CN105148330A - Lumen stent capable of conducting development absorption and preparation method and application thereof - Google Patents
Lumen stent capable of conducting development absorption and preparation method and application thereof Download PDFInfo
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- CN105148330A CN105148330A CN201510604292.4A CN201510604292A CN105148330A CN 105148330 A CN105148330 A CN 105148330A CN 201510604292 A CN201510604292 A CN 201510604292A CN 105148330 A CN105148330 A CN 105148330A
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Abstract
The invention discloses a lumen stent capable of conducting development absorption. The lumen stent is characterized in that the lumen stent is of a hollow tubular structure and made ofacyl amino polysaccharide, the outer surface of the tubular structure is provided with a development coating, and the tube wall is provided with or not provided with a transparent hole structure or a pattern structure. The lumen stent can be used as a blood vessel stent, a biliary stent or a urethral stent and is used for treating narrowing of the blood vessel, the bile duct and the urine tube cavity, capable of conducting development, capable of being degraded and absorbed in a human body, the situation that the lumen stent stays in the body for a long time can be avoided, and the lumen stent has wide market prospect.
Description
Technical field
The invention belongs to biomedical materials field, relate to a kind of intraluminal stent material, particularly relate to intraluminal stent of a kind of absorption of developing and its preparation method and application.
Background technology
Intraluminal stent clinically tool has been widely used, and can be used for Esophageal Stent, biliary tract prosthesis, urethra rack, artificial blood vessel etc.The pancreatic duct that biliary tract prosthesis causes for pancreas gallbladder malignant tumor blocks, the treatment of cholestasis.Urethra rack is for because of prostate hyperplasia, urethra so that urethral stricture are difficult to the treatment of urinating.Artificial blood vessel, particularly small-caliber artificial blood vessel (diameter≤6mm), for replacing the periphery thin vessels of body sufferer or defect, supply with the blood improving body peripheral tissues.Small-caliber artificial blood vessel, biliary tract prosthesis and urethra rack all have a wide range of applications clinically.The chemical macromolecular material support of the intraluminal stent of current Clinical practice mainly metal rack and nonabsorable, the intraluminal stent that can not degrade in vivo longer-term persistence can cause local chronic inflammatory to react, the intraluminal stent material of nonabsorable can not take out simultaneously, brings obstacle to the treatment again of original position.Desirable Absorbable rod intraluminal stent needs enough mechanical strengths and radial support effect, and along with the reparation of pathological lumen, Absorbable rod intraluminal stent is finally degraded gradually and is absorbed by the body, and avoids longer-term persistence in vivo.Therefore, Absorbable rod intraluminal stent is the important directions of support research.
Chitin, chitosan are the degradable macromolecule polysaccharide of biogenetic derivation, biological safety, and degradable absorbs, and have a wide range of applications in degradable biomaterial research.Chitin is a kind of natural macromolecule amylose, and water insoluble and general soda acid solvent, is only soluble in minority organic solvent, as trichloroacetic acid, dichloroacetic acid, hexafluoroisopropanol, dimethyl formamide-LiCl etc.Due to deliquescent restriction, there is technical difficulty in it in actual applications.The catabolite of chitin is micromolecular acetylamino oligosaccharide or acetylamino monosaccharide, and the catabolite of chitosan is micromolecular amino-oligosacchride or amino monosaccharide, is all easily absorbed by body.The physicochemical characteristics of chitin, chitosan and its biological degradability etc., all carry out modification by chemical modification, or macromolecular material different from other mixes or compound, thus is more preferably met the bioabsorbable polymer material of different needs.
Desirable Absorbable rod intraluminal stent material can develop observation in vivo, the time that intraluminal stent exists in vivo should be consistent for repair time with luminal stenosis, after tube chamber reconstruction, intraluminal stent is degraded gradually, finally absorbed completely by human body, degradation process answers homogeneous degraded, should not produce degraded fragment, in order to avoid affect the patency of tube chamber.
Summary of the invention
The object of this invention is to provide intraluminal stent of a kind of developed absorption of natural biologic material and its preparation method and application, to make up the above-mentioned deficiency of prior art.
For achieving the above object, the present invention is achieved by the following technical solutions:
Develop the intraluminal stent absorbed, and it is characterized in that the hollow tubular structure made for material with acylated amino polysaccharide, the outer surface of tubular structure has development coating, and tube wall is with or without penetrating pore space structure or patterning.
The acylated amino polysaccharide that acylated amino polysaccharide of the present invention is is construction unit with acylated amino glucose.
Acylated amino polysaccharide of the present invention can be that chitosan is modified obtained through acyl groupization, also can be that chitin is modified obtained through acyl groupization.
The molecular structure of acylated amino polysaccharide of the present invention is polyamides base glucosamine polysaccharide; total acyl group degree in the molecular structure of described acylated amino polysaccharide is more than or equal to 70%; described acyl group is one or more in acetyl group, propiono, bytyry, caproyl, caprylyl, certain herbaceous plants with big flowers acyl group, lauroyl, palmityl and other aliphatic or aromatic acyl group, and the molecular structural formula of acylated amino polysaccharide is:
In formula, R
1, R
2or R
3h, acetyl group (-C
2h
3o), propiono (-C
3h
5o), bytyry (-C
4h
7o), caproyl (-C
6h
11o), caprylyl (-C
8h
15o) one or more or in certain herbaceous plants with big flowers acyl group, lauroyl, palmityl and other aliphatic or aromatic acyl group, n is greater than 100; The acyl group degree of acylated amino polysaccharide is more than or equal to 70%, and the acyl group quantity namely on average in every 100 sugar units is more than or equal to 70, and the position of acyl group is C6-O position, C3-O position or C2-N position; Described acyl group is one or more in acetyl group, propiono, bytyry, caproyl, caprylyl, certain herbaceous plants with big flowers acyl group, lauroyl, palmityl and other aliphatic or aromatic acyl group, and described acyl group degree is the summation that acylated amino polysaccharide comprises one or more the acyl group degree in acetyl group, propiono, bytyry, caproyl, caprylyl, certain herbaceous plants with big flowers acyl group, lauroyl, palmityl and other aliphatic or aromatic acyl group.
Above-mentioned development coating is the azido benzoyl aminopolysaccharide coating containing developing agent.
