vascular patch.
Summary of the invention
The object of this invention is to provide a kind of heart or vascular patch with anticoagulant effect, overcome the defect that the anticoagulation method of modifying of existing polymeric material causes heart or vascular patch braided material mechanical performance significantly to decline, solved the technical problem that Graft Method and blending method are difficult to braided material to carry out anticoagulation modification, the inventive method is carried out anticoagulation modification to artificial blood vessel with braided material, when keeping its excellent mechanical performance, softness and buckling performance, obtains anticoagulant effect.
The technical scheme that realizes the object of the invention is as follows: a kind of heart or vascular patch with anticoagulant effect, comprise sticking patch base material, it is characterized in that: on the surface of sticking patch base material, adopt coprecipitation to modify sticking patch substrate surface, 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.
Nano-polyurethane (PU) microsphere of described surface phosphoric acid modification is nanometer PU microsphere is soaked with phosphate buffer solution and make.Described nanometer PU microsphere is that diameter is medical grade nanometer PU microsphere prepared by the emulsion method 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 sticking patch substrate surface.
Described binding agent PU is medical grade PU.
Sticking patch substrate surface is modified and is undertaken by coprecipitation, coprecipitation is to using PU solution as binding agent, nanometer PU microsphere after surface phosphoric acid modification is placed in to the ultrasonic dispersion of PU solution, make the suspension of surface phosphoric acid modified Nano PU microsphere in PU solution, described suspension is poured in the container of placing sticking patch base material, centrifugalize, phosphorylation modified Nano PU microsphere is bondd by the PU molecule precipitating at sticking patch substrate surface, completes the modification of sticking patch substrate surface.
The inventive method selects the nanometer PU microsphere of biocompatibility as carrier, with phosphate buffer solution, carries out surface modification, obtains anticoagulant effect; By coprecipitation, the nanometer PU microsphere of surface phosphoric acid modification is embedded to sticking patch substrate surface, thereby make heart or the vascular patch with anticoagulant effect, in the mechanical performance, softness and the buckling performance that keep sticking patch base material excellence, obtain anticoagulant effect.
The described heart with anticoagulant effect or vascular patch can be prepared by following methods:
(1) nanometer PU microsphere is placed in to phosphate buffer solution and soaks 12～36h, realize its surface phosphoric acid;
(2) the nanometer PU microsphere after surface phosphoric acid modification is placed in to the ultrasonic dispersion of PU alcoholic solution, makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution;
(3) suspension step (2) being obtained is poured in the container of placing sticking patch base material, and centrifugalize 5～15 min take out sticking patch base material, after being dried.
Described nanometer PU microsphere is that diameter is medical grade nanometer PU microsphere prepared by the emulsion method 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, and the surface that can find out nano-polyurethane (the inner dark part of microsphere) from photo is by phosphate buffer solution institute modification (microsphere surface light-colored part).
Fig. 2 is the surface 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.
According to heart of the present invention or vascular patch, through multiple calcium experimental result, show, through nanometer PU microsphere surface, modification can make the recalcification time of original sticking patch base material improve 105%-452%.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 to test the cytotoxicity of heart of the present invention or vascular patch, the test result of 24h shows, the toxicity of this heart, vascular patch is 0 grade (being totally nontoxic), can be used safely in organism.
Heart or the vascular patch with anticoagulant effect of the present invention, using the nanometer PU microsphere of surface phosphoric acid modification as carrier, obtain anticoagulant effect, then by coprecipitation, nanometer PU microsphere is embedded to vascular patch substrate surface, thereby make heart or the vascular patch with anticoagulant effect.According to heart of the present invention or vascular patch, overcome the defect that current conventional Graft Method and blending method are difficult to braided material to carry out 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, there is significant anticoagulant effect, when using described patching material to perform the operation, needn't use the anticoagulation medicines such as heparin simultaneously, once thereby after being subject to wound after avoiding patient to perform the operation and bleeding, effect due to anticoagulation medicine, cause blood to condense, jeopardize the problem of patients ' lives.
