CN103068432A - Catheter and method for manufacturing same - Google Patents

Catheter and method for manufacturing same Download PDF

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Publication number
CN103068432A
CN103068432A CN2010800679722A CN201080067972A CN103068432A CN 103068432 A CN103068432 A CN 103068432A CN 2010800679722 A CN2010800679722 A CN 2010800679722A CN 201080067972 A CN201080067972 A CN 201080067972A CN 103068432 A CN103068432 A CN 103068432A
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China
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catheter
photosensitizer
catheter according
manufacture method
present
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CN2010800679722A
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Inventor
金龙禄
郑锡勋
王江均
金多喜
金峰进
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IND ACADEMIC COOP
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IND ACADEMIC COOP
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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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A61L29/18—Materials at least partially X-ray or laser opaque
    • 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00—Radiation therapy
    • A61N5/06—Radiation therapy using light
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00—Catheters; Hollow probes
    • A61M25/0043—Catheters; Hollow probes characterised by structural features
    • A61M2025/0056—Catheters; Hollow probes characterised by structural features provided with an antibacterial agent, e.g. by coating, residing in the polymer matrix or releasing an agent out of a reservoir

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  • Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Engineering & Computer Science (AREA)
  • Epidemiology (AREA)
  • Biomedical Technology (AREA)
  • Optics & Photonics (AREA)
  • Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Radiology & Medical Imaging (AREA)
  • Materials For Medical Uses (AREA)
  • Media Introduction/Drainage Providing Device (AREA)

Abstract

The present invention relates to a catheter and to a method for manufacturing same. More particularly, the catheter according to the present invention comprises: a tubular body and a photosensitizer included in the inner cylindrical surface of the body. The catheter according to the present invention has excellent mechanical properties such as temperature and pH stability and high optophysical characteristics. Also, the catheter can be self-sterilized by the generation of active oxygen species through the excitation of the photosensitizer due to incident light energy, thereby preventing bacteria from forming a biofilm.

