Endless Core-Sheath Fibers on the Basis of Hyaluronan or C11-C18 Acylated Derivatives Thereof, Method of Preparation and Use Thereof, Staple Fibers, Yarn and Textiles Made of These Fibers and Use Thereof

Abstract

The invention relates to two-component biodegradable core-sheath fibers comprising a combination of native and C.sub.11-C.sub.18 acylated hyaluronan or C.sub.11-C.sub.18 acylated hyaluronans. It further relates to method of preparation and use thereof, especially for controlled release of the active agent. Fibers may be further processed into the form of staple fibers, yarn, braided, woven, knitted and non-woven textiles.

Claims

1. Endless fiber of the type core-sheath on the basis of hyaluronan or C.sub.11-C.sub.18 acylated derivative thereof, characterized in that it comprises a combination of hyaluronan and acylated derivative thereof or a combination of acylated derivatives thereof, the fiber core and the sheath being in any of the following arrangements: A) the core contains hyaluronic acid or a salt thereof, the sheath contains C.sub.11-C.sub.18 acylated hyaluronan; B) the core contains C.sub.11-C.sub.18 acylated hyaluronan, the sheath contains hyaluronic acid or a salt thereof; C) the core contains C.sub.11-C.sub.18 acylated hyaluronan, the sheath contains different C.sub.11-C.sub.18 acylated hyaluronan differing in C.sub.11-C.sub.18 acyl from C.sub.11-C.sub.18 acylated hyaluronan of the core, the degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan in the sheath being identical or different from the degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan in the core; or D) the core contains C.sub.11-C.sub.18 acylated hyaluronan, the sheath contains different C.sub.11-C.sub.18 acylated hyaluronan differing in degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan of the sheath.

2. Fiber according to claim 1, characterized in that C.sub.11-C.sub.18 acylated hyaluronan is acylated in primary alcohol of N-acetyl-glucosamine.

3. Fiber according to claim 1, characterized in that molar mass of C.sub.11-C.sub.18 acylated hyaluronan is in the range 110.sup.5 to 710.sup.5 g/mol.

4. Fiber according to claim 1, characterized in that the degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan of arrangement A or B is in the range 5 to 80%.

5. Fiber according to claim 1, characterized in that the degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan contained in the core of arrangement C is in the range 5 to 80%, and the degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan contained in the sheath of arrangement C is in the range 5 to 80%; or the degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan contained in the core of arrangement D is in the range 5 to 29% and the degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan contained in the sheath of arrangement D is in the range 30 to 80.

6. Fiber according to any one of claims 1 to 5, characterized in that C.sub.11-C.sub.18 acylated hyaluronan is selected from a group containing palmitoyl hyaluronan, stearoyl hyaluronan or oleoyl hyaluronan.

7. Fiber according to any one of claims 1 to 4, characterized in that hyaluronic acid and/or a salt thereof has molar mass in the range 110.sup.5 to 210.sup.6 g/mol, the salt of hyaluronic acid being selected from a group containing alkali metal ions, alkaline earth metals ions.

8. Fiber according to any one of claims 1 to 5, characterized in that fiber fineness is in the range 10 to 40 tex.

9. Fiber according to any one of claims 1 to 5, characterized in that the volume ratio core:sheath is in the range 3:1 to 1:6.

10. Fiber according to any one of claims 1 to 5, characterized in that it contains at least one active agent.

11. Fiber according to claim 10, characterized in that both core and sheath contain at least one identical or different active agent.

12. Fiber according to claim 10, characterized in that the active agent is selected from a group containing antibacterial, antiseptic, antibiotic, anti-inflammatory, hemostatic agents, anesthetics, cytostatics, hormones, immunomodulators, immunosuppressives or agents for contrast imagining.

13. Fiber defined in any one of claims 1 to 5 for use in manufacturing of yarns, braided, woven, knitted or non-woven textiles.

14. Method of preparation of fibers defined in any one of claims 1 to 5, characterized in that the first spinning solution containing hyaluronic acid or a salt thereof of concentration in the range 1 to 8 wt % is separately prepared in water and the second spinning solution containing C.sub.11-C.sub.18 acylated hyaluronan of concentration 2 to 8 wt % is prepared in the mixture of water and lower alcohol, wherein water content is in the range 30 v/v % to 90 v/v %, lower alcohol content is in the range 10 v/v % to 70 v/v %, after which both the first and second spinning solution are extruded together into the coagulation bath containing 2 to 40 wt % of organic acid, at least 50 wt % of lower alcohol, and 2 to 48 wt % of water resulting in fiber of arrangement A or B, that is consequently scoured with lower alcohol and dried.