The present invention for material, has prepared the intraluminal stent base material that can develop and absorb with acylated amino polysaccharide.Described intraluminal stent base material has that water absorption rate is low, intensity is high, degradable absorbs, the feature of good biocompatibility.
Azido benzoyl aminopolysaccharide of the present invention; comprise hydrazoic benzoyl chitosan, azido benzoyl hydroxyethyl chitosan, azido benzoyl hydroxypropyl chitosan, azido benzoyl carboxymethyl chitosan, azido benzoyl chitin, azido benzoyl ethoxyl chitin, azido benzoyl Chitofilmer, and chitin, chitosan other azido benzoyl derivant.Described azido benzoyl aminopolysaccharide is when absorbing ultraviolet, and active azido benzoyl group photodissociation is carbene, carbene can with the element generation cross-linking reaction such as C, S, O.
The present invention utilizes this characteristic of azido benzoyl aminopolysaccharide, carries out sensitivity to the intraluminal stent base material of preparation.Prepare the azido benzoyl aminopolysaccharide glue containing developing agent, carry out the outer surface development coating modifying of intraluminal stent base material, so that the radiography in intraluminal stent body is observed.Containing the azido benzoyl aminopolysaccharide coating of developing agent, occur crosslinked under the action of uv light, developing agent is fixed on intraluminal stent base material.
The intraluminal stent absorbed that develops of the present invention, the hollow tubular structure made for material with acylated amino polysaccharide, the outer surface of tubular structure has development coating, and tube wall is with or without penetrating pore space structure or patterning.The preparation method of a kind of intraluminal stent absorbed that develops of the present invention, is characterized in that:
Acylated amino polysaccharide is dissolved in solvent, preparation concentration expressed in percentage by weight be 1% ~ 20% or w/v be 1% ~ 25% acylated amino polysaccharide glue;
Open the tuber with Pipe making mold, by acylated amino polysaccharide glue coating on Pipe making mold, control glue thickness, room temperature or temperature control heat drying become tubulose;
Pipe making mold is put into dilute alkaline aqueous solution, ethanol water or distilled water together with the tubular material prepared soak, de-pipe, is washed to pH neutrality, and dehydration is dry, obtains the intraluminal stent base material of hollow tubular;
Preparation concentration expressed in percentage by weight is the azido benzoyl aminopolysaccharide glue of 0.5% ~ 25%, adds developing agent, and obtained developing agent glue, opens plater, by developing agent glue coating at intraluminal stent substrate outer surface, and ultraviolet light cross-linking;
Drying, the obtained intraluminal stent tubing absorbed that can develop;
The intraluminal stent tubing absorbed that can develop is processed through Laser cutting or machine cuts, and obtained tube wall is with or without the intraluminal stent of the developed absorption of penetrating pore space structure or patterning.
The preparation method of the intraluminal stent absorbed that develops of the present invention, it is characterized in that the molecular structure of described acylated amino polysaccharide is polyamides base glucosamine polysaccharide, the total acyl group degree in molecular structure is more than or equal to 70%; Described acyl group is one or more in acetyl group, propiono, bytyry, caproyl, caprylyl, certain herbaceous plants with big flowers acyl group, lauroyl, palmityl and other aliphatic or aromatic acyl group.Described solvent includes but not limited to aqueous formic acid (concentration expressed in percentage by weight is more than or equal to 70%), hexafluoroisopropanol, oxolane, ethanol, and those skilled in the art other solvent of being familiar with, as trichloroacetic acid, dichloroacetic acid etc.;
The intraluminal stent absorbed that develops of the present invention, is characterized in that described development coating is the azido benzoyl aminopolysaccharide coating containing developing agent.
The intraluminal stent absorbed that develops of the present invention, is characterized in that described developing agent is barium sulfate, cardiografin, and the developing agent that other developing agent of Clinical practice and those skilled in the art predict, as fluorescein, tantalum powder etc.
Above-mentioned a kind of intraluminal stent absorbed that develops, as intravascular stent, is applied to the narrow or embolotherapy of vessel lumen that angiopathy causes.
Above-mentioned a kind of intraluminal stent absorbed that develops, as biliary tract prosthesis, the pancreatic duct caused for pancreas gallbladder malignant tumor blocks, the treatment of cholestasis.
Above-mentioned a kind of intraluminal stent absorbed that develops, as urethra rack, for because of prostate hyperplasia, urethra so that urethral stricture are difficult to the treatment of urinating.
The intraluminal stent absorbed that develops of the present invention has good mechanical strength, and it is good that pressure holds rebound performance; The preparation main raw material(s) of intraluminal stent tubing absorbed that can develop is acylated amino polysaccharide, has good biocompatibility, a feature that degradable absorbs, and coating material azido benzoyl aminopolysaccharide also degradable absorbs.Meanwhile, can be undertaken operating and observing by image when the intraluminal stent developing absorption of the present invention is implanted in vivo.The absorption intraluminal stent that develops of the present invention has wide practical use clinically.
Accompanying drawing explanation
The observation on Growth of Fig. 1: L929 cell on diaphragm
Fig. 2: mtt assay measures the growth of L929 cell on diaphragm
Detailed description of the invention
Embodiment 1
Develop the intraluminal stent absorbed, and it is characterized in that the hollow tubular structure made for material with acylated amino polysaccharide, the outer surface of tubular structure has development coating, and tube wall is with or without penetrating pore space structure or patterning.
Described acylated amino polysaccharide is polyamides base glucosamine polysaccharide; total acyl group degree in its molecular structure is more than or equal to 70%; described acyl group is one or more in acetyl group, propiono, bytyry, caproyl, caprylyl, certain herbaceous plants with big flowers acyl group, lauroyl, palmityl and other aliphatic or aromatic acyl group, and the molecular structural formula of acylated amino polysaccharide is:
In formula, R
1, R
2or R
3h, acetyl group (-C
2h
3o), propiono (-C
3h
5o), bytyry (-C
4h
7o), caproyl (-C
6h
11o), caprylyl (-C
8h
15o) one or more or in certain herbaceous plants with big flowers acyl group, lauroyl, palmityl and other aliphatic or aromatic acyl group, acyl group degree is more than or equal to 70%.
Described development coating is the azido benzoyl aminopolysaccharide coating containing developing agent.