Description

Catheter and manufacture method thereof
Technical field
The present invention relates to a kind of catheter ( Catheter) and manufacture method.More specifically, the present invention relates to a kind of autosterilization catheter and manufacture method thereof with optical property, described catheter has good engineering properties, namely variations in temperature and pH are changed that to have stability and a Photophysical Behaviors remarkable etc., excite photosensitizer to generate active oxygen by radiation source and carry out autosterilization, and can prevent the biomembrane that formed by antibacterial.
Background technology
Usually, catheter is used for medical treatment, is that it can be used on the multiple use of intravascular injection, urethra insertion, trachea insertion, laparoscopic surgery etc. to the general designation of the article that are used for the form of ownership in the direct insertion body.
In operation, owing to this catheter directly will be inserted in the body, need importantly to prevent that the health that is caused by catheter from infecting.
For example, for being used for the catheter of general intravascular injection, because tubular body that will part inserts in the human vas, after using various chemical drugss to clean the outer surface of described main body and inside, reuse, infect to prevent health.
Yet though this cleanout fluid is harmless, problem is, is difficult to clean the inside of described main body by cleanout fluid, and it is also many to clean required expense.
In addition, can cancel after catheter is used once, yet only because there being infected probability, ignore the satisfactory texture that body interior has, the calcellation catheter can be unfavorable for economy, causes the most at last the increase of surgery cost.
In addition, owing to surely grow ( Colonization) the pathogen that is inserted on the catheter of urethra, the urethra catheter ( Urinary catheter) can cause ascending infection.
The insertion of this urethra catheter can become the pathogenicity urinary tract infection ( Nosocomial UTI) reason, particularly, the insertion of the urethra catheter of known short-term and heating and acute pyelonephritis ( Acutepyelonephritis) relevant, the insertion of long-term urethra catheter will cause lithangiuria ( Urinary stone), chronic nephritis ( Chronic renal inflammation) etc. complication.
In the pathogen of described urinary tract infection with escherichia coli ( Escherichia coli) the most common, in the glucose non-fermentative gram-negative bacilli modal pathogen be bacillus pyocyaneus ( Pseudomonas aeruginosa), in gram-positive cocci common pathogen be enterococcus ( Enterococcus spp.), and staphylococcus aureus ( Staphylococcus aureus) also be important pathogen.
In the pathogen that can cause urinary tract infection that is separated recently, most cephalosporin to penicillin, close limit and wide region ( Cephalosporin), carbapenem ( Carbapenem), fluoroquinolone ( Fluoroquinolone), aminoglycoside ( Aminoglycoside) etc. various antibacterial drug resistances, escherichia coli, bacillus pyocyaneus etc. mostly gram negative bacilli can pass through extended spectrumβ-lactamase (ESBL , extended-spectrum β-lactamase), metallo-β-lactamase ( Metallo-β-lactamase) etc. various mutations to drug resistances such as the cephalosporin of wide region, carbapenems.
Therefore, be necessary the catheter with autosterilization function is developed, and need exploitation to be used for preventing the technology of biofilm formation.
Summary of the invention
Technical problem
The invention reside in and address the above problem, the object of the present invention is to provide a kind of autosterilization catheter and manufacture method thereof with optical property, described catheter has good engineering properties, namely variations in temperature and pH are changed that to have stability and a Photophysical Behaviors remarkable etc., excite photosensitizer to generate active oxygen by radiation source and carry out autosterilization, and can prevent by bacterial Biofilm formation.
Technical scheme
In order to reach above-mentioned purpose of the present invention, an aspect of of the present present invention provides a kind of catheter, and described catheter comprises tubular body; With the photosensitizer that is coated on the described body interior face of cylinder.
At this moment, described main body can by silica gel, latex ( Latex) and composition thereof make, described photosensitizer can for be selected from porphyrin ( Porphyrin, H 2TTP), phthalocyanine ( Phthalocyanine), dyestuff ( Dye), more than one the material in porphyrin replacement and the phthalocyanine replacement.
In another aspect of this invention, provide the manufacture method that comprises main body and be contained in the catheter of the photosensitizer in the described main body, described manufacture method comprises, prepares the step of photosensitizer solution by dissolving photosensitizer in solvent; With the step on the inwall that described photosensitizer solution is applied in the catheter main body.
Beneficial effect
As mentioned above, according to catheter of the present invention and manufacture method thereof, described catheter has good engineering properties, namely variations in temperature and pH are changed that to have stability and a Photophysical Behaviors remarkable etc., excite photosensitizer to generate active oxygen by radiation source and carry out autosterilization, and can prevent by bacterial Biofilm formation. ?
Description of drawings
Fig. 1 has showed the manufacture process of the catheter of an embodiment among the present invention.
Fig. 2 has showed the process of the automatic sterilizing of the catheter of an embodiment among the present invention.
Fig. 3 has showed the photo by the catheter of an embodiment among the present invention who utilizes Laser Scanning Confocal Microscope.
Fig. 4 has showed the chart of the extinction spectrum (left side) of the catheter of an embodiment/fluorescence spectrum (right side) among the present invention.
Fig. 5 has showed according to the chart that consists of the organic matter decomposition rate of the porphyrin concentration of the catheter of an embodiment among the present invention.
The chart of the photocatalysis effect that the pH of the catheter of an embodiment changed during Fig. 6 had showed according to the present invention.
The chart of the photocatalysis effect of the variations in temperature of the catheter of an embodiment during Fig. 7 has showed according to the present invention.
Fig. 8 has showed the chart of the stability when testing under the condition of catheter in being similar to body of an embodiment among the present invention.
Fig. 9 has showed the chart of the stability of the catheter of an embodiment among the present invention.