15. Method of preparation of fibers defined in any one of claims 1 to 5, characterized in that the first spinning solution containing C.sub.11-C.sub.18 acylated hyaluronan of concentration in the range 2 to 8 wt % is separately prepared in a mixture of water and lower alcohol and the second spinning solution containing different C.sub.11-C.sub.18 acylated hyaluronan of concentration 2 to 8 wt % is prepared in a mixture of water and lower alcohol, wherein water content in both solutions is in the range 30 v/v % to 90 v/v %, lower alcohol content is in the range 10 v/v % to 70 v/v %, after which both the first and second spinning solution are extruded together into the coagulation bath containing 2 to 40 wt % of organic acid, at least 50 wt % of lower alcohol, and 2 to 48 wt % of water resulting in fiber of arrangement C or D, that is consequently scoured with lower alcohol and dried.

16. Method according to claim 14, characterized in that the first spinning solution and/or the second spinning solution contain an active agent.

17. Method according to claim 14, characterized in that the first spinning solution and/or the second spinning solution contain nanomicellar composition based on acylated hyaluronan containing the active agent.

18. Staple fibers made from fibers defined in any one of claims 1 to 5.

19. Non-woven textile made of staple fibers defined in claim 18.

20. Yarn made of at least one fiber defined in any one of claims 1 to 5.

21. Yarn according to claim 20, characterized in that it is formed of a bundle of fibers containing 2 to 10 fibers.

22. Yarn according to claim 21, characterized in that it is in the form of twisted bundle of fibers.

23. Yarn formed of at least two fibers, characterized in that at least one fiber is fiber defined in any one of claims 1 to 5, and at least one fiber is fiber selected from a group of fibers of other biodegradable materials, the biodegradable material being selected from a group comprising polylactic acid, polyglycolic acid, copolymer of polylactic and polyglycolic acid, polycaprolactone, polydioxanone or polyhydroxyalkanoates.

24. Yarn according to claim 20, characterized in that it has fineness in the range 10 to 400 tex.

25. Braided textile, woven textile or knitted textile, characterized in that it contains at least one yarn defined in claim 20.

26. Braided, woven or knitted characterized in that it is made of yarn defined in claim 20.

27. Braided, woven or knitted textile according to claim 25, characterized in that fiber core and sheath in the yarn are in arrangement A, C or D, whereas in the case of arrangement A there is the degree of substitution C.sub.11-C.sub.18 acylated hyaluronan in the range 30 to 80% in the sheath, preferably 40 to 60% and in the case of arrangement C or D there is the degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan in the core in the range 5 to 29%, and the degree of substitution of C.sub.11-C.sub.18 acylated hyaluronan is in the range 30 to 80% in the sheath.

28. Braided, woven or knitted textile according to claim 25, characterized in that it is in the form of linear, flat or tubular textile.

29. Braided textile according to claim 25, characterized in that it contains at least 8 yarns, containing at least one filling fiber inside the textile.

30. Braided textile according to claim 29, characterized in that the diameter of filling fiber is in the range 0.0001 to 1 mm, preferably 0.01 to 0.1 mm.

31. Braided textile according to claim 29, characterized in that the filling fiber is formed of a polymer selected from a group containing hyaluronic acid or derivatives thereof, polylactic acid, polyglycolic acid, copolymer of polylactic and polyglycolic acid, polycaprolactone, polydioxanone, polyhydroxyalkanoates, polyethylene, polypropylene, polyetherester, polyamide or polyester, preferably polylactic acid or copolymer of polylactic acid and polyglycolic acid.

32. (canceled)

33. (canceled)

34. (canceled)

35. Non-woven textile according to claim 19 for use in the area of medicine, tissue engineering and systems for controlled release.

Description

DESCRIPTION OF THE DRAWINGS

[0110] FIG. 1A Shows the centric arrangement of the core and the sheath in the fiber. The core is illustratively pulled out of the sheath.

[0111] FIG. 1B Shows the core-sheath fiber with the content of magnetic nanoparticles, prepared according to Example 6.

