Antimicrobial alginate fiber, and preparation method for and use of dressing thereof

Abstract

The present disclosure provides an antimicrobial alginate fiber, a method for manufacturing an antimicrobial alginate fiber dressing thereof, and an application thereof. When the cationic polymer polyhexamethylene guanide salt is mixed with the anionic polymer alginate, the antimicrobial activity of the guanide salt is quickly passivated. The present disclosure achieves a lower content of polyhexamethylene guanide salt in an alginate dressing with good long-term antimicrobial activities. The polyhexamethylene guanide salt has a low dissolution rate, and significantly reduces a potential risk of carcinogenicity, mutagenicity and reproductive toxicity.

Claims

1. An antimicrobial alginate fiber, comprising a molecular structure as shown in formula (1): ##STR00006## wherein, X is equal to 10 to 40, n is equal to 10 to 40, and A is anyone of hydrochloric acid, phosphoric acid, propionic acid, and gluconic acid.

2. The antimicrobial alginate fiber according to claim 1, wherein a connection between a polyhexamethylene guanide salt and an alginate fiber is a covalent bond formed by interfacial reaction.

3. The antimicrobial alginate fiber according to claim 2, wherein the alginate is selected from the group consisting of water soluble alginate salt, water insoluble alginate salt, and a blend of the water soluble alginate salt and the water insoluble alginate salt; the water soluble alginate salt is anyone of sodium alginate, potassium alginate, magnesium alginate, and ammonium alginate; the water insoluble alginate salt is anyone of calcium alginate and zinc alginate; the blend of the water soluble alginate salt and the water insoluble alginate salt comprises blends formed of water soluble alginate salts with calcium ions or zinc ions as a crosslinking agent.

4. The antimicrobial alginate fiber according to claim 2, wherein the polyhexamethylene guanide salt is selected from the group consisting of polyhexamethylene guanide hydrochloride, a derivative of the polyhexamethylene guanide hydrochloride, polyhexamethylene biguanide hydrochloride, a derivative of the polyhexamethylene biguanide hydrochloride, polyhexamethylene guanide phosphoric acid, a derivative of the polyhexamethylene guanide phosphoric acid, polyhexamethylene biguanide phosphoric acid, a derivative of the polyhexamethylene biguanide phosphoric acid, polyhexamethylene guanide propionic acid, a derivative of the polyhexamethylene guanide propionic acid, polyhexamethylene biguanide propionic acid, a derivative of the polyhexamethylene biguanide propionic acid, polyhexamethylene guanide gluconate, a derivative of the polyhexamethylene guanide gluconate, polyhexamethylene biguanide gluconate, and a derivative of the polyhexamethylene biguanide gluconate, and; the polyhexamethylene guanide salt has a mass percentage in a range of 0.05% to 2.0%.

5. An application of an antimicrobial alginate fiber dressing, comprising: processing the antimicrobial alginate fiber by combing, laying, and needle-punching, to form alginate nonwoven fabrics; or processing the antimicrobial alginate fiber by weaving, to form alginate gauze; and processing the alginate nonwoven fabrics or the alginate gauze by cutting, packaging, and sterilizing, to form the antimicrobial alginate fiber dressing, and the antimicrobial alginate fiber dressing is applied to acute and chronic wound care; wherein the antimicrobial alginate fiber comprises a molecular structure as shown in formula (1): ##STR00007## X is equal to 10 to 40, n is equal to 10 to 40, and A is anyone of hydrochloric acid, phosphoric acid, propionic acid, and gluconic acid.

6. The application according to claim 5, wherein the antimicrobial alginate fiber is obtained by loading polyhexamethylene guanide salt to an alginate fiber via a covalent bond formed by interfacial reaction.

7. The application according to claim 5, wherein the alginate is selected from the group consisting of water soluble alginate salt, water insoluble alginate salt, and a blend of the water soluble alginate salt and the water insoluble alginate salt; the water soluble alginate salt is anyone of sodium alginate, potassium alginate, magnesium alginate, and ammonium alginate; the water insoluble alginate salt is anyone of calcium alginate and zinc alginate; the blend of the water soluble alginate salt and the water insoluble alginate salt comprises blends formed of water soluble alginate salts with calcium ions or zinc ions as a crosslinking agent.

8. The application according to claim 5, wherein the polyhexamethylene guanide salt is selected from the group consisting of polyhexamethylene guanide hydrochloride, a derivative of the polyhexamethylene guanide hydrochloride, polyhexamethylene biguanide hydrochloride, a derivative of the polyhexamethylene biguanide hydrochloride, polyhexamethylene guanide phosphoric acid, a derivative of the polyhexamethylene guanide phosphoric acid, polyhexamethylene biguanide phosphoric acid, a derivative of the polyhexamethylene biguanide phosphoric acid, polyhexamethylene guanide propionic acid, a derivative of the polyhexamethylene guanide propionic acid, polyhexamethylene biguanide propionic acid, a derivative of the polyhexamethylene biguanide propionic acid, polyhexamethylene guanide gluconate, a derivative of the polyhexamethylene guanide gluconate, polyhexamethylene biguanide gluconate, and a derivative of the polyhexamethylene biguanide gluconate, and; the polyhexamethylene guanide salt has a mass percentage in a range of 0.05% to 2.0%.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an illustration of a reaction process in the present disclosure.

(2) FIG. 2 is an illustration of an interface structure of an alginate fiber and polyhexamethylene biguanide salt.

(3) FIG. 3 is a standard curve to quantify polyhexamethylene biguanide.

DETAILED DESCRIPTION

(4) An optimal embodiment of the antimicrobial alginate fiber includes a molecular structure as shown following.

