CN106620890A - Endoscopic hemostatic clips with thrombin sustained release function and method for preparing endoscopic hemostatic clips - Google Patents
Endoscopic hemostatic clips with thrombin sustained release function and method for preparing endoscopic hemostatic clips Download PDFInfo
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- CN106620890A CN106620890A CN201610726284.1A CN201610726284A CN106620890A CN 106620890 A CN106620890 A CN 106620890A CN 201610726284 A CN201610726284 A CN 201610726284A CN 106620890 A CN106620890 A CN 106620890A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/086—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/252—Polypeptides, proteins, e.g. glycoproteins, lipoproteins, cytokines
- A61L2300/254—Enzymes, proenzymes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/418—Agents promoting blood coagulation, blood-clotting agents, embolising agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
- A61L2300/608—Coatings having two or more layers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/08—Coatings comprising two or more layers
Abstract
The invention provides a method for preparing endoscopic hemostatic clips with a thrombin sustained release function. The method includes steps of (1), carrying out ultrasonic washing and drying on metal matrixes by the aid of deionized water, then soaking the metal matrixes in mixed solution, taking the metal matrixes out of the mixed solution, secondarily drying the metal matrixes and then washing the metal matrixes; (2), soaking the metal matrixes treated at the step (1) in hydroxyapatite suspension, taking the metal matrixes out of the hydroxyapatite suspension and drying the metal matrixes; (3), soaking the metal matrixes treated at the step (2) in thrombin solution and taking the metal matrixes out of the thrombin solution to obtain the endoscopic hemostatic clips which are the metal matrixes. The method has the advantages that medicines to which the thrombin only can be locally applied can be subjected to targeted sustained release, and accordingly targeted sustained release hemostasis can be carried out during endoscopic surgery.
Description
Technical field
The present invention relates to medical apparatus and instruments and its preparation field, more particularly to a kind of thrombin slow release hysteroscope lower hemostasia folder and
The preparation method of related medical apparatus.
Background technology
At present, the doctor of the diagnosis and treatment such as developing rapidly and innovation with medical skill, various hysteroscope technologies, less invasive techniques unification
Learning to do section progressively becomes the emergence of main flow medical skill, but it is normal that hysteroscope also brings some upper gastrointestinal hemorrhage with mis instruments
The digestive tract disease seen, while being also postoperative complication common in treatment under hysteroscope.For in the tradition of upper gastrointestinal hemorrhage
Section's treatment meanss mainly have localized pulverization or injection hemostasis, intravenous applications haemostatic medicament etc., and current hysteroscope lower hemostasia is extensively applied
Targeted drug thrombin acts locally on focus surface, and blood quickly forms stable sludged blood.But exist after targeting sprinkling solidifying
Hemase reduces drug effect by the problem of tissue fluid rapid dilution.Afterwards with the continuous development and improvement of apparatus under hysteroscope, for office
Portion stops blooding and the various anastomosis clamp of closing perforation start appearance.Titanium is pressed from both sides as one of important apparatus treated under hysteroscope, current
Physical containment therapeutical effect is undertaken to local damage.Many scholars attempt target slow-release thrombin, mesh on medical metal base material
Front all of slow release research is all based on bio-inert material surface, and not only biological activity is poor, and heavy metal ion toxicity can be made
Into blood coagulation enzyme killing.(hydroxyapatite, is abbreviated as HA or HAP to hydroxyapatite, and molecular formula is Ca10(OH)2(PO4)6) be
Main (inorganic) composition of tooth and skeleton, medically also serves as ahead of the curve the optimal components of artificial bone.Hydroxylapatite biology
Compatibility is good, is to stimulate or induce bone growth and can form synosteotic natural ceramic material with osseous tissue, raw
Thing compatibility and biological activity are superior to tricalcium phosphate and other phosphorus calcium ceramic materials.The use of hydroxyapatite, contributes to thin
The adhesion of born of the same parents, propagation and Function, it is still unexcellent on the basis of directly as the replacements such as bone, tooth or impairment renovation material
Different bone tissue engineer carrier material, also can be used as other medical science functional materials or the carrier material of medicine.
