CN115538153A - Method for preparing graphene-based antibacterial coating of medical fabric under assistance of visible laser - Google Patents
Method for preparing graphene-based antibacterial coating of medical fabric under assistance of visible laser Download PDFInfo
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- CN115538153A CN115538153A CN202211117863.8A CN202211117863A CN115538153A CN 115538153 A CN115538153 A CN 115538153A CN 202211117863 A CN202211117863 A CN 202211117863A CN 115538153 A CN115538153 A CN 115538153A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 239000004744 fabric Substances 0.000 title claims abstract description 51
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000005507 spraying Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000010926 purge Methods 0.000 claims abstract description 8
- 238000004381 surface treatment Methods 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 abstract description 5
- 238000013532 laser treatment Methods 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 230000003385 bacteriostatic effect Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 4
- 239000000022 bacteriostatic agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000029663 wound healing Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Images
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a method for preparing a graphene-based antibacterial coating of a medical fabric with the assistance of visible laser, which comprises the steps of dissolving nitrate in a graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a uniform dispersion liquid; uniformly spraying the uniform dispersion liquid on the surface of the medical fabric and drying; continuously spraying a graphene oxide aqueous solution with the same volume as the uniform dispersion liquid on the surface of the dried medical fabric; after drying, under the inert gas purging, the medical fabric after surface treatment is rapidly scanned by using low-power visible laser, and finally the brownish black graphene-based antibacterial coating with firm load is formed. According to the invention, metal ions and metal compounds with antibacterial activity can be quickly and efficiently loaded on the surfaces of different medical fabrics through the adhesion effect of graphene, and graphene-based antibacterial coatings with firm loading can be formed on the surfaces of different types of medical fabrics through visible laser treatment, so that the medical fabrics can be efficiently subjected to antibacterial treatment.
Description
Technical Field
The invention belongs to the technical field of preparation of medical fabric antibacterial coatings, and particularly relates to a method for preparing a graphene-based antibacterial coating of a medical fabric with the assistance of visible laser.
Background
The antibacterial coating is constructed on the surface of medical fabrics such as protective clothing, masks, gloves and nursing fabrics, and can effectively block the transmission paths of various pathogens, bacteria and viruses. At present, the technology of loading various antibacterial materials on the medical fabrics has received extensive attention, but the existing problem is that the practicability is not high, and the unified treatment of various fabrics cannot be met. For example, zhandibin, et al propose a preparation method of graphene nano-silver composite non-woven fabric (CN 107794642B), in which a bacteriostatic agent is added into a system in a mixed material, which has the problems of low applicability, most of bacteriostatic agents being embedded in the non-woven fabric instead of surface loading, and the bacteriostatic agent being wrapped in the non-woven fabric is difficult to achieve a good bacteriostatic effect on the surface. Lv Xiumei et al propose a low-cost antibacterial agent for textiles and its preparation method (CN 109778530A), which requires a large amount of organic reagents in the process, and the product mainly faces non-medical industry.
The antibacterial material formed by loading graphene and silver is receiving wide attention. For example: liu Yang et al propose a silver-loaded graphene composite membrane with antibacterial and wound healing promoting functions and its application (CN 106867005B), but it is mainly the bacteriostatic action facing the gel-like substances used for wound healing. The direct graphene and silver composite material used for antibacterial materials has many technical researches and developments, for example, long Jianjun and the like propose a graphene coated nano silver antibacterial material and a preparation method thereof (CN 110089524A); zhang Xiaosui et al propose a durable bactericidal antibacterial liquid of graphene composite silver ions (CN 112335678A); marie et al have proposed a preparation method of graphene and nano-silver composite antibacterial material (CN 110810402 a); gao Peijun and the like propose a silver-loaded graphene material and a preparation method thereof (CN 108286188B). However, these studies have been generally directed to powder materials, and it is difficult to uniformly and firmly support the powder materials. In addition, in the synthesis, more organic solvents and organic small molecules are generally used as reducing agents, which may cause environmental pollution and increase of preparation cost.
At present, some technical schemes involve loading a silver and graphene composite material on different substrates to realize an antibacterial function, for example, feng Pei and the like report a composite bone scaffold material of nano silver/graphene oxide/degradable polymer, an antibacterial bone scaffold and a preparation method thereof (CN 110694116A); wang Feng et al propose a silver-loaded graphene oxide-polyvinyl alcohol ultrafiltration membrane and its preparation and application (CN 106582327B). However, the technical scheme mainly relates to the load of the material on a stationary phase and a smooth surface, and the firm load of the material on the surface of a flexible, porous and fragile fabric is difficult to realize.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing a graphene-based antibacterial coating of a medical fabric under the assistance of visible laser, which can quickly and efficiently load metal ions and metal compounds with antibacterial activity on the surfaces of different medical fabrics under the adhesion action of graphene, and can form the graphene-based antibacterial coating with firm load on the surfaces of different types of medical fabrics through visible laser treatment, thereby realizing efficient antibacterial treatment on the medical fabrics.