Described azido benzoyl aminopolysaccharide is hydrazoic benzoyl chitosan, azido benzoyl hydroxyethyl chitosan, azido benzoyl hydroxypropyl chitosan, azido benzoyl carboxymethyl chitosan, azido benzoyl chitin, azido benzoyl ethoxyl chitin, azido benzoyl Chitofilmer, and chitin, chitosan other azido benzoyl derivant.
Embodiment 2 can be developed the screening of intraluminal stent base material absorbed:
(1) preparation of diaphragm:
The preparation of chitosan diaphragm: take chitosan powder (deacetylation 92.5%) 2g, add aqueous acetic acid (volume fraction) 100ml of 2%, stirring and dissolving, is mixed with the chitosan glue that w/v (w/v) is 2%.Measure 15ml chitosan glue respectively and be placed in the PP square plate that the length of side is 50mm × 50mm, standing and drying in ventilating kitchen.The diaphragm of drying is placed in acid-base neutralization in the NaOH aqueous solution (concentration expressed in percentage by weight, lower same) of 2%, is washed to pH neutrality, dry, obtained chitosan diaphragm.
The preparation of chitin diaphragm: take chitin powder 2g, adds hexafluoroisopropanol solution 100ml, stirring and dissolving, is mixed with the chitin glue (w/v) of 2%.Measure 15ml chitin glue respectively and be placed in the rustless steel square plate that the length of side is 50mm × 50mm, standing and drying in ventilating kitchen, obtained chitin diaphragm.
The preparation of acyl group chitin diaphragm: take chitin powder 10g; add in glass reaction container; add acylating reagent solution of acetic anhydride 20mL; add methanol 150ml; stir, control temperature is 0 DEG C ~ 5 DEG C, then adds the perchloric acid solution (concentration expressed in percentage by weight of 70%; down together) 1ml is as catalyst, stirring reaction 48h.Reaction is finished; filter, solid-liquid separation, puts into the NaOH aqueous solution of 5% by solid content; acid-base neutralization; centrifugal, solid-liquid separation, solid content water washing desalination; 95% ethanol (volume fraction) dewaters; 50 DEG C of heat dryings, obtain acyl group chitin, and it is 115% that elemental microanalysis method (lower same) records its degree of acetylation.Take the acyl group chitin powder 2g that degree of acetylation is 115%, add formic acid solution (concentration expressed in percentage by weight, the lower same) 100ml of 80%, stirring and dissolving, is mixed with the acyl group chitin glue that w/v is 2%.Measure 15ml acyl group chitin glue respectively and be placed in the PP square plate that the length of side is 50mm × 50mm, standing and drying in ventilating kitchen.The diaphragm of drying is placed in the NaOH aqueous acid medium alkali neutralization of 2%, is washed to pH neutrality, dry, obtained acyl group chitin diaphragm.
(2) physical property of diaphragm compares:
Water absorption rate: get the chitosan diaphragm, chitin diaphragm, each 3 of the acyl group chitin diaphragm that are dried to constant weight respectively, specification is 2cm × 2cm, weighs respectively; be placed in distilled water and soak 24h; take out diaphragm filter paper and suck surface moisture, weigh, calculate water absorption rate.Result shows, and the water absorption rate of chitosan film is 416%, and the diaphragm after water suction has certain dilatancy; The water absorption rate of chitin film is 104%, and the diaphragm after water suction also has certain dilatancy, and degrees of expansion is lower than chitosan diaphragm; The water absorption rate of acyl group chitin film is 58%, and diaphragm expands minimum.The water absorption rate of visible acyl group chitin is minimum, and low water absorption decreases the expansion of diaphragm.
Hot strength: three kinds of diaphragms are under hygrometric state, and the hot strength of acyl group chitin diaphragm is maximum, and the hot strength of chitin diaphragm is taken second place, and the hot strength of chitosan diaphragm is the poorest.
(3) biocompatibility of diaphragm and degradability compare:
Cell compatibility: under aseptic condition, obtaining diameter respectively with trepan is 7mm chitosan diaphragm, chitin diaphragm, acyl group chitin diaphragm, is placed in the bottom of 96 porocyte culture plates respectively, adds 10% new-born calf serum fully infiltrate 24h by DMEM culture medium.Choose the L929 cell of the exponential phase through trypsinization, regulate cell density 4 × 10
4individual/ml, cell is inoculated in respectively the chaffy culture hole in bottom, and without the contrast culture hole of diaphragm, culture medium is that DMEM culture medium adds 10% new-born calf serum, every hole 200 μ l, in 37 DEG C, and 5%CO
2cultivate under condition, regularly change liquid.When cultivating 4d, the growth conditions of observation of cell under inverted microscope, and with mtt assay, the light absorption value at microplate reader mensuration 492nm place, calculates relative appreciation rate (RGR).As shown in Figure 1, the growth conditions of cell on acyl group chitin diaphragm is best, and cell density is high for experimental result, and state stretches, and the Growth of Cells on chitin diaphragm takes second place, and the cell quantity on chitosan diaphragm is minimum, and state is poor.The relative appreciation rate of cell the results are shown in Figure 2; the relative appreciation rate of cell on acyl group chitin film is 90.88 ± 26.35%; relative appreciation rate on chitin film is 50.31 ± 12.42%; relative appreciation rate on chitosan film is 15.08 ± 8.67%; as can be seen here, the cell compatibility of acyl group chitin diaphragm is better.
Degeneration: on cell compatibility experiment basis, chitin film has been screened in this research and acyl group chitin film carries out et al. Ke degradation experiment.Take rat as laboratory animal; chitin diaphragm, the acyl group chitin diaphragm of 5mm × 5mm is implanted respectively in subcutaneous rat and muscle; respectively at postoperative 1 week, 2 weeks, January, February, March, April, May, June, July, August, JIUYUE put to death often organize each 3 rats; observe the response situation of implantation film surrounding tissue; and get diaphragm surrounding tissue; 10% formalin fixative is fixed, and makes HE staining tissue slides, carries out pathologic examination.Experimental result shows, and two kinds of diaphragms implant subcutaneous rat and muscle, and acyl group chitin diaphragm has no the tissue inflammation reactions such as obvious encapsulation, capillary injection at the implantation initial stage, and its compatibility in subcutaneous, muscular tissue is good; Chitin diaphragm has slight tissue inflammation reaction at the implantation initial stage, and the degraded inflammatory reaction with diaphragm fades away, and also shows good biocompatibility; Acyl group chitin diaphragm is complete degraded in subcutaneous 7 months, and in muscle degraded in 8 months completely, chitin diaphragm is subcutaneous complete with muscle degraded in 6 ~ 7 months, and degradation speed is slightly faster than acyl group chitin diaphragm.Shown by et al. Ke degradation experiment, chitin film and acyl group chitin film all have good degeneration and histocompatibility, and wherein acyl group chitin diaphragm shows better histocompatibility.