(5) ##STR00002##

(6) X is equal to 30, n is equal to 30, and A is propionic acid. Number a and b are general descriptions of the molecular structure of alginate, and are not in specific numerically limited.

(7) Further, the antimicrobial alginate fiber is obtained by loading polyhexamethylene biguanide to an alginate fiber via an interfacial reaction with covalent bonding.

(8) Further, the alginate is selected from one of water soluble alginates, water insoluble alginates, and a blend of a water soluble alginate and a water insoluble alginate. The water soluble alginate is ammonium alginate. The water insoluble alginate is calcium alginate.

(9) Further, the blend of the water soluble alginate and the water insoluble alginate includes blends formed of water soluble alginates with calcium ions as a crosslinking agent.

(10) Further, the polyhexamethylene guanide salt is polyhexamethylene guanide gluconate and a derivative thereof. The mass of polyhexamethylene guanide salt is of 0.3% (m/m).

(11) A method for manufacturing the above-mentioned antimicrobial alginate fiber dressing includes operations in the following steps.

(12) Block S1, aqueous hydrochloric acid or ethanol hydrochloride solution is provided as an inorganic reaction phase, and chloroform solution is provided as an organic reaction phase. Catalyst is added into the mixed solution. Activation time of an alginate fiber in the mixed solution is 35 minutes, and an activation temperature is 29° C.

(13) Block S2, the alginate fiber treated in block S1 is added into antimicrobial active ethanol solution. Reaction time is 12 hours, and the reaction temperature is 29° C. The antimicrobial active ethanol solution is polyhexamethylene biguanide hydrochloride (PHMB×HCl) ethanol solution.

(14) Block S3, the alginate fiber treated in block S2 is added into chloroform solution. Reaction time is 12 hours, and the reaction temperature is 29° C.

(15) Block S4, the alginate fiber treated in block S3 has an interfacial reaction with polyhexamethylene biguanide hydrochloride with covalent bonding, forming a molecular scaled polyhexamethylene biguanide hydrochloride coating layer. The reaction principle is shown in FIG. 1, and its structural illustration is shown in FIG. 2.

(16) Block S5, the alginate fiber obtained in block S4 is washed once by 40/10000 sodium hydroxide ethanol solution, the ethanol is at the concentration of 70%. The alginate fiber is then washed 4 times by 85% ethanol, and then washed twice by absolute ethanol. The antimicrobial alginate fiber is obtained by vacuum drying in a vacuum pump, for 20 hours at 55° C.

(17) Further, in block S1, the aqueous hydrochloric acid solution contains 1% (m/m) of hydrochloric acid, and 99% (m/m) of water. A mass ratio of the aqueous hydrochloric acid solution to the alginate fiber is 7.0. Activation time of the alginate fiber in the mixed solution is 12 hours, and the activation temperature is 29° C. Further, in block S1, the ethanol hydrochloride solution contains 3% (m/m) of hydrochloric acid, 25% (m/m) of water, and 72% (m/m) of ethanol, and a mass ratio of the ethanol hydrochloride solution to the alginate fiber is 7.0. Activation time of the alginate fiber in the mixed solution is 12 hours, and the activation temperature is 29° C.

(18) Further, the catalyst is a mixture of triphenylphosphine, iodine, and N,N-diisopropylethylamine. The triphenylphosphine and iodine is in equimolar ratio. The mass fraction of triphenylphosphine in the chloroform solution is 1.8%. The mass fraction of iodine in the chloroform solution is 1.8%. The mass fraction of N,N-diisopropylethylamine in the chloroform solution is 4.5%.

(19) The catalyst is prepared by pre-dissolving triphenylphosphine and iodine in chloroform to reach a desired concentration, and then pre-weighed N,N-diisopropylethylamine is rapidly added into the solution with stirring at 90 r/min, and then a primary activated alginate fiber is added.

(20) Further, in block S1, a mass ratio of the mixed solution to the alginate fiber is 18. The activation time of the alginate fiber in the mixed solution is 25 minutes, and the activation temperature is 29° C. Further, in block S2, the concentration of the antimicrobial active ethanol solution is 2.5% (m/m), and the mass of the antimicrobial active ethanol solution is 5 times of the mass of the alginate fiber.

EMBODIMENTS OF THE PRESENT DISCLOSURE

Embodiment 1

(21) A method is provided for manufacturing an antimicrobial alginate fiber dressing. A short alginate fiber with length of 3 to 5 cm is provided with 1000 g, and is placed into 5000 g of aqueous solution containing 0.54% of hydrochloric acid and 9.5% of ethanol, at 20° C. The solution with the alginate fiber is stirred and activated for 3.0 hours, and then the alginate fiber is separated from the aqueous solution by centrifuge. The alginate fiber may be soaked with 2000 g of absolute ethanol for 10 to 15 minutes, and then ethanol is separated by centrifuge to obtain a primary activated alginate fiber. 110 g of N,N-diisopropylethylamine is added into 5500 g of chloroform solution (triphenylphosphine: 0.235%, and iodine: 0.228%) with stirring at 70 r/min, and the stirring time is counted by a timer. After stirring for 1-2 minutes, the primary activated alginate fiber is put into the chloroform solution. The chloroform solution may be stirred for 3 to 5 minutes, and then is activated at 35° C. for 30 minutes. The solution is separated by pressing to obtain a secondary activated fiber. Next, 4000 g of PHMB ethanol solution where PHMB is at 0.028% (m/m) and the secondary activated fiber is mixed and stirred at 25° C. for 40 minutes. The secondary activated fiber is separated from the PHMB ethanol solution by pressing to remove liquid, and is placed in the previous chloroform solution with stirring at 25° C. for 4 hours. Liquid is separated by centrifuge to obtain a PHMB coated alginate fiber. Finally, the PHMB coated alginate fiber is washed once by 15/10000 sodium hydroxide ethanol solution (ethanol at concentration of 70%), then washed by 95% ethanol for 4 times, then washed once by absolute ethanol, and may be dried at 55° C. by vacuum for 24 hours to obtain 925 g of semi-finished product. The alginate fiber, which is covalent bonded with PHMB in the interface, is subjected to needling and hot press drying process. Alginate nonwoven fabrics is obtained by combing, laying, and needle punching, and then is cut, packaged, and sterilized.