[0112] FIG. 2A Shows the braided textile of 16 core-sheath fibers of the invention with inserted filling fibers before wetting in water. The fiber is prepared according to method of preparation stated in Example 6 and processed with braiding according to Example 18a.

[0113] FIG. 2B Shows the braided textile identical with the textile from FIG. 2A after wetting in water, release of hyaluronan and active agent from the core and air-drying.

[0114] FIG. 3 Structure of the braided tube of Example 17a.

[0115] FIG. 4 Core-sheath fibers processed into the form of the weft knitted textile of Example 22.

[0116] FIG. 5 Core-sheath fibers processed into the form of the warp knitted textile of Example 23.

[0117] FIG. 6A The braided thread with filling fibers of Example 18c.

[0118] FIG. 6B The braided thread with filling fibers of Example 18cthe detail showing filling fibers.

EXAMPLES

[0119] Molar mass of hyaluronan was determined using HPLC Shimadzu, with attached light scattering detector midiDAWN Watt Technologies, (so called method SEC-MALLS). If not stated otherwise, stated molecular masses are medium masses.

[0120] Shots of core-sheath fibers were taken on the scanning electron microscope: [0121] 1) Tescan VEGA II LSU with the wolfram cathode and maximal resolution 3 nm. The accelerating voltage of the primary beam was 5 kV, working distance of 3-4 mm images were taken under high vacuum. [0122] 2) ZEISS ULTRA PLUS with Schottky cathode. Microscope reaches maximal resolution 0.8 nm at 30 kV for STEM detector. The accelerating voltage of the primary beam was 5 kV, working distance of 4.6 mm, current value was 40 pA, images were taken with InLens SE detector.

Example 1

[0123] Preparation of Core-Sheath Fibers from Sodium Hyaluronate and Palmitoyl Hyaluronan

[0124] For the preparation of the fiber core, it was 0.49 g of sodium hyaluronate (MW 1.5710.sup.6 g/mol) dissolved in 32.5 mL of demineralized water. Solution of the sheath was made by mixing 1.65 g of palmitoyl hyaluronan (Mw 2.410.sup.5 g/mol, degree of substitution 28%) with 15 mL of demineralized water and 15 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of a mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio of 1:4. The resulting core-sheath fiber went through a 0.4 m long bath with the rate of 0.6 m.Math.min.sup.1 and it was continually pulled out by the winding rollers. The fiber was then scoured with 100% propan-2-ol.

[0125] The core and the sheath were in volume ratio of 1:3.5. The fiber fineness was 19 tex, strength 1.46 N and its breaking elongation 12.3%.

Example 2

[0126] Preparation of Core-Sheath Fibers from Palmitoyl Hyaluronan and Sodium Hyaluronate

[0127] For the preparation of the fiber core, it was 1.5 g of palmitoyl hyaluronate (Mw 2.410.sup.5 g/mol, degree of substitution 28%) dissolved in 11 mL of demineralized water and 11 mL of propan-2-ol. Solution for the sheath was prepared by mixing 0.66 g sodium hyaluronate (Mw 1.5710.sup.6 g/mol) with 22 mL of demineralized water. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulating bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 1.0 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol.

[0128] The core and the sheath were in volume ratio 2.3:1. The fiber fineness was 22 tex.

Example 3

[0129] Preparation of Core-Sheath Fibers from Sodium Hyaluronate and Stearoyl Hyaluronan

[0130] For the preparation of the fiber core, it was 0.49 g of sodium hyaluronate (Mw 1.5710.sup.6 g/mol) dissolved in 32.5 mL of demineralized water. The solution of the sheath was made by mixing 0.95 g of stearoyl hyaluronan (Mw 1.310.sup.6 g/mol, degree of substitution 35%) with 15 mL of demineralized water and 15 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.6 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol.

[0131] The core and the sheath were in volume ratio 1:2.1. The fiber fineness was 15 tex.

Example 4

[0132] Preparation of Core-Sheath Fibers from Sodium Hyaluronate and Palmitoyl Hyaluronan with Addition of Octenidine Dihydrochloride into the Fiber Core

[0133] For the preparation of the fiber core, it was 0.375 g of sodium hyaluronate (Mw 1.5710.sup.6 g/mol) dissolved in 21.6 mL of demineralized water. 10 mg of octenidine dihydrochloride was added to this solution. The solution of the sheath was made by mixing 0.88 g of palmitoyl hyaluronan (Mw 2.410.sup.5 g/mol, degree of substitution 27%) with 11 mL of demineralized water and 11 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 1.0 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol.