Chitosan diaphragm, chitin diaphragm, acyl group chitin diaphragm screen through above-mentioned physical property and biocompatibility, degradability; acyl group chitin diaphragm has better physical property and biology performance; show that aminopolysaccharide water absorption rate after acyl group is low, good biocompatibility further, be better than the aminopolysaccharide without acyl group.Chitosan, chitin are aminopolysaccharide, and the C6-O position in both molecular structures, C3-O position, C2-N position all acylation reaction can occur, and make acylated amino polysaccharide.
Embodiment 3 can be developed the preparation of intraluminal stent tubing 1 absorbed:
Take chitosan powder (deacetylation 92%) 20g, add in glass reaction container, add acylating reagent solution of acetic anhydride 50mL; add methanol 100ml; control temperature is 10 DEG C, adds the perchloric acid solution 1ml of 70% as catalyst, stirring reaction 36h under stirring.Reaction is finished, and filter, solid-liquid separation, puts into the NaOH aqueous solution of 5%, acid-base neutralization by solid content, centrifugal, solid-liquid separation, and solid content washing desalination, 95% ethanol dehydration, 60 DEG C of heat dryings, obtain the acylated amino polysaccharide 1 that acyl group degree is 74.5%.Acylated amino polysaccharide 1 has acetyl group structure, and acetyl content is 74.5%.
Take the above-mentioned acylated amino polysaccharide 1 of 2.5g; add hexafluoroisopropanol solution 61ml (proportion 1.60) and make solvent; low temperature dissolves, and is mixed with the acylated amino polysaccharide glue (w/v is 4.1%) that concentration expressed in percentage by weight is 2.5%.Get the stainless steel bar Pipe making mold of length 10cm, diameter 4mm, be connected to the Pipe making mold seam on tuber, open tuber; by acylated amino polysaccharide glue, coating is surperficial at the stainless steel bar rotated equably; control glue thickness at 5mm ~ 6mm, under room temperature, Rotary drying becomes tubulose.After glue drying, take off above-mentioned stainless steel bar, together with the tubular material of preparation, the ethanol water putting into 50% soaks, de-pipe, tubular material is through washing, ethanol dehydration, drying at room temperature, the Absorbable rod intraluminal stent tubing 1 of obtained hollow tubular, its lumen diameter is 4mm, and pipe thickness is 0.2mm.
Take hydrazoic benzoyl chitosan 0.2g, add 10ml distilled water, stirring and dissolving, obtain the azido benzoyl aminopolysaccharide glue that concentration expressed in percentage by weight is 2%, add developing agent cardiografin 1ml, stir, obtain developing agent glue.Get above-mentioned Absorbable rod intraluminal stent base material 1, two ends connect and are fixed on plater seam, open plater, developing agent glue is evenly injected in the outer surface of the intraluminal stent base material 1 of rotation through the external moveable playpipe of plater, injector head, make developing agent glue uniform coating at the outer surface of intraluminal stent base material 1, control glue thickness 0.5 ~ 1mm, ultraviolet light cross-linking under room temperature, dry, the Absorbable rod intraluminal stent tubing 1 of obtained band developing agent, its lumen diameter is 4mm, and pipe thickness is 0.25mm.
Embodiment 4 can be developed the preparation of intraluminal stent tubing 2 absorbed:
Take chitosan powder (deacetylation 92%) 20g, add in glass reaction container, add acylating reagent propionic andydride solution 120mL; add methanol 100ml; control temperature is 0 ~ 5 DEG C, adds methanesulfonic acid solution 2.0ml as catalyst, stirring reaction 24h under stirring.Reaction is finished, and filter, solid-liquid separation, solid content adds in the KOH aqueous solution of 2% of ice bath, acid-base neutralization, and water washing is neutral to pH, and solid-liquid separation, 95% ethanol dehydration, 50 DEG C of heat dryings, obtain the acylated amino polysaccharide 2 that acyl group degree is 102.3%.Acylated amino polysaccharide 2 has propiono, acetyl group structure, and wherein acetyl content is about 8%, and propionyl content is about 94.3%.
Take the above-mentioned acylated amino polysaccharide 2 of 14.8g; the formic acid solution 60ml (proportion 1.17) adding 75% makes solvent; stirring and dissolving, is mixed with the acylated amino polysaccharide glue (w/v is 24.7%) that concentration expressed in percentage by weight is 17.4%.Get the ceramic rod Pipe making mold of length 10cm, diameter 8mm; be connected to the Pipe making mold seam on tuber; open tuber; by acylated amino polysaccharide glue equably coating rotate ceramic rod on the surface; control glue thickness at 6mm ~ 7mm; temperature control 40 ~ 50 DEG C, Rotary drying becomes tubulose.After glue drying, take off ceramic rod, together with the tubular material of preparation, the NaOH aqueous solution putting into 5% soaks, acid-base neutralization, de-pipe, tubular material is neutral to pH through water washing, and dehydrated alcohol dewaters, 50 ~ 60 DEG C of heat dryings, the Absorbable rod intraluminal stent tubing 2 of obtained hollow tubular, its lumen diameter is about 8mm, and pipe thickness is 1.5mm.
Take azido benzoyl hydroxyethyl chitosan 2.5g, add 10ml distilled water, stirring and dissolving, obtain the azido benzoyl aminopolysaccharide glue that concentration expressed in percentage by weight is 20%, add developing agent barium sulfate 20mg, stir, obtain developing agent glue.Get above-mentioned Absorbable rod intraluminal stent base material 2, two ends connect and are fixed on plater seam, open plater, developing agent glue is evenly injected in the outer surface of the intraluminal stent base material 2 of rotation through the external moveable playpipe of plater, injector head, make developing agent glue uniform coating at the outer surface of intraluminal stent base material 2, control glue thickness 2 ~ 3mm, ultraviolet light cross-linking under room temperature, dry, the Absorbable rod intraluminal stent tubing 2 of obtained band developing agent, its lumen diameter is about 8mm, and pipe thickness is 2mm.