Figure 10 has showed that the catheter of embodiment among the present invention is to the chart of colibacillary antibacterial effect.
Figure 11 has showed that the catheter of an embodiment among the present invention is to the chart of the antibacterial effect of staphylococcus aureus.
Figure 12 has showed that the catheter of an embodiment among the present invention is to the chart of the antibacterial effect of bacillus pyocyaneus.
The catheter that Figure 13 has showed embodiment among the present invention to Candida albicans ( Candida albicans) the chart of antibacterial effect.
Figure 14 has showed that the catheter of embodiment among the present invention is to the photo of colibacillary antibacterial effect.
Figure 15 has showed that the catheter of an embodiment among the present invention is to the photo of the antibacterial effect of staphylococcus aureus.
Figure 16 has showed that the catheter of an embodiment among the present invention is to the photo of the antibacterial effect of bacillus pyocyaneus.
Figure 17 has showed that the catheter of an embodiment among the present invention is to the photo of the antibacterial effect of Candida albicans.
The specific embodiment
Below, with reference to the accompanying drawings, will explain the catheter of an embodiment among the present invention.Accompanying drawing only to specify the present invention as purpose, is not limited to technical scope of the present invention for showing the figure of embodiments of the invention.
The present invention relates to a kind of catheter, described catheter comprises tubular body and is coated in photosensitizer on the face of cylinder of described body interior.
Wherein, described main body can by silica gel, latex ( Latex) and composition thereof make, described photosensitizer can for be selected from porphyrin ( Porphyrin, H 2TTP), phthalocyanine ( Phthalocyanine), dyestuff ( Dye), more than one the material in porphyrin replacement and the phthalocyanine replacement.
The catheter of an embodiment can be used on the multiple uses such as intravascular injection, urethra insertion, air flue insertion, laparoscopic surgery among the present invention, the below for convenience of explanation, the catheter of an embodiment refers to the urethra catheter (namely among the present invention, when using the urethra catheter, become polluter), the photosensitizer that consists of the catheter of an embodiment among the present invention refers to porphyrin.
Fig. 1 has showed the manufacture process of the catheter of an embodiment among the present invention, and Fig. 2 has showed the process of the autosterilization of the catheter of an embodiment among the present invention.
The urethra catheter of an embodiment comprises tubular body and is coated in porphyrin (H on the periphery of described body interior among the present invention 2TPP).
Wherein, described main body can by as silica gel, silica gel-latex ( Silicone-latex) mixture or latex etc. makes, but being not limited to these, it is inside and outside that described main body has, the inner flowing space that forms the fluids such as medicine that inject.Described porphyrin (H 2TPP) as photoactive substance, when by light source irradiation, form active oxygen by the process to oxygen conduction electron or conduction energy.
Described active oxygen be divided into the oxygen-derived free radicals that formed by the electronics transmission ( Radical oxygen) and the singlet oxygen that formed by energy delivery ( Singlet oxygen), and have respectively different active efficient and energy response.
On the one hand, by various papers, known activity oxygen can be eliminated virus, antibacterial and cancerous cell, and among the present invention the urethra catheter of an embodiment be by with light source irradiation to porphyrin, eliminate various antibacterials according to the different active efficient of oxygen-derived free radicals and singlet oxygen.
In addition, porphyrin is organic compound, can easily stick on the inwall of catheter main body.
Porphyrin is coated on the inner circular cylinder of catheter main body with the thickness less than 0.5mm, thereby prevents that the active oxygen that generates from passing through the external cylindrical surface of catheter to external diffusion.
Fig. 3 be the catheter of an embodiment among the present invention the photo that passes through Laser Scanning Confocal Microscope (begin from the left side for light field ( Bright field), fluorescence, merging ( Merged) photo).
The Laser Scanning Confocal Microscope photo of the catheter of an embodiment in according to the present invention can confirm that photosensitizer smears evenly at the catheter inwall.Thereby, by on the catheter inwall, smearing equably photosensitizer, can induce from inwall and generate on the whole active oxygen.
Fig. 4 has showed the chart of the extinction spectrum (left side) of the catheter of an embodiment/fluorescence spectrum (right side) among the present invention.
The Absorption and fluorescence spectrum of the catheter of an embodiment in according to the present invention will be led into photosensitizer (H 2TPP) optical property catheter use respectively Hitach company U-2800 UV/Vis spectrophotometer ( Spectrophotometer) and the V550 Reflectance UV/Vis spectrophotometer of Jasco company test its stable state absorption spectrum ( Steady-state absorption spectrum), result's demonstration, the peak value of the absorbing wavelength that porphyrin itself has ( Peak) B-band (400nm) and Q-band (510,530,580,630nm) also appear at and lead on the absorption spectrum of the catheter of porphyrin.
Therefore, the absorption peak of the stable state absorption spectrum of described porphyrin can be between wavelength 350～700nm, be preferably 400～650nm, because described porphyrin has wide stable state absorbing wavelength, the catheter of an embodiment can use the light source in the wide visible region among the present invention, activate the active oxygen that photosensitizer generates and to carry out autosterilization by shining described light source, thereby prevent the biomembrane that formed by antibacterial.
In addition, by with the F-4500 spectrophotometer measurement of Hitachi company (excitation wavelength ( Excitation wavelength): 510nm) led into photosensitizer (H 2The steady-state fluorescence spectrum of the catheter with optical property TPP) ( Steady-state Fluorescence spectrum), as can be known from the results, the photoluminescence peak that itself has appears at 650nm, 720nm place.
According to the above results, the luminescence generated by light of described porphyrin ( Photoluminescence) be by phosphorescence ( Phosphorescence) process is finished, so the life time of porphyrin is relatively long, thereby can induce high active oxygen production rate.