The invention adopts the following technical scheme for solving the technical problems, and the method for preparing the graphene-based antibacterial coating of the medical fabric with the assistance of the visible laser is characterized by comprising the following specific steps:
step S1, dissolving nitrate in a graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a uniform dispersion liquid, wherein the nitrate is one or more of silver nitrate, manganese nitrate, zinc nitrate, copper nitrate or ferric nitrate;
step S2, uniformly spraying the uniform dispersion liquid obtained in the step S1 on the surface of the medical fabric and drying;
s3, continuously spraying a graphene oxide aqueous solution with the same volume as the uniform dispersion liquid on the surface of the medical fabric dried in the step S2;
and S4, after drying, rapidly scanning the medical fabric subjected to surface treatment by using 0.1-5W visible laser for 0.5-2min under the purging of inert gas, and finally forming the brownish black graphene-based antibacterial coating with firm load.
Further, the concentration of the graphene oxide aqueous solution in the step S1 is 0.001-0.1mg/mL, and the concentration of the nitrate in the uniform dispersion liquid is 0.1-5mmol/L.
Further limiting, the concentration of the graphene oxide aqueous solution in the step S3 is 0.001-0.05mg/mL.
Further, the visible laser in step S4 is an infrared laser.
Further, the inert gas in step S4 is nitrogen.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation process does not add organic additives and use organic solvents, and has the advantages of green process, good benefit and low cost;
2. according to the invention, the reduction and structure regulation of the graphene oxide and the growth of various transition metal compounds are completed in one step by using a visible laser method, so that the process is simple and the controllability is strong;
3. the high heat effect of the visible laser ensures that the bacteriostatic coating is firmly loaded on the surface and is not easy to fall off, thereby showing better bacteriostatic effect.
Drawings
Fig. 1 is a scanning electron microscope image and an element distribution analysis image of the antibacterial graphene-based coating prepared in example 1.
FIG. 2 is a graph comparing the bacteriostatic performance of the examples and the comparative examples on Escherichia coli under the same test conditions.
Detailed Description
The present invention will be described in further detail below with reference to specific experiments, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all the technologies realized based on the above-described subject matter of the present invention are within the scope of the present invention.
Example 1
Dissolving silver nitrate into graphene oxide aqueous solution with the concentration of 0.01mg/mL, and uniformly stirring and mixing to obtain uniform dispersion liquid, wherein the concentration of the silver nitrate is 0.1mmol L -1 (ii) a Uniformly spraying the obtained uniform dispersion liquid on the surface of the medical fabric and drying at 50 ℃; continuously spraying a graphene oxide aqueous solution with the same volume as the uniform dispersion liquid and the concentration of 0.05mg/mL on the surface of the dried medical fabric, drying at 50 ℃, and rapidly scanning the medical fabric subjected to surface treatment by using 0.1W infrared laser for 1min under nitrogen purging to finally form a brownish black graphene-based antibacterial coating with firm load.
Example 2
Dissolving silver nitrate and manganese nitrate in 0.05mg/mL graphene oxide aqueous solution, and uniformly stirring and mixing to obtain uniform dispersion liquid, wherein the concentrations of the silver nitrate and the manganese nitrate are both 0.2mmol L -1 (ii) a Uniformly spraying the obtained uniform dispersion liquid on the surface of the medical fabric and drying at 80 ℃; continuously spraying a graphene oxide aqueous solution with the same volume as the uniform dispersion liquid and the concentration of 0.01mg/mL on the surface of the dried medical fabric, drying at 80 ℃, and rapidly scanning the medical fabric subjected to surface treatment by using 0.5W infrared laser for 2min under nitrogen purging to finally form a brownish black graphene-based antibacterial coating with firm load.
Example 3
Dissolving zinc nitrate, copper nitrate and ferric nitrate in 0.1mg/mL graphene oxide aqueous solution, and uniformly stirring and mixing to obtain uniform dispersion liquid, wherein the concentrations of the zinc nitrate, the copper nitrate and the ferric nitrate are all 2mmol L -1 (ii) a Uniformly spraying the obtained uniform dispersion liquid on the surface of the medical fabric and drying at 60 ℃; continuously spraying a graphene oxide aqueous solution with the same volume as the uniform dispersion liquid and the concentration of 0.005mg/mL on the surface of the dried medical fabric, drying at 60 ℃, and rapidly scanning the medical fabric subjected to surface treatment by using 2W infrared laser for 0.5min under nitrogen purging to finally form a brownish black graphene-based antibacterial coating with firm load.