(22) A nonwoven antimicrobial alginate dressing containing 0.056% of PHMB is obtained, and the weight of the dressing is 148 g/m.sup.2.

Embodiment 2

(23) A method is for manufacturing an antimicrobial alginate fiber dressing. A short alginate fiber with length of 3 to 5 cm may be provided with 1000 g, and is placed into 5000 g of aqueous solution containing 0.54% of hydrochloric acid and 9.5% of ethanol, at 20° C. The alginate fiber in the aqueous solution is stirred and activated for 3.0 hours, and then the alginate fiber is separated from the aqueous solution by centrifuge. The fiber alginates may be then soaked with 2000 g of absolute ethanol for 10 to 15 minutes, and the ethanol is separated by centrifuge to obtain a primary activated alginate fiber. 110 g of N,N-diisopropylethylamine is added into 5500 g of chloroform solution (triphenylphosphine: 0.235%, and iodine: 0.228%) with stirring at 70 r/min, and the stirring time is counted by a timer. After stirring for 1-2 minutes, the primary activated alginate fiber is placed into the chloroform solution. The alginate fiber in the chloroform solution is stirred for 3 to 5 minutes, and activated at 35° C. for 30 minutes. The fiber is taken out of the solution, and is compressed to remove remaining liquid, obtaining a secondary activated fiber. Next, 4000 g of PHMB ethanol solution where PHMB is at a concentration of 0.038% (m/m) and the secondary activated fiber is mixed and stirred at 25° C. for 40 minutes. The secondary activated fiber is separated from the PHMB ethanol solution by pressing to remove liquid, and placed in the previous chloroform solution with stirring at 25° C. for 4 hours. Liquid is separated by centrifuge to obtain a PHMB coated alginate fiber. Finally, the PHMB coated alginate fiber is washed once by 15/10000 sodium hydroxide alcohol solution (alcohol at concentration of 70%), then washed by 95% alcohol for 4 times, then washed once by absolute ethanol, and is dried at 55° C. by vacuum for 24 hours to obtain 941 g of semi-finished product. The alginate fiber, which is covalent bonded with PHMB in the interface, is subjected to needling and hot press drying process. Alginate nonwoven fabrics is obtained by combing, laying, and needle punching, and then is cut, packaged, and sterilized.

(24) A nonwoven antimicrobial alginate dressing containing 0.076% of PHMB is obtained, and the weight of the dressing is 136 g/m.sup.2.

Embodiment 3

(25) A method is for manufacturing an antimicrobial alginate fiber dressing. A long alginate fiber is provided with 1000 g, and is placed into 5000 g of aqueous solution containing 0.54% of hydrochloric acid and 9.5% of ethanol, at 20° C. The alginate fiber in the aqueous solution is stirred and activated for 3.0 hours, and then the alginate fiber is separated from the aqueous solution by centrifuge to remove liquid. The alginate fiber may be soaked with 2000 g of absolute ethanol for 10 to 15 minutes, and then ethanol is separated by centrifuge to obtain a primary activated alginate fiber. 110 g of N,N-diisopropylethylamine is added into 5500 g of chloroform solution (triphenylphosphine: 0.235%, and iodine: 0.228%) with stirring at 70 r/min, and the stirring time is counted by a timer. After stirring for 1-2 minutes, the primary activated alginate fiber is placed into the chloroform solution. The chloroform solution is stirred for 3 to 5 minutes, and then the primary activated alginate fiber is activated at 35° C. for 30 minutes. The fiber is then taken out of the solution, and is compressed to remove remaining liquid, to obtain a secondary activated fiber. Next, 4000 g of PHMB ethanol solution where PHMB is at the concentration of 0.052% (m/m) and the secondary activated fiber is mixed and stirred at 25° C. for 40 minutes. The secondary activated fiber is separated from the PHMB ethanol solution by pressing to remove liquid, and is placed in the previous chloroform solution with stirring at 25° C. for 4 hours. Liquid is separated by centrifuge to obtain a PHMB coated alginate fiber. Finally, the PHMB coated alginate fiber is washed once by 15/10000 sodium hydroxide alcohol solution (alcohol at the concentration of 70%), then washed by 95% alcohol for 4 times, then washed once by absolute ethanol, and then dried at 55° C. by vacuum for 24 hours to obtain 930 g of semi-finished product. The long alginate fiber, which is covalent bonded with PHMB in the interface, is processed to obtain gauze, which is then cut, packaged, and sterilized.

(26) A gauze antimicrobial alginate dressing containing 0.115% of PHMB is obtained, and the weight of the dressing is 167 g/m.sup.2.