For example, the photoluminescence peak of the fluorescence spectrum of described porphyrin but is not limited to above-mentioned wave band between wavelength 600～750nm.Therefore, generate active oxygen by the phosphorescence process, thereby can in long life time, can keep Photophysical Behaviors.
According to foregoing, can determine with photosensitizer (porphyrin, H2TPP) lead in silica gel catheter material after, also can keep the steady-state light physical characteristic of photosensitizer.
Fig. 5 has showed according to the chart that consists of the organic matter decomposition rate of the porphyrin concentration of the catheter of an embodiment among the present invention.
As shown in Figure 5, the porphyrin (H to being imported into 2TPP) concentration is regulated and control, and by using the autosterilization catheter with optical property of various concentration, carries out Organic substance (Rhodamine B) decomposition experiment, then according to the Strength Changes of steady-state fluorescence spectrophotometric spectra, determines the porphyrin (H that is imported into 2TPP) relation between concentration and the organic matter decomposition rate is elected the porphyrin concentration that consists of the catheter of an embodiment among the present invention as 6.5 * 10 -8～2.4 * 10 -6Mol/mL.
According to reference to the accompanying drawings, the manufacture method of the catheter with said structure and performance will be explained.
The present invention relates to a kind of manufacture method of catheter that comprises main body and be coated in the photosensitizer of described body interior, described manufacture method comprises, prepares the step of photosensitizer solution by dissolving photosensitizer in solvent; With the step of smearing described photosensitizer solution in the catheter main body inner wall.
According to an embodiment, described manufacture method comprises, by the dichloromethane of 1mL ( Dichloromethane, solvent) and middle step of dissolving porphyrin (photosensitizer) the preparation porphyrin solution of 0.4mg; With by utilize swelling ( Swelling) porphyrin solution is led step on the main body inner wall with syringe etc.
Wherein, the concentration of described porphyrin solution can be 6.5 * 10 -8～2.4 * 10 -6Mol/mL, after heating with 25～135 ℃ temperature, by finish remove solvent and deswelling ( Deswelling) step of process, and with the step that ultrasonic cleaner cleans catheter, make catheter.
Below, the stability that the variations in temperature of the catheter of an embodiment in examining according to the present invention or pH are changed etc., the chart of the photocatalysis effect that the PH of the catheter of an embodiment changed during Fig. 6 had showed according to the present invention, the chart of the photocatalysis effect of the variations in temperature of the catheter of an embodiment during Fig. 7 has showed according to the present invention, Fig. 8 have been showed the chart of the stability when testing under the condition of catheter in being similar to body of an embodiment among the present invention.
As shown in Figure 6, the catheter that can confirm an embodiment among the present invention has the photocatalysis effect that is caused by active oxygen under various PH conditions, as shown in Figure 7, behind the lower processing of sterilization temperature condition (about 135 ℃) catheter, it still keeps photocatalysis efficiency, and by variations in temperature, still keep stability.
Fig. 8 is the condition (pH6.8 in being similar to body, 37 ℃, 27 hours) whether lower the detection overflowed the chart of photosensitizer from leading into the catheter of photosensitizer, thus can determine under the condition in being similar to body that the catheter of an embodiment has stability among the present invention.
Fig. 9 is for being led the chart of the forward and backward Photophysical Behaviors of organic substance decomposing being tested into the catheter of photosensitizer by utilizing, thereby can determine, by the forward and backward process of organic substance decomposing, the catheter of an embodiment has identical Photophysical Behaviors among the present invention.
Figure 10～Figure 17 has showed the experimental result of the antibacterial effect of the catheter of an embodiment among the present invention.
Particularly, except as can in silicone catheter, form biomembranous main contaminated bacteria escherichia coli ( Escherichia coliATCC 25922-Figure 10 and Figure 14) outside, to by use 3 kinds of antibacterials [staphylococcus aureus ( Staphylococcus aureusATCC 25923-Figure 11 and Figure 15), bacillus pyocyaneus ( Pseudomonas. AeruginosaATCC 27853-Figure 12 and Figure 16), Candida albicans ( Candida albicansATCC 90228-Figure 13 and Figure 17)] antibacterial effect of the autosterilization catheter with optical property that makes ( Antibacterial effect) test.
BHI meat soup (brain heart leachate meat soup ( Oxoid)) in, by under 37 ℃ the aerobic condition with antibacterial culturing more than 24 hours.At the PBS(phosphate buffer) in, 4 kinds of suspensions the antibacterial at a night being cultivated are diluted to 2.0x10 5Cfu.
The PBS of described buffer 10ml (pH=7.0), and at pre-irradiation, in the darkroom, carry out first 30 minutes freely stir ( Free stirring).Then, utilize light source 10ns Nd-YAG laser (510nm, 8mW) to carry out 1 hour irradiation.
After finishing irradiation, from suspension, respectively get 10 μ L and 20 μ L, the 20 μ L that get are used as matched group, then in maconkey agar (Mac Conkey agar:MAC), plant ( Plating).
All plates are in the cultivation of carrying out under 37 ℃ more than 16 hours, then to the survival antibacterial carry out the viable bacteria numeration ( Viable counting).
Experimental result shows, under this experiment condition, have in 5 minutes 100% escherichia coli, staphylococcus aureus, bacillus pyocyaneus downright bad ( Necrosis), Candida albicans then has about 60% necrosis.
The below will specify the autosterilization method of the catheter that makes by said method.After in the patient with operation body, inserting the urethra catheter of an embodiment among the present invention, microminiature laser spots (laser point etc.) is close on the external end (being exposed to external part) of catheter, then by carrying out periodic laser (light source) irradiation, the generation of induced activity oxygen.
At this moment, laser can inject the inside of catheter, and goes upward in the body of catheter terminal along the catheter inwall.
Therefore, not only be convenient to provide light source and operation, and need not other equipments or device.Above-mentioned the specific embodiment of the present invention of showing only is used for being exemplified as purpose, so those skilled in the art can carry out various modifications, change, interpolation in thought of the present invention and scope, and this modification, change and interpolation all should belong within the scope of claim of the present invention.