Below in conjunction with specific embodiment, describe the present invention.Protection scope of the present invention is not limited with the specific embodiment, but is limited by claim.
Accompanying drawing explanation
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, nanometer PU microsphere used is the standby medical grade nanometer PU microsphere of commercially available emulsion legal system, and PA, PTFE, PET base material are braiding PA, PTFE and PET material for commercially available artificial blood vessel; PU is commercially available medical grade PU.
Embodiment 1
Heart or a vascular patch with anticoagulant effect, the artificial blood vessel of take is base material 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 sticking patch base material is about 0.4mg/cm
2.
Described heart or the vascular patch with anticoagulant effect prepared by the following method: by the nanometer PU microsphere 1g of diameter 100nm, the ionic strength that is placed in 200mL is 0.1M, and the phosphate buffer solution that pH value is 7 soaks 24h, realizes its surface phosphoric acid; Then the nanometer PU microsphere 5mg after surface phosphoric acid modification is placed in to 50mL, in the PU alcoholic solution of 0.1mg/ mL, ultrasonic 20min disperses, and makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution; Bottom finally this suspension being poured into, placed the artificial blood vessel of diameter 4cm with weaving in the large centrifuge tube of PA base material, 3000rpm centrifugalize 10min, takes out braiding PA, be dried.
Embodiment 2
Heart or a vascular patch with anticoagulant effect, the artificial blood vessel of take is base material 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 sticking patch base material is about 0.96mg/cm
2.
Described heart or the vascular patch with anticoagulant effect prepared by the following method: by the nanometer PU microsphere 1g of diameter 300nm, the ionic strength that is placed in 200mL is 0.1M, and the phosphate buffer solution that pH value is 7 soaks 24h, realizes its surface phosphoric acid; Then the nanometer PU microsphere 12mg after surface phosphoric acid modification is placed in to 50mL, in the PU alcoholic solution of 0.1mg/ mL, ultrasonic 20min disperses, and makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution; Bottom finally this suspension being poured into, placed the artificial blood vessel of diameter 4cm with weaving in the large centrifuge tube of PA base material, 3000rpm centrifugalize 10min, takes out braiding PA, be dried.
Embodiment 3
Heart or a vascular patch with anticoagulant effect, the artificial blood vessel of take is base material 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 sticking patch base material is about 0.48mg/cm
2.
Described heart or the vascular patch with anticoagulant effect prepared by the following method: by the nanometer PU microsphere 1g of diameter 200nm, the ionic strength that is placed in 200mL is 0.1M, and the phosphate buffer solution that pH value is 7 soaks 24h, realizes its surface phosphoric acid; Then the nanometer PU microsphere 6mg after surface phosphoric acid modification is placed in to 50mL, in the PU alcoholic solution of 0.1mg/ mL, ultrasonic 20min disperses, and makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution; Bottom finally this suspension being poured into, placed the artificial blood vessel of diameter 4cm with weaving in the large centrifuge tube of PA base material, 3000rpm centrifugalize 10min, takes out braiding PA, be dried.
Embodiment 4
Heart or a vascular patch with anticoagulant effect, the artificial blood vessel of take is base material 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 sticking patch base material is about 0.32mg/cm
2.
Described heart or the vascular patch with anticoagulant effect prepared by the following method: by the nanometer PU microsphere 1g of diameter 100nm, the ionic strength that is placed in 200mL is 0.1M, and the phosphate buffer solution that pH value is 7 soaks 24h, realizes its surface phosphoric acid; Then the nanometer PU microsphere 4mg after surface phosphoric acid modification is placed in to 50mL, in the PU alcoholic solution of 0.1mg/ mL, ultrasonic 20min disperses, and makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution; Bottom finally this suspension being poured into, placed the artificial blood vessel of diameter 4cm with weaving in the large centrifuge tube of PTFE base material, 3000rpm centrifugalize 10min, takes out braiding PTFE, be dried.
Embodiment 5
Heart or a vascular patch with anticoagulant effect, the artificial blood vessel of take is base material 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 sticking patch base material is about 0.96mg/cm
2.