Embodiment 4

(27) A method is for manufacturing an antimicrobial alginate fiber dressing. A short alginate fiber with length of 3 to 5 cm may be provided with 1000 g, and is placed into 5000 g of aqueous solution containing 0.54% of hydrochloric acid and 9.5% of ethanol, at 20° C. The alginate fiber in the aqueous solution is stirred and activated for 3.0 hours, and then the alginate fiber is separated from the aqueous solution by centrifuge to remove liquid. The alginate fiber may be soaked with 2000 g of absolute ethanol for 10 to 15 minutes, and then ethanol is separated by centrifuge to obtain a primary activated alginate fiber. 110 g of N,N-diisopropylethylamine is added into 5500 g of chloroform solution (triphenylphosphine: 0.235%, and iodine: 0.228%) with stirring at 70 r/min, and stirring time is counted by a timer. After stirring for 1-2 minutes, the primary activated alginate fiber is placed into the chloroform solution. The chloroform solution is stirred for 3 to 5 minutes, and the primary activated alginate fiber is activated at 35° C. for 30 minutes. The fiber is taken out of the solution, and is compressed to remove remaining liquid, to obtain a secondary activated fiber. Next, 4000 g of PHMB ethanol solution where PHMB is at the concentration of 0.082% (m/m) and the secondary activated fiber is mixed and stirred at 25° C. for 40 minutes. The secondary activated fiber is separated from the PHMB ethanol solution by pressing to remove liquid, and is placed in the previous chloroform solution with stirring at 25° C. for 4 hours. Liquid is separated by centrifuge to obtain a PHMB coated alginate fiber. Finally, the PHMB coated alginate fiber is washed once by 15/10000 sodium hydroxide alcohol solution (alcohol at the concentration of 70%), then washed by 95% alcohol for 4 times, then washed once by absolute ethanol, and is dried at 55° C. by vacuum for 24 hours to obtain 921 g of semi-finished product. The alginate fiber, which is covalent bonded with PHMB in the interface, is subjected to needling and hot press drying process. Alginate nonwoven fabrics is obtained by combing, laying, and needle punching, and then is cut, packaged, and sterilized.

(28) A nonwoven antimicrobial alginate dressing containing 0.181% of PHMB is obtained, and the weight of the dressing is 145 g/m.sup.2.

Embodiment 5

(29) A method is for manufacturing an antimicrobial alginate fiber dressing. A short alginate fiber with length of 3 to 5 cm may be provided with 1000 g, and is placed into 5000 g of aqueous solution containing 0.54% of hydrochloric acid and 9.5% of ethanol, at 20° C. The aqueous solution is stirred and activated for 3.0 hours, and then the alginate fiber is separated from the aqueous solution by centrifuge to remove liquid. The alginate fiber may be soaked with 2000 g of absolute ethanol for 10 to 15 minutes, and then ethanol is separated by centrifuge to obtain a primary activated alginate fiber. 110 g of N,N-diisopropylethylamine is added into 5500 g of chloroform solution (triphenylphosphine: 0.235%, and iodine: 0.228%) with stirring at 70 r/min, and stirring time is counted by a timer. After stirring for 1-2 minutes, the primary activated alginate fiber is placed into the chloroform solution. The chloroform solution may be stirred for 3 to 5 minutes, and the primary activated alginate fiber is activated at 35° C. for 30 minutes. The fiber is taken out of the solution and is compressed to remove remaining liquid, to obtain a secondary activated fiber. Next, 4000 g of PHMB ethanol solution where PHMB is at the concentration of 0.104% (m/m) and the secondary activated fiber is mixed and stirred at 25° C. for 40 minutes. The secondary activated fiber is separated from the PHMB ethanol solution by pressing to remove liquid, and is placed in the previous chloroform solution with stirring at 25° C. for 4 hours. Liquid is separated from the chloroform solution by centrifuge to obtain a PHMB coated alginate fiber. Finally, the PHMB coated alginate fiber is washed once by 15/10000 sodium hydroxide alcohol solution (alcohol at the concentration of 70%), then washed by 95% of alcohol for 4 times, then washed once by absolute ethanol, and is dried at 55° C. by vacuum for 24 hours to obtain 925 g of semi-finished product. The alginate fiber, which is covalent bonded with PHMB in the interface, is subjected to needling and hot press drying process. Alginate nonwoven fabrics is obtained by combing, laying, and needle punching, and then cut, packaged, and sterilized.

(30) A nonwoven antimicrobial alginate dressing containing 0.249% of PHMB is obtained, and the weight of the dressing is 119 g/m.sup.2.

Embodiment 6

(31) A method is for manufacturing an antimicrobial alginate fiber dressing. A short alginate fiber with length of 3 to 5 cm may be provided with 1000 g, and is placed into 5000 g of aqueous solution containing 0.54% of hydrochloric acid and 9.5% of ethanol, at 20° C. The aqueous solution is stirred and activated for 3.0 hours, and then the alginate fiber is separated from the aqueous solution by centrifuge to remove liquid. The alginate fiber may be soaked with 2000 g of absolute ethanol for 10 to 15 minutes, and then ethanol is separated by centrifuge to obtain a primary activated alginate fiber. 110 g of N,N-diisopropylethylamine is added into 5500 g of chloroform solution (triphenylphosphine: 0.235%, and iodine: 0.228%) with stirring at 70 r/min, and stirring time is counted by a timer. After stirring for 1-2 minutes, the primary activated alginate fiber is placed into the chloroform solution. The chloroform solution is stirred for 3 to 5 minutes, and the primary activated alginate fiber is activated at 35° C. for 30 minutes. The fiber is taken out of the solution and is compressed to remove remaining liquid, to obtain a secondary activated fiber. Next, 4000 g of PHMB ethanol solution where PHMB is at the concentration of 0.183% (m/m) and the secondary activated fiber is mixed and stirred at 25° C. for 40 minutes. The secondary activated fiber is separated from the PHMB ethanol solution by pressing to remove liquid, and is placed in the previous chloroform solution with stirring at 25° C. for 4 hours. Liquid is separated from the chloroform solution by centrifuge to obtain a PHMB coated alginate fiber. Finally, the PHMB coated alginate fiber is washed once by 15/10000 sodium hydroxide alcohol solution (alcohol at the concentration of 70%), then washed by 95% alcohol for 4 times, then washed once by absolute ethanol, and is dried at 55° C. by vacuum for 24 hours to obtain 918 g of semi-finished product. The alginate fiber, which is covalent bonded with PHMB in the interface, is subjected to needling and hot press drying process. Alginate nonwoven fabrics is obtained by combing, laying, and needle punching, and then cut, packaged, and sterilized.