[0134] The core and the sheath were in the volume ratio 1:2.3. The fiber fineness was 20 tex.

Example 5

[0135] Preparation of Core-Sheath Fibers from Sodium Hyaluronate and Palmitoyl Hyaluronan with Addition of Dexamethasonsodium Phosphate

[0136] For the preparation of the fiber core, it was 0.3 g of sodium hyaluronate (Mw 1.5710.sup.6 g/mol) dissolved in 18 mL of demineralized water. 15 mg of dexamethasonsodium phosphate was added to this solution. The solution for sheath was made by mixing 1.32 g of palmitoyl hyaluronan (Mw 2.410.sup.5 g/mol, degree of substitution 28%) with 11 mL of demineralized water and 11 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.6 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol.

[0137] The core and the sheath were in volume ratio 1:3.6. The fiber fineness was 28 tex.

Example 6

[0138] Preparation of Core-Sheath Fibers from Sodium Hyaluronate and Palmitoyl Hyaluronan with Addition of Magnetic Nanoparticles

[0139] For the preparation of the fiber core, it was 0.48 g of sodium hyaluronate (Mw 1.5710.sup.6 g/mol) dissolved in 32 mL of demineralized water. 7 mg of dispersed magnetic nano-particles based on iron oxides in ethanol at density of 8.55 g.Math.cm.sup.3 (nano-particle size 6 to 10 nm, covered by triethylen glycol) was added to this solution. Solution for the sheath was made by mixing 2.33 g of palmitoyl hyaluronan (Mw 2.7010.sup.5 g/mol, degree of substitution 37%) with 16 mL of demineralized water and 16 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. Resulting core-sheath fiber went through 0.4 m long bath with the rate 0.6 m.Math.min.sup.1 and was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol.

[0140] The core and the sheath were in volume ratio 1:5. The fiber fineness was 32 tex, strength 2.62 N and its breaking elongation 8.1%.

Example 7

[0141] Preparation of Core-Sheath Fibers from Sodium Hyaluronate with Low Molar Mass and Palmitoyl Hyaluronan with High Molar Mass

[0142] For the preparation of the fiber core it was 1 g of sodium hyaluronate (Mw 310.sup.5 g/mol) dissolved in 24 mL of demineralized water. Solution for the sheath was made by mixing 1.87 g of palmitoyl hyaluronan (Mw 6.4010.sup.5 g/mol, degree of substitution 44%) with 17 mL of demineralized water and 17 mL of popan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into coagulation bath. Extrusion rate was 250 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 1.0 m.Math.min.sup.1 and was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol and acetone.

[0143] The core and the sheath were in volume ratio 1:1.3. The fiber fineness was 28 tex, strength 2.35 N and its breaking elongation 21.1%.

Example 8

Preparation of the Core-Sheath Fiber of Low Value of Fineness

[0144] For the preparation of the fiber core, it was 0.38 g of sodium hyaluronate (Mw 1.6610.sup.6 g/mol) dissolved in 25 mL of demineralized water. Solution for the sheath was made by mixing 1.6 g of palmitoyl hyaluronan (Mw 2.8010.sup.5 g/mol, degree of substitution 36%) with 17 mL of demineralized water and 17 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of a mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 1.3 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol and acetone.

[0145] The core and the sheath were in volume ratio 1:3. The fiber fineness was 11 tex, strength 1.41 N and its breaking elongation 15.5%.

Example 9

[0146] Preparation of the Core-Sheath Fiber from Sodium Hyaluronate and Palmitoyl Hyaluronan with Addition of Octenidin Dihydrochloride in the Fiber Sheath

[0147] For the preparation of the fiber core, it was 0.45 g of sodium hyaluronate (Mw 6.8010.sup.5 g/mol) dissolved in 25 mL of demineralized water. Solution for the sheath was made by mixing 1.59 g of palmitoyl hyaluronan (Mw 2.4010.sup.5 g/mol, degree of substitution 55%) with 17 mL of demineralized water and 17 mL of propan-2-ol. 30 mg of octenidine dihydrochloride was added to this solution. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.8 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol and acetone.

[0148] The core and the sheath were in volume ratio 1:2.5. The fiber fineness was 20 tex, strength 1.97 N and its breaking elongation 15.4%.