The content of the invention
Present invention aim to address subproblem present in existing thrombin slow release medical instruments field, there is provided a kind of
Thrombin slow release hysteroscope lower hemostasia is pressed from both sides.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of thrombin slow release hysteroscope lower hemostasia folder, comprises the steps：
(1) will be soaked in mixed solution after metallic substrates deionized water supersound washing drying, taking-up carries out secondary dry
Washing after dry；
(2) metallic substrates after step (1) process are soaked in hydroxyapatite suspension, take out drying；
(3) metallic substrates after step (2) process are soaked in be taken out in thrombin solution and are obtained final product；
The metallic substrates are pressed from both sides for the hysteroscope lower hemostasia of metal matrix.
Preferably, the drying in the step (1) and step (2) be in drying baker 55-65 DEG C be dried 6-8 minutes or
25-28 DEG C of air drying 1.2-1.8 hour.
Preferably, the soaking temperature in the step (1) is 25-28 DEG C, and the time is 1-2 minutes.
Preferably, the redrying in the step (1) is dried 5-8 minutes or 25-28 DEG C of sky for 60-65 DEG C in drying baker
1.2-1.8 hours are dried in gas.
Preferably, the mixed solution in the step (1) for 5mol/l 1-hydroxy ethylidene-1,1-diphosphonic acid solution 30-50 parts,
Orthophosphoric acid solution 3-5 parts of 3mol/l, hydrogen peroxide or sodium bromate 1-2 parts mix.
Preferably, the hydroxyapatite turbid liquid concentration in the step (2) is 25g/l, and soaking temperature is 28-30 DEG C,
Time is 6-8 minutes.
Preferably, concentration of thrombin is 4500-4800U/l in the thrombin solution in the step (3), is frozen by thrombin
It is prepared by dry powder and 0.9% normal saline.
Preferably, the soaking temperature in the step (3) is 20-25 DEG C, and the time is 1-1.5 hours.
The another aspect of the present invention is that a kind of thrombin slow release hysteroscope lower hemostasia is pressed from both sides, including the Metal Substrate of hysteroscope lower hemostasia folder
Bottom, is coated with successively chemical conversion film layer, phosphate layer, hydroxyapatite layer and blood coagulation in the metallic substrates of the metallic substrates
Enzyme layer.
Preferably, the thickness of the metallic substrates is 0.1-0.8 millimeters, and the thickness of phosphate layer is 4-40 microns, chemical
The thickness of film layer is changed into 1-10 nanometers, the thickness of hydroxyapatite layer is 0.02-0.06 millimeters, and the thickness of thrombin layer is
0.1-1 microns.
Preferably, the metallic substrates be rustless steel, carbon steel, screw-thread steel, cold-rolled steel, hot-rolled steel, manganese steel, aluminum, aluminium alloy,
Titanium, titanium alloy, cobalt alloy, one kind of magnalium.
Beneficial effects of the present invention：
1. present invention achieves prepared by the thrombin controlled-release coating of the bioactivity surface of hysteroscope lower hemostasia folder Metal Substrate, can
Realize the upgrading from simple " naked " apparatus to the compound apparatus of " feature " medicine.
2. achievable thrombin of the present invention etc. is only capable of the target slow-release of the medicine of topical application, can be used for " the function of preparing
Property " the compound hysteroscope lower hemostasia folder of medicine can be placed directly in human body target organ and operation target site.
3. the present invention is capable of achieving the stable sustained-releases of the medicine on metal based coating systems such as thrombin, and medicine may be implemented in finger
Determine position slow release so as to sustainable increase surrounding tissue concentration, solve the medicine of localized pulverization by tissue fluid rapid dilution shadow
Ring the problem of drug effect.