Embodiment 5 can be developed the preparation of intraluminal stent tubing 3 absorbed:
Take chitosan powder (deacetylation 85%) 20g; add in glass reaction container; add acylating reagent butyryl oxide. solution 200mL; add methanol 100ml; control temperature is 20 DEG C; add under stirring concentration expressed in percentage by weight be the sulfuric acid solution 2ml of 70% as catalyst, stirring reaction 48h.Reaction is finished, and filter, solid-liquid separation, solid content puts into the NaOH aqueous solution of 5%, acid-base neutralization, water washing desalination, solid-liquid separation, and dehydrated alcohol dewaters, and natural drying, obtains the acylated amino polysaccharide 3 that acyl group degree is 135%.Acylated amino polysaccharide 3 has bytyry, acetyl group structure, and wherein acetyl content is about 15%, and bytyry content is about 120%.
Take the above-mentioned acylated amino polysaccharide 3 of 6.2g; add concentration expressed in percentage by weight be 80% formic acid solution 60ml (proportion 1.18) make solvent; low temperature dissolves, and is mixed with the acylated amino polysaccharide glue (w/v is 10.3%) that concentration expressed in percentage by weight is 8.1%.Get the PP rod Pipe making mold of length 10cm, diameter 10mm, be connected to the Pipe making mold seam on tuber, open tuber; by acylated amino polysaccharide glue equably coating rotate PP rod surface on; control glue thickness at 5mm ~ 6mm, temperature control 40 ~ 50 DEG C, Rotary drying becomes tubulose.After glue drying, stop operating, take off PP rod, together with the tubular material of preparation, the NaOH aqueous solution putting into 4% soaks, acid-base neutralization, de-pipe, tubular material is neutral to pH through water washing, dehydrated alcohol dewaters, 50 ~ 60 DEG C of heat dryings, the Absorbable rod intraluminal stent tubing 3 of obtained hollow tubular, its lumen diameter is 10mm, and pipe thickness is 1.0mm.
Take azido benzoyl hydroxypropyl chitosan 1.1g, add 10ml distilled water, stirring and dissolving, obtain the azido benzoyl aminopolysaccharide glue that concentration expressed in percentage by weight is 10%, add developing agent cardiografin 1ml, stir, obtain developing agent glue.Get above-mentioned Absorbable rod intraluminal stent base material 3, two ends connect and are fixed on plater seam, open plater, developing agent glue is evenly injected in the outer surface of the intraluminal stent base material 3 of rotation through the external moveable playpipe of plater, injector head, make developing agent glue uniform coating at the outer surface of intraluminal stent base material 3, control glue thickness 1.5 ~ 2mm, ultraviolet light cross-linking under room temperature, dry, the Absorbable rod intraluminal stent tubing 3 of obtained band developing agent, its lumen diameter is 10mm, and pipe thickness is 1.2mm.
Embodiment 6 can be developed the preparation of intraluminal stent 4 absorbed:
Take chitosan powder (deacetylation 92%) 10g, add in glass reaction container, add acylating reagent caproic anhydride 200ml, control temperature is 0 DEG C, adds 70% perchloric acid solution 5.0ml as catalyst, stirring reaction 36h under stirring.Reaction is finished, and leach reaction solid content, by the NaOH aqueous solution acid-base neutralization of 2%, water washing desalination, solid-liquid separation, 50 ~ 60 DEG C of heat dryings, obtain the acylated amino polysaccharide 4 that acyl group degree is 108.7%.Acylated amino polysaccharide 4 has caproyl, acetyl group structure, and wherein acetyl content is about 8%, and caproyl content is about 100.7%.
Take the above-mentioned acylated amino polysaccharide 4 of 2g, add dehydrated alcohol 60ml (proportion 0.79) and make solvent, stirring and dissolving, be mixed with the acylated amino polysaccharide glue (w/v is 3.3%) that concentration expressed in percentage by weight is 4%.Get the stainless steel bar Pipe making mold of length 10cm, diameter 3mm; be connected to the Pipe making mold seam on tuber; open tuber; by acylated amino polysaccharide glue equably coating rotate stainless steel bar on the surface; control glue thickness at 4mm ~ 5mm; temperature control 40 ~ 50 DEG C, Rotary drying becomes tubulose.After glue drying, take off stainless steel bar, together with the tubular material of preparation, put into distilled water and soak, de-pipe, 50 ~ 60 DEG C of heat dryings, the Absorbable rod intraluminal stent tubing 4 of obtained hollow tubular, its lumen diameter is about 3mm, and pipe thickness is 0.6mm.
Take azido benzoyl carboxymethyl chitosan 0.5g, add 10ml distilled water, stirring and dissolving, obtain the azido benzoyl aminopolysaccharide glue that concentration expressed in percentage by weight is 5%, add developing agent barium sulfate 200mg, stir, obtain developing agent glue.Get above-mentioned Absorbable rod intraluminal stent base material 4, two ends connect and are fixed on plater seam, open plater, developing agent glue is evenly injected in the outer surface of the intraluminal stent base material 4 of rotation through the external moveable playpipe of plater, injector head, make developing agent glue uniform coating at the outer surface of intraluminal stent base material 4, control glue thickness 0.5 ~ 1mm, ultraviolet light cross-linking under room temperature, dry, the Absorbable rod intraluminal stent tubing 4 of obtained band developing agent, its lumen diameter is about 3mm, and pipe thickness is 0.65mm.
Embodiment 7 can be developed the preparation of intraluminal stent tubing 5 absorbed:
Take chitin powder (acetyl content 85%) 20g; add in glass reaction container; add acylating reagent butyryl oxide. solution 150mL; add methanol 100ml; controlling reaction temperature is 0 ~ 5 DEG C; add under stirring concentration expressed in percentage by weight be the perchloric acid solution 2ml of 70% as catalyst, stirring reaction 48h.Reaction is finished, and filter, solid-liquid separation, puts into the NaOH aqueous solution of 5%, acid-base neutralization, solid-liquid separation by solid content, solid content water washing is to center, and 95% ethanol dehydration, natural drying, obtains the acylated amino polysaccharide 5 of acyl group degree 235%.Acylated amino polysaccharide 5 has bytyry, acetyl group structure, and wherein acetyl content is about 85%, and bytyry content is about 150%.