Example 10

[0149] Preparation of the Core-Sheath Fiber from Sodium Hyaluronate and Palmitoyl Hyaluronan with Addition of Naproxen into the Fiber Core and Octenidine Dihydrochloride into the Fiber Sheath

[0150] For the preparation of the fiber core, it was 1.05 g of sodium hyaluronate (Mw 310.sup.5 g/mol) dissolved in 20 mL of demineralized water. 40 mg of sodium hyaluronate derivative with covalently bound naproxen (17% naproxen) was added to this solution. Solution for the fiber sheath was made by mixing 1.59 g palmitoyl hyaluronan (Mw 2.4010.sup.5 g/mol, degree of substitution 55%) with 17 mL of demineralized water and 17 mL of propan-2-ol. 30 mg of octenidine dihydrochloride was added to this solution. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulation bath. Extrusion rate was 250 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 1.0 m.Math.min.sup.1 and was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol and acetone.

[0151] The core and the sheath were in volume ratio 1.2:1. The fiber fineness was 26 tex, strength 1.58 N and its breaking elongation 19.2%.

Example 11

[0152] Preparation of Core-Sheath Fibers from Sodium Hyaluronate and Palmitoyl Hyaluronan, Wherein Different Volume Ratio of Demineralized Water and Propan-2-Ol or Another Lower Alcohol is Used in Spinning Solution of Palmitoyl Hyaluronan

[0153] For the preparation of the fiber core, it was 0.45 g of sodium hyaluronate (Mw 6.8010.sup.5 g/mol) dissolved in 25 mL demineralized water. Solution for the fiber sheath was made by mixing [0154] a) 1.60 g of palmitoyl hyaluronan (Mw 2.1210.sup.5 g/mol, degree of substitution 58%) with 17 mL of demineralized water and 17 mL of propan-2-ol (1:1), [0155] b) 1.84 g of palmitoyl hyaluronan (Mw 2.1210.sup.5 g/mol, degree of substitution 58%) with 16 mL of demineralized water and 24 mL of propan-2-ol (4:6) [0156] c) 1.80 g of palmitoyl hyaluronan (Mw 2.1210.sup.5 g/mol, degree of substitution 58%) with 31.5 mL of demineralized water and 3.5 mL of propan-2-ol (9:1) [0157] d) 1.60 g of palmitoyl hyaluronan (Mw 2.1210.sup.5 g/mol, degree of substitution 58%) with 17 mL of demineralized water and 17 mL of ethanol (1:1)

[0158] Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.8 m.Math.min.sup.1 and was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol and acetone. [0159] a) The core and the sheath were in volume ratio 1:2.5. The fiber fineness was 17 tex, strength 1.99 N and its breaking elongation 18.2%. [0160] b) The core and the sheath were in volume ratio 1:2.5. The fiber fineness was 17 tex, strength 1.74 N and its breaking elongation 17.8%. [0161] c) The core and the sheath were in volume ratio 1:2.8. The fiber fineness was 17 tex. [0162] d) The core and the sheath were in volume ratio 1:2.6. The fiber fineness was 15 tex, strength 1.67 N and its breaking elongation 12.6%.

Example 12

[0163] Preparation of Core-Sheath Fibers from Sodium Hyaluronate and Palmitoyl Hyaluronan in Coagulation Baths with Different Ratios of Lactic Acid, Propan-2-Ol and Water

[0164] For the preparation of the fiber core, it was 0.36 g of sodium hyaluronate (Mw 1.6610.sup.6 g/mol) dissolved in 25 mL of demineralized water. Solution for the fiber sheath was made by mixing 1.60 g of palmitoyl hyaluronan (Mw 2.8010.sup.5 g/mol, degree of substitution 36%) with 17 mL of demineralized water and 17 ml of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components.

[0165] The coagulation bath was made by: [0166] a) The mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4 [0167] b) The mixture of 80% D,L-lactic acid and 100% propan-2-ol and demineralized water in volume ratio 2:7:1 [0168] c) The mixture of 80% D,L-lactic acid and 100% propan-2-ol and demineralized water in volume ratio 0.5:6:3.5

[0169] The resulting core-sheath fiber went through 0.4 m long bath with the rate 1 m.Math.min.sup.1 and was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol and acetone. [0170] a) The core and the sheath were in volume ratio 1:3. The fiber fineness was 16 tex, strength 2.13 N and its breaking elongation 12.8%. [0171] b) The core and the sheath were in volume ratio 1:3. The fiber fineness was 16 tex, strength 1.58 N and its breaking elongation 14.2%. [0172] c) The core and the sheath were in volume ratio 1:3. The fiber fineness was 16 tex.