Description of the drawings
Fig. 1 is the product diagram of the application thrombin slow release hysteroscope lower hemostasia folder；
Fig. 2 is the stable hydroxyapatite nano/submicron coating for preparing；
Fig. 3 is the thrombin layer of hydroxyapatite nano/submicron coating surface；
Fig. 4 is the XPS curves of hydroxyapatite layer；
Fig. 5 is the XPS curves of thrombin layer；
Fig. 6 is thrombin mean concentration curve chart under different time；
Fig. 7 is the post figure of different time sections thrombin.
Specific embodiment
In order to the present invention is better described, with reference to the accompanying drawing in the embodiment of the present invention, in the embodiment of the present invention
Technical scheme is clearly and completely described.
The thrombin slow release hysteroscope lower hemostasia folder of the present invention, as shown in figure 1, including the metallic substrates of hysteroscope lower hemostasia folder
12nd, metal surface 13, phosphate layer 15, chemical conversion film layer 14, hydroxyapatite layer 16 and thrombin layer 17.The Metal Substrate
The thickness at bottom 12 is 0.1-0.8 millimeters, and the thickness of phosphate layer 15 is 4-40 microns, and the thickness of chemical conversion film layer 14 is 1-10
Nanometer, the thickness of hydroxyapatite layer 16 is 0.02-0.06 millimeters, and the thickness of thrombin layer 17 is 0.1-1 microns.
Specific embodiment 1：
12 deionized water supersound washing of 1.SU304 austenitic stainless steels metallic substrates 5 minutes, removes metal surface 13
Greasy dirt or corrosion.After surface is clean, 60 DEG C of dryings 8 minutes are positioned in drying baker, with surface noresidue water droplet as qualified；Institute
The thickness for stating stainless steel metal substrate 12 is 0.5 millimeter.
2. by 40 parts of the 1-hydroxy ethylidene-1,1-diphosphonic acid solution of 5mol/l, 5 parts of the orthophosphoric acid solution of 3mol/l, 1 part of system of hydrogen peroxide
Standby mixed solution；1 part of the solution is 1l, and 1 part of hydrogen peroxide is 1g.By stainless steel metal substrate 12 be soaked in 25 DEG C it is above-mentioned mixed
Close 2 minutes in solution, carry out the phosphate layer 15 of metal surface 13 and the preparation of chemical conversion film layer 14.
3. after taking out after redundant solution is flowed down, 60 DEG C of dryings 8 minutes are positioned in drying baker, make the phosphate layer of preparation
15 and chemical conversion film layer 14 be dried.The chemical conversion film layer 14 is thin film very thin on metal surface 13.
4. sample surfaces are treated without obvious liquid or colloid, and deionized water is rinsed 5 minutes to metal surface 13, rinsed out many
Remaining phosphatization crystallization residual, the phosphate layer 15 on the remaining surface of chemical conversion film layer 14 for being difficult to be rinsed, its thickness is 10
Nanometer, the thickness of phosphate layer 15 is 0.1 micron.It is positioned over hydroxyapatite (HA) suspension that 25g/l is constantly stirred
In, 28 DEG C are soaked 8 minutes.Prepared by the self assembly for completing the hydroxyapatite layer 16 in chemical conversion film layer 14, gained hydroxyl phosphorus
The thickness of grey rock layers 16 is 0.03 millimeter.Retaining a part of sample carries out the photoelectron spectroscopy and atomic force of hydroxyapatite layer 16
Microscope is characterized, and sees accompanying drawing 2-5.
5. take out the product for preparing of step 4 and be put in drying baker 60 DEG C of dryings 8 minutes, after surface noresidue water droplet.
It is put into thrombin lyophilized powder and 0.9% normal saline is prepared in 4800U/l thrombin solutions, 25 DEG C is soaked 1.5 hours, are prepared solidifying
Hemase layer 17, its thickness is 0.5 micron.