Example 4
Dissolving silver nitrate and ferric nitrate in 0.1mg/mL graphene oxide aqueous solution, and uniformly stirring and mixing to obtain uniform dispersion liquid, wherein the concentrations of the silver nitrate and the ferric nitrate are both 5mmol L -1 (ii) a Uniformly spraying the obtained uniform dispersion liquid on the surface of the medical fabric and drying at 80 ℃; continuously spraying a graphene oxide aqueous solution with the same volume as the uniform dispersion liquid and the concentration of 0.05mg/mL on the surface of the dried medical fabric, drying at 80 ℃, and rapidly scanning the medical fabric subjected to surface treatment by using 5W infrared laser for 2min under nitrogen purging to finally form a brownish black graphene-based antibacterial coating with firm load.
Example 5
Dissolving zinc nitrate and copper nitrate in 0.02mg/mL graphene oxide aqueous solution, and uniformly stirring and mixing to obtain uniform dispersion liquid, wherein the concentration of silver nitrate is 0.6mmol L -1 (ii) a Uniformly spraying the obtained uniform dispersion liquid on the surface of the medical fabric and drying at 80 ℃; continuously spraying graphene oxide aqueous solution with the same volume as the uniform dispersion liquid and the concentration of 0.001mg/mL on the surface of the dried medical fabric, drying at 80 ℃, and rapidly scanning the medical fabric subjected to surface treatment by using 0.3W infrared laser for 1min under nitrogen purging to finally form a brownish black graphene-based antibacterial coating with firm load.
Comparative example
Dissolving silver nitrate into graphene oxide aqueous solution with the concentration of 0.01mg/mL, and stirring and mixingMixing to obtain uniform dispersion with silver nitrate concentration of 0.1mmol L -1 (ii) a Uniformly spraying the obtained uniform dispersion liquid on the surface of the medical fabric and drying at 50 ℃; continuously spraying graphene oxide aqueous solution with the same volume as the uniform dispersion liquid and the concentration of 0.05mg/mL on the surface of the dried medical fabric, drying at 50 ℃, and treating the medical fabric for 2 hours by using the traditional heating method to raise the temperature to 80 ℃ in a nitrogen atmosphere to finally form the brownish-black graphene-based antibacterial coating with firm load.
Compared with the bacteriostatic coatings formed on the surfaces of the medical fabrics in the embodiments 1-5, the bacteriostatic coating obtained in the comparative example has a greatly reduced bacteriostatic effect on escherichia coli, so that the firmness of adhesion and bacteriostatic effect of the visible laser treatment on the bacteriostatic coating in the embodiments 1-5 are obviously improved.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (5)
1. A method for preparing a graphene-based antibacterial coating of a medical fabric with the assistance of visible laser is characterized by comprising the following specific steps:
step S1, dissolving nitrate in a graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a uniform dispersion liquid, wherein the nitrate is one or more of silver nitrate, manganese nitrate, zinc nitrate, copper nitrate or ferric nitrate;
step S2, uniformly spraying the uniform dispersion liquid obtained in the step S1 on the surface of the medical fabric and drying;
s3, continuously spraying a graphene oxide aqueous solution with the same volume as the uniform dispersion liquid on the surface of the medical fabric dried in the step S2;
and S4, after drying, rapidly scanning the medical fabric subjected to surface treatment by using 0.1-5W visible laser for 0.5-2min under the purging of inert gas, and finally forming the brownish black graphene-based antibacterial coating with firm load.
2. The visible laser-assisted preparation method of the graphene-based antibacterial coating for medical fabrics according to claim 1, characterized by comprising the following steps: the concentration of the graphene oxide aqueous solution in the step S1 is 0.001-0.1mg/mL, and the concentration of the nitrate in the uniform dispersion liquid is 0.1-5mmol/L.
3. The visible laser-assisted preparation method of the graphene-based antibacterial coating for medical fabrics according to claim 1, characterized by comprising the following steps: the concentration of the graphene oxide aqueous solution in the step S3 is 0.001-0.05mg/mL.
4. The visible laser-assisted preparation method of the graphene-based antibacterial coating for medical fabrics according to claim 1, characterized by comprising the following steps: and the visible laser in the step S4 is infrared laser.
5. The visible laser-assisted preparation method of the graphene-based antibacterial coating for medical fabrics according to claim 1, characterized by comprising the following steps: in step S4, the inert gas is nitrogen.
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Cited By (1)
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