Claims (14)

1. catheter, it comprises tubular body and is coated in photosensitizer on the described body interior face of cylinder.
2. catheter according to claim 1 is characterized in that, described main body is made by silica gel, latex and composition thereof.
3. catheter according to claim 1 is characterized in that, described photosensitizer can be for being selected from more than one the material in porphyrin, phthalocyanine, dyestuff, porphyrin replacement and the phthalocyanine replacement.
4. catheter according to claim 1 is characterized in that, the absorption peak of the stable state absorption spectrum of described photosensitizer is between wavelength 350～700nm.
5. catheter according to claim 1 is characterized in that, the absorption peak of the stable state absorption spectrum of described photosensitizer is between wavelength 600～760nm.
6. catheter according to claim 1 is characterized in that, is coated in the thickness of the photosensitizer on the face of cylinder of described body interior less than 0.5mm.
7. manufacture method that comprises the catheter of photosensitizer, the method comprises: the step for preparing photosensitizer solution by dissolving photosensitizer in solvent; With the step of smearing described photosensitizer solution in the main body inner wall of catheter.
8. the manufacture method of catheter according to claim 7 is characterized in that, described main body is made by silica gel, latex and composition thereof.
9. the manufacture method of catheter according to claim 7 is characterized in that, described photosensitizer can be for being selected from more than one the material in porphyrin, phthalocyanine, dyestuff, porphyrin replacement and the phthalocyanine replacement.
10. the manufacture method of catheter according to claim 7 is characterized in that, described photosensitizer concentration is 6.5 * 10 -8～2.4 * 10 -6Mol/mL.
11. the manufacture method of catheter according to claim 7 is characterized in that, is coated in the thickness of the described photosensitizer on the face of cylinder of described body interior less than 0.5mm.
12. the manufacture method of catheter according to claim 7 is characterized in that, the manufacture method of described catheter comprises: the step of removing solvent and deswelling process after heating with 25～135 ℃ temperature; With the step of cleaning main body with ultrasonic cleaner.
13. the manufacture method of catheter according to claim 7 is characterized in that, the step of smearing photosensitizer solution in the main body inner wall of catheter is by the swelling that utilizes main body photosensitizer solution to be imported main body inner wall to finish.
14. the manufacture method of catheter according to claim 7 is characterized in that, is coated in the thickness of the described photosensitizer on the face of cylinder of described body interior less than 0.5mm.
CN2010800679722A 2010-07-09 2010-07-09 Catheter and method for manufacturing same Pending CN103068432A (en)