Example 13

[0173] Preparation of Core-Sheath Fibers from Sodium Hyaluronate and Oleoyl Hyaluronan

[0174] For the preparation of the fiber core was 0.38 g of sodium hyaluronate (Mw 1.6610.sup.6 g/mol) dissolved in 25 mL of demineralized water. Solution for the sheath was made by mixing 1.43 g of oleoyl hyaluronan (Mw 2.810.sup.5 g/mol, degree of substitution 28%) with 17 mL of demineralized water and 17 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.9 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol.

[0175] The core and the sheath were in volume ratio 1:2.8. The fiber fineness was 13 tex, strength 1.35 N and its breaking elongation 11.2%.

Example 14

[0176] Preparation of Core-Sheath Fibers from Oleoyl Hyaluronan and Palmitoyl Hyaluronan

[0177] a) Degree of Substitution in the Core 28%, Degree of Substitution in the Sheath 36%

[0178] For the preparation of the fiber core, it was 0.77 g of oleoyl hyaluronan (Mw 2.810.sup.5 g/mol, degree of substitution 28%) dissolved in 14 mL of demineralized water. Solution for the sheath was made by mixing 1.77 g of palmitoyl hyaluronan (Mw 2.810.sup.5 g/mol, degree of substitution 36%) with 17 mL of demineralized water and 17 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.9 m.Math.min.sup.1 and was continually pulled out by the winding roller. The fiber was then scoured with 100% ethanol.

[0179] The core and the sheath were in volume ratio 1:2. The fiber fineness was 20 tex, strength 1.31 N and its breaking elongation 16.9%.

[0180] b) Degree of Substitution in the Core 24%, Degree of Substitution in the Sheath 50%

[0181] For the preparation of the fiber core, it was 0.77 g of oleoyl hyaluronan (Mw 2.1610.sup.5 g/mol, degree of substitution 24%) dissolved in 12 mL of demineralized water and 12 mL of propan-2-ol. Solution for the sheath was made by mixing 1.41 g of palmitoyl hyaluronan (Mw 2.0410.sup.5 g/mol, degree of substitution 50%) with 15 mL of demineralized water and 15 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of a mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.9 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% ethanol and additional 4 hours in acetone.

[0182] The core and the sheath were in volume ratio 1:1.5. The fiber fineness was 20 tex, strength 2.03 N and its breaking elongation 22.1%.

Example 15

[0183] Preparation of Core-Sheath Fibers from Palmitoyl Hyaluronan of Different Degree of Substitution in the Fiber Core and Sheath

[0184] a) Degree of Substitution in the Core 16%, Degree of Substitution in the Sheath 75%

[0185] For the preparation of the fiber core, it was 0.77 g of palmitoyl hyaluronan (Mw 2.1610.sup.5 g/mol, degree of substitution 16%) dissolved in 14 mL of demineralized water and 14 mL of propan-2-ol. Solution for the sheath was made by mixing 1.87 g of palmitoyl hyaluronan (Mw 2.810.sup.5 g/mol, degree of substitution 75%) with 17 mL of demineralized water and 17 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulation bath. Extrusion rate was 200 L.Math.min for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.9 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% ethanol.

[0186] The core and the sheath were in volume ratio 1:2. The fiber fineness was 20 tex, strength 1.11 N and its breaking elongation 9.5%.

[0187] b) Degree of Substitution in Core 12%, Degree of Substitution in Sheath 60%

[0188] For the preparation of the fiber core was 0.77 g of palmitoyl hyaluronan (Mw 3.210.sup.5 g/mol, degree of substitution 12%) dissolved in 12 mL of demineralized water and 12 mL of propan-2-ol. Solution for the sheath was made by mixing 1.41 g of palmitoyl hyaluronan (Mw 2.0310.sup.5 g/mol, degree of substitution 60%) with 15 mL of demineralized water and 15 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.9 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% ethanol and additional 4 hours in acetone.

[0189] The core and the sheath were in volume ratio 1:1.5. The fiber fineness was 20 tex, strength 1.96 N and its breaking elongation 23.0%.