Take the above-mentioned acylated amino polysaccharide 5 of 1.0g, add tetrahydrofuran solution 60ml (proportion 0.89) and make solvent, stirring and dissolving, preparation concentration expressed in percentage by weight is the acylated amino polysaccharide glue (w/v is 1.7%) of 1.8%.Get the stainless steel bar Pipe making mold of length 10cm, diameter 4mm; be connected to the Pipe making mold seam on tuber, open tuber, by acylated amino polysaccharide glue, coating is surperficial at the stainless steel bar rotated equably; control glue thickness at 5mm ~ 6mm, Rotary drying becomes tubulose.After glue drying, take off stainless steel bar, together with the tubular material of preparation, put into 50% ethanol water to soak, de-pipe, 50 ~ 60 DEG C of heat dryings, the Absorbable rod intraluminal stent tubing 5 of obtained hollow tubular, its lumen diameter is about 4mm, and pipe thickness is 0.4mm.
Take azido benzoyl chitin 0.5g, add 10ml distilled water, stirring and dissolving, obtain the azido benzoyl aminopolysaccharide glue that concentration expressed in percentage by weight is 5%, add developing agent barium sulfate 50mgl, stir, obtain developing agent glue.Get above-mentioned Absorbable rod intraluminal stent base material 5, two ends connect and are fixed on plater seam, open plater, developing agent glue is evenly injected in the outer surface of the intraluminal stent base material 5 of rotation through the external moveable playpipe of plater, injector head, make developing agent glue uniform coating at the outer surface of intraluminal stent base material 5, control glue thickness 0.5 ~ 1mm, ultraviolet light cross-linking under room temperature, dry, the Absorbable rod intraluminal stent tubing 5 of obtained band developing agent, its lumen diameter is about 4mm, and pipe thickness is 0.5mm.
Embodiment 8 can be developed the preparation of intraluminal stent tubing 6 absorbed:
Take chitin powder (acetyl content 85%) 20g, add in glass reaction container, add acylating reagent solution of acetic anhydride 300mL; add methanol 50ml; control temperature is 10 DEG C, adds the sulfuric acid solution 2ml of 70% as catalyst, stirring reaction 72h under stirring.Reaction is finished, and filter, solid-liquid separation, solid content puts into the NaOH aqueous solution of 5% of ice bath, acid-base neutralization, water washing desalination, solid-liquid separation, 95% ethanol dehydration, natural drying, obtains the acylated amino polysaccharide 6 that acyl group degree is 275%.Acylated amino polysaccharide 6 has acetyl group structure, and acetyl content is about 275%.
Take the above-mentioned acylated amino polysaccharide 6 of 3.5g; add concentration expressed in percentage by weight be 80% formic acid solution 60ml (proportion 1.18) make solvent; stirring and dissolving, preparation concentration expressed in percentage by weight is the acylated amino polysaccharide glue (w/v is 5.8%) of 4.7%.Get the Glass rod Pipe making mold of length 10cm, diameter 5mm; be connected to the Pipe making mold seam on tuber; open tuber; by acylated amino polysaccharide glue equably coating rotate Glass rod on the surface; control glue thickness at 5mm ~ 6mm; temperature control 40 ~ 50 DEG C, Rotary drying becomes tubulose.After glue drying, take off Glass rod, together with the tubular material of preparation, put into containing 2%NaOH 50% ethanol water soak, de-pipe, tubular material water washing is neutral to pH, the ethanol dehydration of 95%, dry at 30 ~ 40 DEG C, the Absorbable rod intraluminal stent tubing 6 of obtained hollow tubular, its lumen diameter is about 5mm, and pipe thickness is 0.7mm.
Take azido benzoyl ethoxyl chitin 1.1g, add 10ml distilled water, stirring and dissolving, obtain the azido benzoyl aminopolysaccharide glue that concentration expressed in percentage by weight is 10%, add developing agent barium sulfate 50mg, stir, obtain developing agent glue.Get above-mentioned Absorbable rod intraluminal stent base material 6, two ends connect and are fixed on plater seam, open plater, developing agent glue is evenly injected in the outer surface of the intraluminal stent base material 6 of rotation through the external moveable playpipe of plater, injector head, make developing agent glue uniform coating at the outer surface of intraluminal stent base material 6, control glue thickness 0.5 ~ 1mm, ultraviolet light cross-linking under room temperature, dry, the Absorbable rod intraluminal stent tubing 6 of obtained band developing agent, its lumen diameter is about 5mm, and pipe thickness is 0.8mm.
Embodiment 9 can be developed the preparation of intraluminal stent tubing 7 absorbed:
Take the acylated amino polysaccharide 2 that the above-mentioned acyl group degree of 1.5g is 102.3%; 2.5g acyl group degree is the acylated amino polysaccharide 6 of 275%; add concentration expressed in percentage by weight be 88% formic acid solution 60ml (proportion 1.20) make solvent; low temperature dissolves, and is mixed with the acylated amino polysaccharide glue (w/v is 2.5%) that concentration expressed in percentage by weight is 4.6%.Get the stainless steel bar Pipe making mold of length 10cm, diameter 8mm; be connected to the Pipe making mold seam on tuber; open tuber; by acylated amino polysaccharide glue equably coating rotate stainless steel bar on the surface; control glue thickness at 6mm ~ 8mm; temperature control 30 ~ 40 DEG C, Rotary drying becomes tubulose.After glue drying, take off stainless steel bar, together with the tubular material of preparation, the aqueous solution put into containing 3%NaOH soaks, acid-base neutralization, de-pipe, tubular material is neutral to pH through water washing, ethanol dehydration, drying at room temperature, the Absorbable rod intraluminal stent tubing 7 of obtained hollow tubular, its lumen diameter is about 8mm, and pipe thickness is 0.8mm.