Described heart or the vascular patch with anticoagulant effect prepared by the following method: by the nanometer PU microsphere 1g of diameter 300nm, the ionic strength that is placed in 200mL is 0.1M, and the phosphate buffer solution that pH value is 7 soaks 24h, realizes its surface phosphoric acid; Then the nanometer PU microsphere 12mg after surface phosphoric acid modification is placed in to 50mL, in the PU alcoholic solution of 0.1mg/ mL, ultrasonic 20min disperses, and makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution; Bottom finally this suspension being poured into, placed the artificial blood vessel of diameter 4cm with weaving in the large centrifuge tube of PTFE base material, 3000rpm centrifugalize 10min, takes out braiding PTFE, be dried.
Embodiment 6
Heart or a vascular patch with anticoagulant effect, the artificial blood vessel of take is base material 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 sticking patch base material is about 0.48mg/cm
2.
Described heart or the vascular patch with anticoagulant effect prepared by the following method: by the nanometer PU microsphere 1g of diameter 200nm, the ionic strength that is placed in 200mL is 0.1M, and the phosphate buffer solution that pH value is 7 soaks 24h, realizes its surface phosphoric acid; Then the nanometer PU microsphere 6mg after surface phosphoric acid modification is placed in to 50mL, in the PU alcoholic solution of 0.1mg/ mL, ultrasonic 20min disperses, and makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution; Bottom finally this suspension being poured into, placed the artificial blood vessel of diameter 4cm with weaving in the large centrifuge tube of PTFE base material, 3000rpm centrifugalize 10min, takes out braiding PTFE, be dried.
Embodiment 7
Heart or a vascular patch with anticoagulant effect, the artificial blood vessel of take is base material 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 sticking patch base material is about 0.4mg/cm
2.
Described heart or the vascular patch with anticoagulant effect prepared by the following method: by the nanometer PU microsphere 1g of diameter 100nm, the ionic strength that is placed in 200mL is 0.1M, and the phosphate buffer solution that pH value is 7 soaks 24h, realizes its surface phosphoric acid; Then the nanometer PU microsphere 5mg after surface phosphoric acid modification is placed in to 50mL, in the PU alcoholic solution of 0.1mg/ mL, ultrasonic 20min disperses, and makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution; Bottom finally this suspension being poured into, placed the artificial blood vessel of diameter 4cm with weaving in the large centrifuge tube of PET base material, 3000rpm centrifugalize 10min, takes out braiding PET, be dried.
Embodiment 8
Heart or a vascular patch with anticoagulant effect, the artificial blood vessel of take is base material 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 sticking patch base material is about 0.96mg/cm
2.
Described heart or the vascular patch with anticoagulant effect prepared by the following method: by the nanometer PU microsphere 1g of diameter 300nm, the ionic strength that is placed in 200mL is 0.1M, and the phosphate buffer solution that pH value is 7 soaks 24h, realizes its surface phosphoric acid; Then the nanometer PU microsphere 12mg after surface phosphoric acid modification is placed in to 50mL, in the PU alcoholic solution of 0.1mg/ mL, ultrasonic 20min disperses, and makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution; Bottom finally this suspension being poured into, placed the artificial blood vessel of diameter 4cm with weaving in the large centrifuge tube of PET base material, 3000rpm centrifugalize 10min, takes out braiding PET, be dried.
Embodiment 9
Heart or a vascular patch with anticoagulant effect, the artificial blood vessel of take is base material 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 sticking patch base material is about 0.48mg/cm
2.
Described heart or the vascular patch with anticoagulant effect prepared by the following method: by the nanometer PU microsphere 1g of diameter 200nm, the ionic strength that is placed in 200mL is 0.1M, and the phosphate buffer solution that pH value is 7 soaks 24h, realizes its surface phosphoric acid; Then the nanometer PU microsphere 6mg after surface phosphoric acid modification is placed in to 50mL, in the PU alcoholic solution of 0.1mg/ mL, ultrasonic 20min disperses, and makes the suspension of surface phosphoric acid modified Nano PU microsphere in PU alcoholic solution; Bottom finally this suspension being poured into, placed the artificial blood vessel of diameter 4cm with weaving in the large centrifuge tube of PET base material, 3000rpm centrifugalize 10min, takes out braiding PET, be dried.