(32) A nonwoven antimicrobial alginate dressing containing 0.512% of PHMB is obtained and the weight of the dressing is 107 g/m.sup.2.

Embodiment 7

(33) An antimicrobial alginate fiber may include a molecular structure as shown following.

(34) ##STR00003##

(35) X is equal to 10, n is equal to 10, and A is hydrochloric acid. Numbers a and b are general descriptions of the molecular structure of alginate, and are not in specific numerically limited.

(36) Further, the antimicrobial alginate fiber is obtained by loading polyhexamethylene biguanide salt to an alginate fiber via covalent bond formed by interfacial reaction.

(37) Further, the alginate may be one of water soluble alginate, water insoluble alginate, and a blend of a water soluble alginate and a water insoluble alginate. The water soluble alginate is sodium alginate. The water insoluble alginate is calcium alginate.

(38) Further, the blend of the water soluble alginate and the water insoluble alginate may include blends formed of water soluble alginate with calcium ions as a crosslinking agent.

(39) Further, the polyhexamethylene guanide salt is polyhexamethylene guanidine hydrochloride and a derivative thereof. The polyhexamethylene guanide salt has a mass percentage of 0.5%.

(40) A method for manufacturing the above-mentioned antimicrobial alginate fiber dressing includes operations in the following blocks.

(41) Block S1, aqueous hydrochloric acid solution or ethanol hydrochloride solution is provided as an inorganic reaction phase, and chloroform solution is provided as an organic reaction phase. Catalyst is added into the mixed solution. Activation time of an alginate fiber in the mixed solution is 10 minutes, and an activation temperature is 10° C.

(42) Block S2, the alginate fiber treated in block S1 is added into antimicrobial active ethanol solution. Reaction time is 0.5 hours, and the reaction temperature is 10° C. The antimicrobial active ethanol solution is polyhexamethylene biguanide hydrochloride (PHMB×HCl) ethanol solution.

(43) Block S3, the alginate fiber treated in block S2 is added into chloroform solution. Reaction time is 0.5 hours, and the reaction temperature is 10° C.

(44) Block S4, the alginate fiber treated in block S3 is covalent bonded with polyhexamethylene biguanide hydrochloride in the interface, forming a molecular scaled polyhexamethylene biguanide hydrochloride coating layer. The reaction principle is shown in FIG. 1, and its structural illustration is shown in FIG. 2.

(45) Block S5, the alginate fiber obtained in block S4 is washed once by 10/10000 sodium hydroxide alcohol solution and the alcohol is at the concentration of 70%. The alginate fiber is then washed 6 times by 80% alcohol, and then washed once by absolute ethanol. The alginate fiber is then dried by a vacuum pump at 40° C. for 12 hours, to obtain the antimicrobial alginate fiber.

(46) Further, in block S1, the aqueous hydrochloric acid solution contains 0.1% (m/m) of hydrochloric acid, and 99.9% (m/m) of water. A mass ratio of the aqueous hydrochloric acid solution to the alginate fiber is 4.0. The alginate fiber is activated in the mixed solution for 0.5 hours at 10° C. Further, in block S1, the ethanol hydrochloride solution contains 0.5% (m/m) of hydrochloric acid, 10% (m/m) of water, and 89.5% (m/m) of ethanol. A mass ratio of the ethanol hydrochloride solution to the alginate fiber mass ratio is 4.0. Activation time of the alginate fiber in the mixed solution is 0.5 hours, and the activation temperature is 10° C.

(47) Further, the catalyst is a mixture of triphenylphosphine, iodine, and N,N-diisopropylethylamine. The triphenylphosphine and iodine is in equimolar ratio. The chloroform solution may contain 0.05% (m/m) of triphenylphosphine, 0.05% (m/m) of iodine, and 0.5 (m/m) of N,N-diisopropylethylamine.

(48) The catalyst is prepared by pre-dissolving triphenylphosphine and iodine in chloroform to reach a desired concentration, and then pre-weighed N,N-diisopropylethylamine is rapidly added under stirring at 50 r/min, and then a primary activated alginate fiber is added.

(49) Further, in block S1, a mass ratio of the mixed solution to the alginate fiber is 4.0. The activation time of the alginate fiber in the mixed solution is 10 minutes, and the activation temperature is 10° C. Further, in block S2, mass concentration of the antimicrobial active ethanol solution is 0.01%, and the mass of the antimicrobial active ethanol solution is 2 times of the mass of the alginate fiber.

(50) An application of the above-mentioned antimicrobial alginate fiber dressing is provided. The above-mentioned antimicrobial alginate fiber may be processed by combing, laying, and needle-punching, to produce alginate nonwoven fabrics. The alginate nonwoven fabrics may be processed by cutting, packaging, and sterilizing, to produce an antimicrobial alginate fiber dressing product, such as an antimicrobial alginate towel, antimicrobial alginate nonwoven fabrics, and antimicrobial alginate gauze. The antimicrobial alginate fiber dressing product may be applied to acute and chronic wound care.

Embodiment 8

(51) An antimicrobial alginate fiber includes a molecular structure as shown following.

(52) ##STR00004##

(53) X is equal to 40, n is equal to 40, and A is gluconic acid. Number a and b are general descriptions of the molecular structure of alginate, and not in specific numerically limited.

(54) Further, the antimicrobial alginate fiber is obtained by loading polyhexamethylene biguanide salt to an alginate fiber via covalent bond formed by interfacial reaction.