[0190] c) Degree of Substitution in the Core 5%, Degree of Substitution in the Sheath 44%

[0191] For the preparation of the fiber core, it was 0.77 g of palmitoyl hyaluronan (Mw 3.210.sup.5 g/mol, degree of substitution 5%) dissolved in 12 mL of demineralized water and 12 mL of propan-2-ol. Solution for sheath was made by mixing 1.41 g of palmitoyl hyaluronan (Mw 2.0410.sup.5 g/mol, degree of substitution 44%) with 15 mL of demineralized water and 15 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. Coagulation bath was made of a mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.9 m.Math.min.sup.1 and it was continually pulled out by the winding roller. The fiber was then scoured with 100% ethanol and additional 4 hours in acetone.

[0192] The core and the sheath were in volume ratio 1:1.5. The fiber fineness was 24 tex, strength 2.45 N and its breaking elongation 24.3%.

Example 16

[0193] Preparation of Core-Sheath Fibers from Sodium Hyaluronate and Oleoyl Hyaluronan with Addition of Micelles Containing Fluorescent Agent into the Fiber Core

[0194] For the preparation of the fiber core was 0.38 g of sodium hyaluronate (Mw 1.6610.sup.6 g/mol) dissolved in 25 mL of demineralized water. 7.6 mg of aqueous solution of the nano-micellar composite on the basis of polysaccharide containing dye Nile red (solution concentration 2 wt %) was added to this solution. Solution for the sheath was made by mixing 1.43 g of oleoyl hyaluronan (Mw 2.810.sup.5 g/mol, degree of substitution 28%) with 17 mL of demineralized water and 17 mL of propan-2-ol. Resulting solutions were degassed and co-extruded using the pair of dosage systems through the two-way coaxial spinneret into the coagulation bath. Extrusion rate was 200 L.Math.min.sup.1 for both components. The coagulation bath was made of the mixture of 80% D,L-lactic acid and 100% propan-2-ol in volume ratio 1:4. The resulting core-sheath fiber went through 0.4 m long bath with the rate 0.9 m.Math.min.sup.1 and it continually pulled out by the winding roller. The fiber was then scoured with 100% propan-2-ol and acetone.

[0195] The core and the sheath were in volume ratio 1:2.8. The fiber fineness was 14 tex, strength 1.49 N and its breaking elongation 16.6%.

Example 17

[0196] Preparation of the Braided Textile from Core-Sheath Fibers Based on Hyaluronan

[0197] a) Preparation of the Braided Tube from Core-Sheath Fibers Based on Hyaluronan

[0198] Yarn made of the single core-sheath fiber (monofilament) from palmitoyl hyaluronan and sodium hyaluronate with content of magnetic nanoparticles prepared according to Example 6 was rewound to 16 bobbins using the winding machine and then processed using STEEGER horizontal braiding machine with the braid body set with 16 bobbins. The winding speed was 30 m/min, braiding head speed was 50 rpm. The resulting braided tube from 16 monofilament/yarns in twill showed braiding density 13 cm.sup.1, braiding angle 30.sup.0 and diameter 1.25 mm.

[0199] b) Preparation of the Braided Thread from Mixed Yarn

[0200] First was produced yarn from the bundle of two fibers (monofilaments): the core-sheath fiber from palmitoyl hyaluronan and sodium hyaluronate with content of magnetic nano-particles made according to Example 6 and polypropylene fiber of diameter 0.08 mm and fineness 5.2 tex by Wetelen. Yarn was made by grouping of these monofilaments during rewinding on a STEEGER winding machine. The winding speed was 27 m/min and tension 8 cN. 8 bobbins with upwound blended yarn was gradually prepared. The yarn fineness was 37 tex. Yarn was then processed using a STEEGER horizontal braiding machine with the braid body set with 8 bobbins. The braiding head speed was 30 rpm. The resulting braided thread made of 8 yarns showed braiding density 10 cm.sup.1, braiding angle 20 and diameter 0.9 mm.