Take azido benzoyl Chitofilmer 0.5g, add 10ml distilled water, stirring and dissolving, obtain the azido benzoyl aminopolysaccharide glue that concentration expressed in percentage by weight is 5%, add developing agent barium sulfate 500mg, stir, obtain developing agent glue.Get above-mentioned Absorbable rod intraluminal stent base material 6, two ends connect and are fixed on plater seam, open plater, developing agent glue is evenly injected in the outer surface of the intraluminal stent base material 7 of rotation through the external moveable playpipe of plater, injector head, make developing agent glue uniform coating at the outer surface of intraluminal stent base material 7, control glue thickness 0.8 ~ 1.2mm, ultraviolet light cross-linking under room temperature, dry, the Absorbable rod intraluminal stent tubing 7 of obtained band developing agent, its lumen diameter is about 7mm, and pipe thickness is 1.0mm.
Embodiment 10 can be developed the mechanical experimental results of intraluminal stent tubing absorbed
The intraluminal stent tubing of the developed absorption in above-described embodiment all has good mechanical strength, by electronic universal puller system, the test of mechanical property is carried out to the above-mentioned intraluminal stent tubing 1 ~ 7 absorbed that develops, the hot strength of intraluminal stent is at 1.8 ~ 3.7N, elongation at break, 50 ~ 70%, shows the better mechanical property of intraluminal stent tubing.
Embodiment 11 can be developed the Laser cutting of intraluminal stent absorbed:
Femto-second laser is erected on operation control platform, connects to form intraluminal stent process operation system with computer for controlling, pneumatic motor, the first-class auxiliary facilities of cutting.The intraluminal stent tubing 4 of the intraluminal stent tubing 1 of the developed absorption of above-described embodiment 3, the developed absorption of embodiment 6 is individually fixed on the rotatable chuck in support process operation system, computer is according to the cutting pattern programming preset, control support process operation system works, by the movement of the focal beam spot of femto-second laser, laser pulse carries out Laser cutting to intraluminal stent tubing.The intraluminal stent 1 pipe range 4cm of the developed absorption after processing, lumen diameter 4mm, pipe thickness 0.25mm; Can be developed the intraluminal stent 4 pipe range 3cm absorbed, lumen diameter 3mm, pipe thickness 0.65mm; Tube wall all has penetrating rule or irregular pore space structure or patterning.
Embodiment 12 can develop absorb intraluminal stent machine cuts processing:
The intraluminal stent tubing 2 of the developed absorption in above-described embodiment 4, embodiment 7, the intraluminal stent tubing 5 absorbed that can develop are individually fixed on support process operation platform, machine cuts processing is carried out to intraluminal stent tubing.The intraluminal stent 2 pipe range 2cm of the developed absorption after processing, lumen diameter 8mm, pipe thickness 2mm; Can be developed the intraluminal stent 5 pipe range 2cm absorbed, lumen diameter 4mm, pipe thickness 0.5mm; Tube wall does not have penetrating pore space structure or patterning.
In embodiment 13 body, Ink vessel transfusing implants experiment:
Respectively in Example 11 in the intraluminal stent 4 of the developed absorption of Laser cutting and embodiment 12 through the intraluminal stent 5 of developed absorptions of machine cuts processing, respectively get 2, pack separately, ethane via epoxyethane sterilizing, do the implantation of dog femoral artery.Experiment beasle dog 4, water 12h is prohibited in fasting, sleep peaceful II by after 0.05ml/kg dosage intramuscular injection anesthesia with land, dog dorsal position is fixed on operating-table, remove right inboard leg near abdominal part place hair, with iodophor disinfection, cut skin and muscular tissue successively, ligation thin vessels, separate dog femoral artery blood vessel, intravenous injection heparin (1mg/Kg body weight), proximal part and the distal end blocking blood flow of femoral artery is clamped respectively with vascular clamp, longitudinally 1cm otch is cut at the femoral artery place of blocking blood flow, the intravascular stent of sterilizing is cut along femoral artery and puts into femoral artery, 4 dogs respectively put an intravascular stent, with 6-0 blood vessel suture blood vessel otch, unclamp near, after distal end vascular clamp, examine anastomotic stoma with or without oozing of blood, determine without layer-by-layer suture muscular tissue and skin after oozing of blood, skin surface smears povidone iodine, and wrap up with sterile gauze.Postoperative animal gives penicillin 800,000 U intramuscular injection 3d, and prevention infection, normally raises.Test the intraluminal stent of the developed absorption that latter 1 day observes to implant with X-ray, the visible image implanting tube chamber, tests the unobstructed situation of femoral artery blood flow of latter 3 months Doppler observation operative sites, and display femoral artery blood flow is unobstructed, observes obvious vascular pulsation.
In embodiment 14 body, bile duct is implanted into experiment:
The Absorbable rod intraluminal stent 1 got through Laser cutting in 2 embodiments 11 is packed separately, and ethane via epoxyethane sterilizing is for subsequent use.Domesticated dog 2 is used in experiment, 1 female 1 is male, body weight 20, 22kg, water 12h is prohibited in fasting, sleep peaceful II by after 0.05ml/kg dosage intramuscular injection anesthesia respectively with land, dog dorsal position is fixed on operating-table, remove abdominal operation district hair, with iodophor disinfection, open abdomen, free common bile duct, apart from duodenum upper limb 2cm place longitudinal incision common bile duct, otch is about 0.5cm, aseptic Absorbable rod intraluminal stent 1 is put into bile duct along incision, every domesticated dog places an intraluminal stent, sew up bile duct otch, examine after determining anastomotic stoma ne-leakage, sebific duct drain is placed under liver, layer-by-layer suture muscular tissue and skin, skin surface smears povidone iodine, and wrap up with sterile gauze.Postoperative animal gives penicillin 800,000 U intramuscular injection 3d, and prevention infection, normally raises.The intraluminal stent of the developed absorption observing to implant with X-ray for postoperative 1 day, the visible image implanting intraluminal stent, observes drainage tube and draws without yellow green bile.Month after operation puts to death laboratory animal, opens abdomen, cuts the bile duct position of implant chamber support under operation, and observe display bile duct without obvious stenosis, bile duct inner surface is smooth, without inflammatory reactions such as rednesses, intraluminal stent form is complete, has mucosa to cover.