(55) Further, the alginate may be one of water soluble alginate, one of water insoluble alginate, and a blend of a water soluble alginate and a water insoluble alginate. The water soluble alginate is magnesium alginate. The water insoluble alginate is zinc alginate.

(56) Further, the blend of the water soluble alginate and the water insoluble alginate includes blends formed of water soluble alginate with zinc ions as a crosslinking agent.

(57) Further, the polyhexamethylene guanide salt is polyhexamethylene guanide phosphoric acid and a derivative thereof. The polyhexamethylene guanide salt is in a mass percentage of 0.05%.

(58) A method for manufacturing the above-mentioned antimicrobial alginate fiber dressing includes operations in the following blocks.

(59) Block S1, aqueous hydrochloric acid solution or ethanol hydrochloride solution may be provided as an inorganic reaction phase, and chloroform solution is provided as an organic reaction phase. Catalyst is added into the mixed solution. Activation time of an alginate fiber in the mixed solution is 60 minutes, and an activation temperature is 40° C.

(60) Block S2, the alginate fiber treated in block S1 is added into antimicrobial active ethanol solution. Reaction time is 24 hours, and the reaction temperature is 40° C. The antimicrobial active ethanol solution is polyhexamethylene biguanide hydrochloride (PHMB×HCl) ethanol solution.

(61) Block S3, the alginate fiber treated in block S2 is added into chloroform solution. Reaction time is 24 hours, and the reaction temperature is 40° C.

(62) Block S4, the alginate fiber treated in block S3 is covalent bonded with polyhexamethylene biguanide hydrochloride in the interface, to form a molecular scaled polyhexamethylene biguanide hydrochloride coating layer. The reaction principle is shown in FIG. 1, and its structural illustration is shown in FIG. 2.

(63) Block S5, the alginate fiber obtained in block S4 is washed once by 50/10000 sodium hydroxide alcohol solution and the alcohol is at the concentration of 70%. The alginate fiber is then washed 3 times by 95% alcohol, and then washed 3 times by absolute ethanol. The alginate fiber is dried by a vacuum pump at 65° C. for 24 hours, to obtain the antimicrobial alginate fiber.

(64) Further, in block S1, the aqueous hydrochloric acid solution contains 5.0% (m/m) of hydrochloric acid, and 85.0% (m/m) of water. A mass ratio of the aqueous hydrochloric acid solution to the alginate fiber is 10.0. Activation time of the alginate fiber in the mixed solution is 24 hours, and the activation temperature is 40° C.

(65) Further, the catalyst is a mixture of triphenylphosphine, iodine, and N,N-diisopropylethylamine. The triphenylphosphine and iodine is in equimolar ratio. The chloroform solution contains 3.0% (m/m) of triphenylphosphine, 3.0% (m/m) of iodine, and 8.0% of N,N-diisopropylethylamine.

(66) The catalyst is prepared by pre-dissolving triphenylphosphine and iodine in chloroform to reach a desired concentration, and then pre-weighed N,N-diisopropylethylamine is rapidly added under stirring at 100 r/min, and then a primary activated alginate fiber is added.

(67) Further, in block S1, a mass ratio of the mixed solution to the alginate fiber is 20.0. The activation time of the alginate fiber in the mixed solution is 60 minutes, and the activation temperature is 40° C. Further, in block S2, mass concentration of the antimicrobial active ethanol solution is at 5.0%, and the mass of the antimicrobial active ethanol solution is 10 times of the mass of the alginate fiber.

(68) An application of the above-mentioned antimicrobial alginate fiber dressing is provided. The antimicrobial alginate fiber is processed by combing, laying, and needle-punching, to form an alginate nonwoven. The alginate nonwoven is processed by cutting, packaging, and sterilizing, to form an antimicrobial alginate fiber dressing product, such as an antimicrobial alginate towel, an antimicrobial alginate nonwoven fabrics, and antimicrobial alginate gauze. The antimicrobial alginate fiber dressing product may be applied to acute and chronic wound care.

Embodiment 9

(69) An antimicrobial alginate fiber includes a molecular structure as shown following.

(70) ##STR00005##

(71) X is equal to 20, n is equal to 20, and A is phosphoric acid. Number a and b are general descriptions of the molecular structure of alginate, and not in specific numerically limited.

(72) Further, the antimicrobial alginate fiber is obtained by loading polyhexamethylene biguanide to an alginate fiber via covalent bond formed by interfacial reaction.

(73) Further, the alginate may be one of water soluble alginate, one of water insoluble alginate, and a blend of the water soluble alginate and the water insoluble alginate. The water soluble alginate is potassium alginate. The water insoluble alginate is calcium alginate.

(74) Further, the blend of the water soluble alginate and the water insoluble alginate includes blends formed of water soluble alginate with calcium ions as a crosslinking agent.

(75) Further, the polyhexamethylene guanide salt is polyhexamethylene propionate and a derivative thereof. The polyhexamethylene guanide salt is at the concentration of 0.5% (m/m).

(76) A method for manufacturing the above-mentioned antimicrobial alginate fiber dressing includes operations in the following blocks.

(77) Block S1, aqueous hydrochloric acid solution or ethanol hydrochloride solution is provided as an inorganic reaction phase, and chloroform solution is provided as an organic reaction phase. Catalyst is added into the mixed solution. Activation time of an alginate fiber in the mixed solution is 30 minutes, and an activation temperature is 25° C.

(78) Block S2, the alginate fiber treated in block S1 is added into antimicrobial active ethanol solution. Reaction time is 8 hours, and the reaction temperature is 25° C. The antimicrobial active ethanol solution is polyhexamethylene biguanide hydrochloride (PHMB×HCl) ethanol solution.