Example 18

[0201] Preparation of the Braided Tube from Core-Sheath Fibers Based on Hyaluronan Containing Filling Fibers

[0202] a) Filling Fibers from PLLA of Diameter 0.076 mm

[0203] In manufacturing of the braided tube according to the method from Example 17a, the bundle of 30 filling fibers of polylactic acid (PLLA) of diameter 0.076 mm by Luxilon was inserted into the hollow. The resulting braided tube showed braiding density 13 cm.sup.1, braiding angle 30 and diameter 1.25 mm. The resulting tube was submerged in water, wherein the fibers swelled during several minutes, the sheath thereof started to rupture and after 10 minutes core with active agent release was apparent. After 4 hours was the core completely spilled out.

[0204] b) Filling Fibers from Polyester of Diameter 0.018 mm

[0205] In manufacturing of braided tube according to method from Example 17b, the multifilament made of 200 fibers of polyester of diameter 0.018 mm was inserted in the hollow. The resulting braided tube showed braiding density 10 cm.sup.1, braiding angle 28 and diameter 0.95 mm.

[0206] c) Filling Fibers from Polycaprolactone of Diameter 0.00054 mm (Nano-Fibers)

[0207] In manufacturing of braided tube according to method from Example 17b, the polyester multifilament with its surface covered with nano-fiber layer of polycaprolactone (Mw 8.010.sup.4 g/mol; nano-fiber layer was made using method of electrostatic spinning on apparatus 4SPIN) was inserted into the hollow. Nano-fiber diameter was 0.00054 mm. The resulting braided tube showed braiding density 10 cm.sup.1, braiding angle 310 and diameter 1.5 mm.

Example 19

Preparation of the Yarn of Core-Sheath Fibers Based on Hyaluronan

[0208] a) Simple Yarn of Fineness 60 Tex

[0209] 3 monofilaments of core-sheath fibers from sodium hyaluronate and palmitoyl hyaluronan (fibers made according to Example 1) were twisted on a ring-twisting machine at the feeding speed of 8 m/min and spindle rotation speed 1000 min.sup.1. The resulting yarn had fineness 60 tex and twist 125 m.sup.1.

[0210] b) Plied Yarn of Fineness 300 Tex

[0211] 3 monofilaments of core-sheath fibers from sodium hyaluronate and palmitoyl hyaluronan (fibers prepared according to Example 6) were twisted on the ring-twisting machine at the feeding speed 9 m/min and spindle rotation speed 1000 min.sup.1. This simple yarn had fineness 100 tex and left twist 110 m.sup.1. Then 3 such simple yarns were grouped and twisted on the ring-twisting machine at the feeding speed 12 m/min and spindle rotation speed 1000 min.sup.1. The resulting plied yarn had fineness 300 tex and right twist 85 m.sup.1.

Example 20

[0212] Preparation of the Blended Yarn from Core-Sheath Fibers Based on Hyaluronan and PLLA Fibers

[0213] 1 monofilament of the core-sheath fiber of native hyaluronan and palmitoyl hyaluronan (fibers were made according to Example 12b) and 2 monofilaments of polylactic acid (PLLA) of diameter 0.076 mm were twisted on the ring-twisting machine at the feeding speed 8 m/min and spindle rotation speed 1000 min.sup.1. The resulting yarn had fineness 30 tex and twist 125 m.sup.1.

Example 21

[0214] Preparation of the Braided Tube from Blended Yarn Containing Core-Sheath Fibers Based on Hyaluronan and PLLA Fiber
Yarn prepared according to Example 20 was rewound using the winding machine for 8 bobbins and then processed on STEEGER horizontal braiding machine with the braiding body set with 8 bobbins. The winding speed was 30 m/min, braiding body speed was 70 rpm. The resulting braided thread made of 8 yarns in twill showed braiding density of 15 cm.sup.1, braiding angle 30 and diameter 0.8 mm.

Example 22

Preparation of the Weft-Knitted Textile Containing Core-Sheath Fibers Based on Hyaluronan

[0215] Yarn manufactured according to Example 19 was further textile processed on the semi-production hand driven weft-knitting machine (in gauge of 10 needles/inchknitted with omitting every second needle) into double-faced knitted textile. The density of resulting knitted textile was 8 wales per centimeter and 4 courses per centimeter.

Example 23

Preparation of the Warp Knitted Textile Containing Core-Sheath Fibers Based on Hyaluronan

[0216] Yarn made according to Example 19 was further textile processed on the warp knitting machineraschel machine by COMEZ (in gauge 12 needles/inch) into the form of single-faced knitted textile in the tricot pattern. The density of resulting knitted textile was 4 wales per centimeter and 5 courses per centimeter.