In embodiment 15 body, urinary catheter is implanted into experiment:
Get in 3 embodiments 12 and pack separately through the Absorbable rod intraluminal stent 5 of machine cuts processing, ethane via epoxyethane sterilizing is for subsequent use.Domesticated dog 3 is used in experiment, male, body weight 20-25kg, water 12h is prohibited in fasting, sleep peaceful II by after 0.05ml/kg dosage intramuscular injection anesthesia respectively with land, dog dorsal position is fixed on operating-table, with the aseptic stainless steel bar of diameter 4.5mm, the Absorbable rod intraluminal stent 5 of sterilizing is driven in the wrong direction insertion urethra to row gland position by the urethral orifice of dog.Postoperative dog is normally raised, and urethra is unobstructed, urinates normal.The intraluminal stent of the developed absorption observing to implant with X-ray for postoperative 1 day, the visible image implanting intraluminal stent.Month after operation puts to death laboratory animal, cuts urethra implantable tubular support portions under operation, and observe display urinary catheter without obvious stenosis, intraluminal stent is close to urethra, and urethra inner surface is smooth, without inflammatory reactions such as rednesses, intraluminal stent form is complete.
The intraluminal stent absorbed that develops of the present invention, has the feature of degradable absorption, good biocompatibility; The preparation of the intraluminal stent of described developed absorption, can according to different purposes needs, the diameter of adjustment Pipe making mold and length and glue thickness, thus prepare the tubular bracket that internal diameter varies in size, pipe thickness different, length is different.The intraluminal stent absorbed that develops of the present invention has broad application prospects clinically, can by Operation body, as intravascular stent, is applied to the narrow or embolotherapy of vessel lumen that angiopathy causes; As biliary tract prosthesis, the pancreatic duct caused for pancreas gallbladder malignant tumor blocks, the treatment of cholestasis; As urethra rack, for because of prostate hyperplasia, urethra so that urethral stricture are difficult to the treatment of urinating.The intraluminal stent of absorption of developing of the present invention, along with the reparation of pathological changes, is finally degraded and absorbed in vivo, avoids longer-term persistence in vivo, have wide market prospect.
Claims (10)
1. can develop the intraluminal stent absorbed, and it is characterized in that: the hollow tubular structure made for material with acylated amino polysaccharide, the outer surface of tubular structure has development coating, and tube wall is with or without penetrating pore space structure or patterning.
2. can develop intraluminal stent as claimed in claim 1 that absorb, it is characterized in that:
The molecular structure of described acylated amino polysaccharide is polyamides base glucosamine polysaccharide; total acyl group degree in the molecular structure of described acylated amino polysaccharide is more than or equal to 70%; described acyl group is one or more in acetyl group, propiono, bytyry, caproyl, caprylyl, certain herbaceous plants with big flowers acyl group, lauroyl, palmityl and other aliphatic or aromatic acyl group, and the molecular structural formula of acylated amino polysaccharide is:
In formula, R
1, R
2or R
3be one or more in H, acetyl group, propiono, bytyry, caproyl, caprylyl or certain herbaceous plants with big flowers acyl group, lauroyl, palmityl and other aliphatic or aromatic acyl group, acyl group degree is more than or equal to 70%.
3. the intraluminal stent of a kind of absorption of developing as claimed in claim 1, is characterized in that: described development coating is the azido benzoyl aminopolysaccharide coating containing developing agent.
4. azido benzoyl aminopolysaccharide as claimed in claim 3; it is characterized in that described azido benzoyl aminopolysaccharide is one or more in hydrazoic benzoyl chitosan, azido benzoyl hydroxyethyl chitosan, azido benzoyl hydroxypropyl chitosan, azido benzoyl carboxymethyl chitosan, azido benzoyl chitin, azido benzoyl ethoxyl chitin, azido benzoyl Chitofilmer, and chitin, chitosan other azido benzoyl derivant.
5. the preparation method of a kind of intraluminal stent absorbed that develops according to claim 1, is characterized in that:
Acylated amino polysaccharide is dissolved in solvent, preparation concentration expressed in percentage by weight be 1% ~ 20% or w/v be 1% ~ 25% acylated amino polysaccharide glue; Open the tuber with Pipe making mold, by acylated amino polysaccharide glue coating on Pipe making mold, control glue thickness, room temperature or temperature control heat drying become tubulose;
Pipe making mold is put into dilute alkaline aqueous solution, ethanol water or distilled water together with the tubular material prepared soak, de-pipe, is washed to pH neutrality, and dehydration is dry, obtains the Absorbable rod intraluminal stent base material of hollow tubular;
Preparation concentration expressed in percentage by weight is the azido benzoyl aminopolysaccharide glue of 0.5% ~ 25%, adds developing agent, obtained developing agent glue, by developing agent glue coating at Absorbable rod intraluminal stent substrate outer surface, and ultraviolet light cross-linking;
Drying, the intraluminal stent tubing of the developed absorption of obtained band developing agent;
The intraluminal stent tubing absorbed that can develop is processed through Laser cutting or machine cuts, and obtained tube wall is with or without the intraluminal stent of the developed absorption of penetrating pore space structure or patterning.
6. the preparation method of the intraluminal stent of a kind of absorption of developing as claimed in claim 5, is characterized in that:
Described solvent is selected from hexafluoroisopropanol, oxolane, ethanol, trichloroacetic acid, dichloroacetic acid, concentration expressed in percentage by weight be more than or equal to 70% aqueous formic acid.
7. the preparation method of the intraluminal stent of a kind of absorption of developing as claimed in claim 5, is characterized in that:
Described developing agent is one or more in barium sulfate, cardiografin, fluorescein, tantalum powder.
8. can develop intraluminal stent as claimed in claim 1 that absorb, as intravascular stent, is applied to the narrow or embolotherapy of vessel lumen that angiopathy causes.
9. can develop intraluminal stent as claimed in claim 1 that absorb, and as biliary tract prosthesis, the pancreatic duct caused for pancreas gallbladder malignant tumor blocks, the treatment of cholestasis.
10. can develop intraluminal stent as claimed in claim 1 that absorb, as urethra rack, for because of prostate hyperplasia, urethra so that urethral stricture are difficult to the treatment of urinating.
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| CN105999425A (en) * | 2016-05-24 | 2016-10-12 | 德州海利安生物科技股份有限公司 | Developing type degradable repairing stent |
| CN106039426A (en) * | 2016-05-24 | 2016-10-26 | 德州海利安生物科技股份有限公司 | Developing type degradable restoration pancreatic duct bracket |
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| CN111281599A (en) * | 2020-03-19 | 2020-06-16 | 中国海洋大学 | Enhanced artificial nerve conduit and preparation method and application thereof |
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| CN105148330B (en) | 2018-01-23 |
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