Claims (6)
1. heart or a vascular patch with anticoagulant effect, comprise sticking patch base material, it is characterized in that: on the surface of sticking patch base material, adopt following method to modify sticking patch substrate surface, by binding agent, be the polyurethane in polyurethane alcoholic solution, through the nano-polyurethane microsphere embedding sticking patch substrate surface of surface phosphoric acid modification;
The described method that sticking patch substrate surface is modified is:
(1) nano-polyurethane microsphere is placed in to phosphate buffer solution and soaks 12～36h, realize its surface phosphoric acid;
(2) the nano-polyurethane microsphere after surface phosphoric acid modification is placed in to the ultrasonic dispersion of polyurethane alcoholic solution, makes the suspension of surface phosphoric acid modified Nano polyaminoester microball in polyurethane alcoholic solution;
(3) suspension step (2) being obtained is poured in the container of placing sticking patch base material, and centrifugalize 5～15 min take out sticking patch base material, after being dried.
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 braided polyamide of artificial blood, polyethylene terephthalate or polytetrafluoroethylmaterial material.
3. heart or the vascular patch with anticoagulant effect according to claim 1, is characterized in that the concentration of the described nano-polyurethane microsphere through phosphorylation modification on sticking patch base material is 0.3-1.0mg/cm
2.
4. heart or the vascular patch with anticoagulant effect according to claim 1, is characterized in that described nano-polyurethane microsphere is medical grade nano-polyurethane microsphere prepared by emulsion method, and its diameter is 100-300nm.
5. heart or the vascular patch with anticoagulant effect according to claim 1, is characterized in that the ionic strength of described phosphate buffer solution is 0.05～0.3M, and pH value is 7.
6. heart or the vascular patch with anticoagulant effect according to claim 1, is characterized in that the alcoholic solution that described polyurethane alcoholic solution is medical grade polyurethane, and the concentration of polyurethane 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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| CN108853587B (en) * | 2017-05-10 | 2021-08-03 | 上海交通大学 | Magnesium alloy and high polymer wire material mixed-woven 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 |
| CN113907915B (en) * | 2021-09-27 | 2022-07-29 | 浙江大学 | Suture-free blood coagulation auxiliary fixing heart patch and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1799649A (en) * | 2005-12-09 | 2006-07-12 | 清华大学 | Blood compatible biological material and preparation method thereof |
| CN101584612A (en) * | 2009-06-12 | 2009-11-25 | 广州迈普再生医学科技有限公司 | Regeneration type artificial blood vessel based on in-situ self stem cell technology and preparation method thereof |
| CN101602860A (en) * | 2009-07-01 | 2009-12-16 | 南京师范大学 | Polyurethane nanometer powder of a kind of surface phosphoric acid modification and preparation method thereof |
| WO2010017282A1 (en) * | 2008-08-05 | 2010-02-11 | Biomimedica, Inc. | Polyurethane-grafted hydrogels |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITPD940011A1 (en) * | 1994-01-28 | 1995-07-28 | Fidia Advanced Biopolymers Srl | COATING OF BIOMEDICAL OBJECTS USING MICROSPHERES OBTAINED FROM BIOCOMPATIBLE POLYMERS |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1799649A (en) * | 2005-12-09 | 2006-07-12 | 清华大学 | Blood compatible biological material and preparation method thereof |
| WO2010017282A1 (en) * | 2008-08-05 | 2010-02-11 | Biomimedica, Inc. | Polyurethane-grafted hydrogels |
| CN101584612A (en) * | 2009-06-12 | 2009-11-25 | 广州迈普再生医学科技有限公司 | Regeneration type artificial blood vessel based on in-situ self stem cell technology and preparation method thereof |
| CN101602860A (en) * | 2009-07-01 | 2009-12-16 | 南京师范大学 | Polyurethane nanometer powder of a kind of surface phosphoric acid modification and preparation method thereof |
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