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CN108607151A (en) * 2018-05-21 2018-10-02 青岛杰圣博生物科技有限公司 A kind of antibiotic catheters and preparation method thereof

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Publication number Priority date Publication date Assignee Title
ES2801524B2 (en) 2019-06-28 2022-07-28 Univ Madrid Complutense PHOTO-STERILIZABLE MEDICAL DEVICE

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CN101426539A (en) * 2006-02-28 2009-05-06 贝克顿·迪金森公司 Antimicrobial compositions and methods for locking catheters
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US5456661A (en) * 1994-03-31 1995-10-10 Pdt Cardiovascular Catheter with thermally stable balloon
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US20020095197A1 (en) * 2000-07-11 2002-07-18 Lardo Albert C. Application of photochemotherapy for the treatment of cardiac arrhythmias
US20100078336A1 (en) * 2002-10-04 2010-04-01 Ethicon, Inc. Packaged antimicrobial medical device and method of preparing same
CN101237883A (en) * 2005-04-07 2008-08-06 照片诊断设备（Pdd）有限公司 Photosensitizers and MRI enhancers
CN101426539A (en) * 2006-02-28 2009-05-06 贝克顿·迪金森公司 Antimicrobial compositions and methods for locking catheters
CN101012234A (en) * 2007-02-16 2007-08-08 福州大学 Non-periphery substituted phthalocyanine metal complex and preparing method thereof
CN101023945A (en) * 2007-02-16 2007-08-29 福州大学 Use of non-periphery substituted phthalocyaniu metal complex
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Publication number Priority date Publication date Assignee Title
CN108607151A (en) * 2018-05-21 2018-10-02 青岛杰圣博生物科技有限公司 A kind of antibiotic catheters and preparation method thereof
CN108607151B (en) * 2018-05-21 2021-06-01 青岛杰圣博生物科技有限公司 Antibacterial catheter and preparation method thereof

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