(79) Block S3, the alginate fiber treated in block S2 is added into chloroform solution. Reaction time is 8 hours, and the reaction temperature is 25° C.

(80) Block S4, the alginate fiber treated in block S3 is covalent bonded with polyhexamethylene biguanide hydrochloride in the interface, to form a molecular scaled polyhexamethylene biguanide hydrochloride coating layer. The reaction principle is shown in FIG. 1, and its structural illustration is shown in FIG. 2.

(81) Block S5, the alginate fiber obtained in block S4 is washed once by 30/10000 sodium hydroxide alcohol solution and the alcohol is at the concentration of 70%. The alginate fiber is then washed 5 times by 90% alcohol, and then washed twice by absolute ethanol. The alginate fiber is dried by a vacuum pump at 50° C. for 18 hours, to obtain the antimicrobial alginate fiber.

(82) Further, in block S1, the aqueous hydrochloric acid solution contains 2.0% (m/m) of hydrochloric acid, and 88% (m/m) of water. A mass ratio of the aqueous hydrochloric acid solution to the alginate fiber is 6.0. Activation time of the alginate fiber in the mixed solution is 8 hours, and the activation temperature is 25° C. Further, in block S1, the ethanol hydrochloric acid solution contains 2% (m/m) of hydrochloric acid, 20% (m/m) of water, and 78% (m/m) of ethanol, and a mass ratio of the ethanol hydrochloride solution to the alginate fiber is 6. Activation time of the alginate fiber in the mixed solution is 8 hours, and the activation temperature is 25° C.

(83) Further, the catalyst is a mixture of triphenylphosphine, iodine, and N,N-diisopropylethylamine. The triphenylphosphine and iodine is in equimolar ratio. A mass fraction of the triphenylphosphine in the chloroform solution is 1.0%. A mass fraction of the iodine in the chloroform solution is 1.0%. A mass fraction of the N,N-diisopropylethylamine in the chloroform solution the N,N-diisopropylethylamine is 3.0%.

(84) The catalyst is prepared by pre-dissolving triphenylphosphine and iodine in chloroform to reach a desired concentration, and then pre-weighed N,N-diisopropylethylamine is rapidly added under stirring at 80 r/min, and then a primary activated alginate fiber is added.

(85) Further, in block S1, a mass ratio of the mixed solution to the alginate fiber is 6.0. The activation time of the alginate fiber in the mixed solution is 30 minutes, and the activation temperature is 25° C. Further, in block S2, mass concentration of the antimicrobial active ethanol solution is at 2.0%, and the mass of the antimicrobial active ethanol solution is 6 times of the mass of the alginate fiber.

(86) An application of the above-mentioned antimicrobial alginate fiber dressing is provided. An antimicrobial alginate fiber may be processed by combing, laying, and needle-punching, to form an alginate nonwoven. The alginate nonwoven may be processed by cutting, packaging, and sterilizing, to form an antimicrobial alginate fiber dressing product, such as an antimicrobial alginate towel, an antimicrobial alginate nonwoven fabrics, and antimicrobial alginate gauze. The antimicrobial alginate fiber dressing product may be applied to acute and chronic wound care.

(87) Antimicrobial effect tests of embodiments are provided in the present disclosure.

(88) 1. An antimicrobial property test may be performed as the following description.

(89) The quantitative evaluation method of antimicrobial activity refers to “AATCC 100-2012 Antimicrobial Finishes on Textile Materials Assessment of Fulltext Information”, which is briefly described as the following description.

(90) (1) Test strains: Gram-positive bacteria, Enterococcus faecalis (ATCC 51575); Gram-negative bacteria, Pseudomonas aeruginosa (ATCC 9027).

(91) (2) Medium: nutrient broth, and agar medium (NB, NA).

(92) (3) Diluent: sterile phosphate buffered saline (PBS).

(93) (4) Simulated wound fluid (SWF): PBS containing 10% (V/V) fetal bovine serum.

(94) (5) Live bacteria concentration: 2×10.sup.6 cfu/ml to 4×10.sup.6 cfu/ml.

(95) (6) Test sample: a circular alginate dressing with a diameter of 4.8 cm±0.1 cm (1.9±0.03 inches).

(96) (7) Inoculum: PBS containing 1.0±0.1 ml 10% (V/V) fetal bovine serum, and live bacteria concentration 2×10.sup.6 cfu/ml to 4×10.sup.6 cfu/ml.

(97) (8) Neutralizing reagent: lecithin at the concentration of 20 g/L, 100 ml of TPS solution containing 20 g/L of Tween-80.

(98) (9) Antimicrobial period: 24 hours, 7 days/168 hours, and 14 days/336 hours.

(99) The test results are shown in the following table.

(100) TABLE-US-00001 Con- Anti- Anti- Anti- tent microbial microbial microbial of rate in 24 rate in rate in PHMB hours 7 days 14 days Strains Sample (%) (%) (%) (%) Enterococcus Embodiment 1 0.056 — 99.5 99.7 faecalis Embodiment 2 0.076 99.96 99.99 99.99 Embodiment 3 0.115 99.99 100 100 Embodiment 4 0.181 100 99.99 99.99 Embodiment 5 0.249 100 100 100 Embodiment 6 0.512 100 99.99 100 control sample 0 N/A N/A N/A Pseudomonas Embodiment 1 0.056 — 99.6 99.7 aeruginosa Embodiment 2 0.076 99.94 99.98 99.99 Embodiment 3 0.115 99.99 99.99 100 Embodiment 4 0.181 99.99 99.99 100 Embodiment 5 0.249 99.99 100 99.99 Embodiment 6 0.512 99.99 100 100 control sample 0 N/A N/A N/A Remark: The control sample is an alginate dressing without the antimicrobial component.