6. take out in 30 DEG C of air dryings 2 hours, carry out photoelectron spectroscopy and characterize with atomic force microscope, atomic force shows
Micro mirror characterization test result is shown in accompanying drawing 2-3, can be seen that preparation front and rear surfaces from AFM comparison diagrams and significant change, light area occurs
Domain is prothrombin molecule.Photoelectron spectroscopy characterization test result is shown in accompanying drawing 4-5, through XPS contrasts as can be seen that (1) thrombin
Molecule successful application has certain thickness in hydroxyapatite surface；(2) from the point of view of high-resolution XPS spectrum unscramblings, without new chemistry
Key and generation, slow release product is thrombin.Composition generates significantly change with pattern before and after the above results explanation thrombin coating
Change, define stable coating, coating is thrombin layer；Produce without new chemical bonds, illustrate that thrombin is dirty without other
Dye thing is produced.
7. step 5 sample is taken out in 30 DEG C of air dryings 2 hours, 6 pieces of samples are taken per group, using microplate reader in 450nm
Determine the absorbance of variable concentrations standard substance under wavelength respectively, standard is drawn according to various criterion product concentration and corresponding absorbance
Curve.The average concentration of thrombin for going out for calculating under different time on this basis as shown in Figure 6, is understood in 0- from accompanying drawing 6
Intravascular coagulation enzyme r e lease is rapid within 60 minutes, and very slowly but still certain concentration can be maintained from 60-180 minute blood coagulations enzyme r e lease.
To be coated with during the metallic substrates of thrombin (totally 6 pieces) are soaked in respectively the beaker for filling 200ml normal saline, respectively
This liquid 100ul is sampled in 0h, 1h, 2h, 3h, 4h, 5h to be placed in the good EP pipes of labelling, after every sub-sampling original physiology salt is discarded
Water, determines the absorbance of the lower six groups of solution of different time and calculates meansigma methodss using microplate reader.Immersion is discarded under different time molten
The absorbance application t inspections that liquid is measured are compared two-by-two P values and are all higher than 0.05 between group, no significant difference was abandoned every 1 hour
Go the absorbance of the solution measured before soaking solution without significant difference, one can consider that medication coat metal in same time period
Substrate can stablize sustained release thrombin.Concrete outcome is as shown in Figure 7.
The above results explanation thrombin as a child reached stable sustained-release value 1, and can be steady in the solution for persistently changing
Fixed slow release thrombin.
Above-mentioned experimental study shows " thrombin-hydroxyapatite-non-oxidation nitride layer-metal " steel plate in normal saline solution
In it is sustainable stably discharge thrombin, so as to ensure solution in thrombin concentration, with thrombin slow release effect, i.e. such as
The thrombin slow release metal matrix hysteroscope lower hemostasia folder that this is prepared also has good thrombin slow release effect.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
All should be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection of claims
Scope is defined.
Claims (10)
1. the preparation method that a kind of thrombin slow release hysteroscope lower hemostasia is pressed from both sides, it is characterised in that comprise the steps：
(1) will be soaked in mixed solution after metallic substrates deionized water supersound washing drying, taking-up is carried out after redrying
Washing；
(2) metallic substrates after step (1) process are soaked in hydroxyapatite suspension, take out drying；
(3) metallic substrates after step (2) process are soaked in be taken out in thrombin solution and are obtained final product；
The metallic substrates are pressed from both sides for the hysteroscope lower hemostasia of metal matrix.
2. preparation method according to claim 1, it is characterised in that the drying in the step (1) and step (2) be
55-65 DEG C is dried 6-8 minutes or 25-28 DEG C of air drying 1.2-1.8 hour in drying baker.
3. preparation method according to claim 1, it is characterised in that the soaking temperature in the step (1) is 25-28
DEG C, the time is 1-2 minutes.
4. preparation method according to claim 1, it is characterised in that the mixed solution in the step (1) is 5mol/l
1-hydroxy ethylidene-1,1-diphosphonic acid solution 30-50 parts, orthophosphoric acid solution 3-5 parts of 3mol/l, hydrogen peroxide or sodium bromate 1-2 parts mixing and
Into.