(101) 2. A method for the detection of the content of polyhexamethylene guanide salt may be performed as the following.

(102) Aqueous solution containing 1.5% (m/m) of agar is prepared, and when the agar solution is cooled to 50-55° C., 25.00±0.05 g of the solution is poured into a watch glass, to form an agar gel with a diameter of 90 mm and thickness of 3-4 mm to simulate the skin. PBS is added to an alginate fiber dressing with an area of 5×5 cm, to form an alginate gel, wherein the weight of PBS is 8 times of that of the alginate fiber dressing. The alginate gel may be hung up to drip dry for approximately 1 minute, when it has excessive free water. The alginate gel is spread on the surface of the agar gel, and is covered by a watch glass. The gel with the watch glass cover is sealed by a PE film for protection, and is placed in an incubator at a temperature of 37° C. for 72 hours and 168 hours. The agar gel is immersed by pure water, wherein the water is in twice amount of the agar gel, to establish an extraction system. The extraction system is sealed, and is placed in an incubator at a temperature of 37° C. for 24 hours, to obtain extraction solution. The extraction solution is filtered by a filter paper, the content of PHMB in the extraction solution is measured, and the amount of PHMB filtered out of the alginate dressing is calculated.

(103) The measurement results are shown in the following table.

(104) TABLE-US-00002 Content of Filtration Rate in Filtration Rate in Sample PHMB (%) 72 hours (%) 168 hours (%) Embodiment 1 0.056 1.09 1.25 Embodiment 2 0.076 1.01 1.15 Embodiment 3 0.115 0.73 0.95 Embodiment 4 0.181 0.58 0.76 Embodiment 5 0.249 1.33 1.71 Embodiment 6 0.512 0.42 0.55 control sample 0.409 9.23 11.81 Remark: The control sample is a commercially available PHMB foam dressing approved by the US FDA.

(105) 3. A test of the content of PHMB in alginate fiber may be performed as the following:

(106) (1) Principle: a color reaction occurs between guanidyl and eosin (a dye), and color change can be measured by the absorbance at the wavelength of 546 nm.

(107) (2) Indicating solution: 500 ml of aqueous solution containing 0.2891 g/L of Eosin Y is prepared; and is filtered by a membrane filter having a pore size of 0.45 m, and the filtered solution is stored in dark.

(108) (3) Buffer solution: 500 ml of aqueous solution of acetic acid and sodium acetate trihydrate in a mass ratio of 1:0.9514 is prepared where the molar concentration of [CH.sub.3COO].sup.− is 3.8532 mol/L; the aqueous solution is filtered by a membrane filter having a pore size of 0.45 m, and is sealed at room temperature for later use.

(109) (4) Stabilizer solution: 2.000±0.0005 g of a blank alginate dressing, 10.5800±0.0005 g of trisodium citrate dihydrate, and 187.42±0.05 g of distilled water are provided; the trisodium citrate dihydrate is dissolved in 187.42 g of the distilled water in a 500 ml beaker; when the trisodium citrate dehydrate is completely dissolved, the blank alginate dressing is added into the solution; and the solution may be stirred by a stirring disperser to dissolve the blank alginate dressing at a low speed for 3 to 5 minutes; when the solution is stable, stirring speed of the stirring disperser is slowly increased, and finally the solution is stirred at the speed of 2200 r/min for 1.5 hours; lost distilled water is quantitatively replenished into the aqueous solution; the aqueous solution is filtered by a membrane filter having a pore size of 0.45 m, and the filtered aqueous solution is sealed at room temperature for later use.

(110) (5) Standard curve drawing: guanidyl concentration and absorbance values are used to generate a standard curve, and a linear fitting curve equation is shown in FIG. 3.

(111) The equation of the obtained standard curve is Y=0.12326*X+0.00942. The curve shows that polyhexamethylene biguanide hydrochloride (PHMB×HCl) at the concentration of 0.253 ppm to 4.380 ppm has a good linear relationship against the absorbance, and a correlation coefficient of the standard curve is 0.99763.

(112) The content of PHMB in the alginate fiber dressings is calculated based on the above standard curve, the results are shown in the following table.

(113) TABLE-US-00003 Sample Content of PHMB (%) Embodiment 1 0.056 Embodiment 2 0.076 Embodiment 3 0.115 Embodiment 4 0.181 Embodiment 5 0.249 Embodiment 6 0.512

(114) To the skilled personnel in the art, the present disclosure should not be limited to the details of the above-described exemplary embodiments, and the present disclosure may be embodied in other specific forms without departing from the spirit or essential characteristics of the disclosure. Therefore, the present embodiments should be considered as illustrative and not restrictive, and the scope of the present disclosure is defined by the appended claims, but not by the above embodiments and descriptions, all changes in the meaning and scope of equivalent elements are included in the present disclosure. Any reference signs in the claims should not be treated as limitation of the claims.

(115) In addition, it should be understood that although the description is described in terms of embodiments, not every embodiment includes only one independent technical solution. The description of the specification is merely for clarity, and the skilled personnel in the art should treat the specification as a whole, and the technical solutions in the respective embodiments may also be combined as appropriate to form other embodiments that can be understood by any skilled personnel in the art. It should be noted that the technical features not described in detail in the present disclosure may be implemented by any prior art.

(116) Industrial application of the present disclosure is provided. The above-mentioned antimicrobial alginate fiber may be processed by combing, laying, and needle-punching, to form an alginate nonwoven. The alginate nonwoven may be processed by cutting, packaging, and sterilizing, to form an antimicrobial alginate fiber dressing product, such as an antimicrobial alginate towel, antimicrobial alginate nonwoven fabrics, and antimicrobial alginate gauze. The antimicrobial alginate fiber dressing product may be applied to acute and chronic wound care.