5. preparation method according to claim 1, it is characterised in that the redrying in the step (1) is drying baker
Middle 60-65 DEG C is dried 5-8 minutes.
6. preparation method according to claim 1, it is characterised in that the hydroxyapatite suspension in the step (2)
Concentration is 25g/l, and soaking temperature is 28-30 DEG C, and the time is 6-8 minutes.
7. preparation method according to claim 1, it is characterised in that blood coagulation in the thrombin solution in the step (3)
Enzyme concentration is 4500-4800U/l, is prepared by thrombin lyophilized powder and 0.9% normal saline.
8. preparation method according to claim 1, it is characterised in that the soaking temperature in the step (3) is 20-25
DEG C, the time is 1-1.5 hours.
9. a kind of thrombin slow release hysteroscope lower hemostasia is pressed from both sides, it is characterised in that by the arbitrary methods described preparation of claim 1-8
, including hysteroscope lower hemostasia folder metallic substrates, be coated with successively on the metal surface of the metallic substrates chemical conversion film layer,
Phosphate layer, hydroxyapatite layer and thrombin layer.
10. thrombin slow release hysteroscope lower hemostasia according to claim 9 is pressed from both sides, it is characterised in that the thickness of the metallic substrates
Spend for 0.1-0.8 millimeters, the thickness of phosphate layer is 4-40 microns, the thickness of chemical conversion film layer is 1-10 nanometers, hydroxyl phosphorus
The thickness of grey rock layers is 0.02-0.06 millimeters, and the thickness of thrombin layer is 0.1-1 microns.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610726284.1A CN106620890A (en) | 2016-08-25 | 2016-08-25 | Endoscopic hemostatic clips with thrombin sustained release function and method for preparing endoscopic hemostatic clips |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610726284.1A CN106620890A (en) | 2016-08-25 | 2016-08-25 | Endoscopic hemostatic clips with thrombin sustained release function and method for preparing endoscopic hemostatic clips |
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| CN106620890A true CN106620890A (en) | 2017-05-10 |
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| CN201610726284.1A Pending CN106620890A (en) | 2016-08-25 | 2016-08-25 | Endoscopic hemostatic clips with thrombin sustained release function and method for preparing endoscopic hemostatic clips |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010115504A (en) * | 1998-05-19 | 2010-05-27 | American National Red Cross | Hemostatic sandwich bandage |
| MD372Y (en) * | 2010-11-30 | 2011-05-31 | Gheorghe Anghelici | Endoscopic method of hemostasis of bleeding ulcer in decompensated hepatic cirrhosis |
| US20120288705A1 (en) * | 2010-11-08 | 2012-11-15 | The Board Of Regents For Oklahoma State University | Hydroxyapatite coated metal surface and method for producing |
| CN203506820U (en) * | 2013-09-26 | 2014-04-02 | 安瑞医疗器械(杭州)有限公司 | Hemostatic clip |
| CN104606722A (en) * | 2013-11-01 | 2015-05-13 | 上海交通大学医学院附属第九人民医院 | Degradable gasket with anti-bacterial anti-adhesion performance |
-
2016
- 2016-08-25 CN CN201610726284.1A patent/CN106620890A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010115504A (en) * | 1998-05-19 | 2010-05-27 | American National Red Cross | Hemostatic sandwich bandage |
| US20120288705A1 (en) * | 2010-11-08 | 2012-11-15 | The Board Of Regents For Oklahoma State University | Hydroxyapatite coated metal surface and method for producing |
| MD372Y (en) * | 2010-11-30 | 2011-05-31 | Gheorghe Anghelici | Endoscopic method of hemostasis of bleeding ulcer in decompensated hepatic cirrhosis |
| CN203506820U (en) * | 2013-09-26 | 2014-04-02 | 安瑞医疗器械(杭州)有限公司 | Hemostatic clip |
| CN104606722A (en) * | 2013-11-01 | 2015-05-13 | 上海交通大学医学院附属第九人民医院 | Degradable gasket with anti-bacterial anti-adhesion performance |
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