Ion locking fixed cyclodextrin cross-linked polymer functionalized cellulose-based textile material and preparation method thereof

Abstract

The invention discloses an ion locking fixed cyclodextrin cross-linked polymer functionalized cellulose-based textile material and a preparation method thereof, and the method comprises the following steps: cross-linking hydroxypropyl-beta-cyclodextrin (HP-beta-CD) by using 1, 2, 3, 4-butanetetracarboxylic acid (BTCA) to prepare a cross-linked polymer containing carboxyl / carboxylate groups, and carrying out cross-linking on the cross-linked polymer containing carboxyl / carboxylate groups to prepare the ion locking fixed cyclodextrin cross-linked polymer functionalized cellulose-based textile material. Polyphenols active molecules (such as luteolin) are clathrated and / or loaded; depositing the cross-linked polymer loaded with the active molecules on the surface of a cellulose-based textile base material which is subjected to cationization modification and has quaternary ammonium salt cationic groups on the surface through electrostatic interaction; divalent metal ions (preferably Ca < 2 + >) are further introduced to coordinate with carboxyl / carboxylate groups in the cross-linked polymer to form physical cross-linking points, so that locking and fixation of a functional layer are realized, and the release behavior of active molecules is regulated and controlled. The material has the comprehensive performance of stable fixation, washability, durability, breathability, comfort and maintenance and controllable release mode, and can be applied to application scenes such as skin contact textiles and dressing materials.

Description

Technical Field

[0001] This invention relates to the field of functional textile materials technology, specifically to a surface functionalized finishing material for cellulose-based textile materials (such as cotton, linen, viscose, lyocell, modal and their blends) and its preparation method. The material can be used in hygiene and health textiles, skin contact textiles and dressing materials, and can achieve the loading of active molecules and the controlled release during use. Background Technology

[0002] Polyphenolic active molecules (such as curcumin, luteolin, and quercetin) possess antibacterial and reactive oxygen species (ROS) scavenging properties, making them promising candidates for use in functional sanitary textiles and medical dressings. However, polyphenolic molecules are generally hydrophobic, while cellulose-based fabrics are hydrophilic and lack specific binding sites, meaning that achieving efficient, stable loading and controlled release of polyphenols on fabric surfaces still requires improvement in some cases.

[0003] In existing technologies, the construction of polyphenol molecules on cellulose-based fabrics includes physical adsorption, film formation / resin finishing, and the introduction of host molecules (such as cyclodextrins and their derivatives) to achieve host-guest inclusion loading. Physical adsorption is simple, but active molecules are prone to migration or loss in environments such as washing, water immersion, or perspiration, resulting in insufficient functional durability. Film formation or resin finishing can improve adhesion to some extent, but when the coating amount or degree of cross-linking is high, it may clog fabric pores, reduce water vapor permeability, and affect hand feel and fit comfort, which is unfavorable for close-fitting wear or dressings requiring "lightweight and breathable" applications. Cyclodextrins and their derivatives have molecular inclusion properties and can be used for loading and regulating the release of active molecules. However, there is still room for improvement in existing technologies for constructing cyclodextrin-related functional layers with better durability on the surface of cellulose-based fabrics, while maintaining fabric breathability and comfort and achieving controllable and responsive regulation of release behavior.

[0004] Furthermore, from a usage perspective, different application scenarios have varying requirements for release behavior: in some cases, rapid release is needed to achieve initial quick effects, while in others, a more moderate and sustained release is required in specific environments (such as acidic microenvironments) to maintain a long-lasting effect. Existing technologies, in some cases, struggle to simultaneously achieve the combined performance of "stable adhesion, washability, durability, breathability, and comfort" with "adjustable or switchable release modes" within the same material system. Meanwhile, the ability of functional layers to undergo reversible structural changes under mild conditions and trigger accelerated release or structural relaxation would improve operability and adaptability during use, but related systems still require further improvement.

[0005] Therefore, it is necessary to provide a functional textile material that can form a stable and fixed drug-loaded controlled-release structural layer on the surface of cellulose-based fabrics and has a relatively simple process, so as to achieve effective loading of polyphenolic active molecules, washability and durability, and controllable release and response regulation while maintaining the breathability and comfort of the fabric, thereby meeting the application needs of medical dressings and functional sanitary textiles. Summary of the Invention

[0006] This invention aims to address the following problems that existing drug-loaded textile materials may encounter in practical use: insufficient fixation of active molecules on the surface of cellulose-based fabrics, limited wash resistance, and difficulty in achieving effective loading and controlled release while maintaining fabric breathability and comfort; furthermore, the release behavior is not easily controlled under different usage requirements (e.g., the need for rapid onset of action or more sustained release). Therefore, this invention provides an ion-locked, cyclodextrin crosslinked polymer-functionalized cellulose-based textile material, aiming to achieve stable fixation, controllable release, and response regulation during use.

[0007] To achieve the above objectives, the present invention adopts the following technical solution.

[0008] A cellulose-based textile material functionalized with an ion-locked and immobilized cyclodextrin crosslinked polymer includes a cellulose-based textile substrate and a drug-controlled release structural layer immobilized on the surface of the cellulose-based textile substrate. The cellulose-based textile substrate is cation-modified to have quaternary ammonium salt cationic groups on its surface. The drug-controlled release structural layer comprises a hydroxypropyl-β-cyclodextrin (HP-β-CD) crosslinked polymer formed by crosslinking 1,2,3,4-butanetetracarboxylic acid (BTCA), and polyphenolic active molecules encapsulated and loaded by the cyclodextrin polymer. The drug-controlled release structural layer is immobilized on the surface of the cellulose-based textile substrate through a dual mechanism of electrostatic adsorption and coordination crosslinking initiated by divalent metal ions.

[0009] Preferably, the cellulose-based textile substrate is selected from cotton, linen, viscose, lyocell, modal fabrics, and their blends; the cationization modification uses 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC) as the modifier, and the nitrogen content of the modified cellulose-based textile substrate is 0.1–1.0 wt%; the polyphenolic active molecule is selected from one or more of curcumin, luteolin, or quercetin; the divalent metal ion is Ca. 2+ .

[0010] As a preferred embodiment of the present invention, the Ca is provided 2+ The calcium salts are selected from calcium chloride and / or calcium acetate, and the surface loading of polyphenolic active molecules on the material is 0.05–1.0 mg / cm². 2 .

[0011] This invention also provides a method for preparing ion-locked cyclodextrin crosslinked polymer-functionalized cellulose-based textile materials, the method comprising the following steps:

[0012] Step 1. Synthesis and loading of cyclodextrin polymer: HP-β-CD crosslinked polymer was prepared by esterification and crosslinking of hydroxypropyl-β-cyclodextrin with 1,2,3,4-butanetetracarboxylic acid in an aqueous phase; polyphenolic active molecules were introduced to be included and / or loaded onto the HP-β-CD crosslinked polymer to obtain a dispersion;

[0013] Step 2. Substrate modification: Quaternization modification of cellulose-based textile substrate to make its surface positively charged;

[0014] Step 3. Electrostatic assembly: The modified substrate from step 2 is immersed in the dispersion from step 1, and the cyclodextrin polymer is deposited on the surface of the cellulose-based textile substrate by electrostatic adsorption.

[0015] Step 4. In-situ locking: The substrate treated in step 3 is brought into contact with an aqueous solution containing divalent metal ions to initiate a coordination crosslinking reaction. After cleaning and drying, the product is obtained.

[0016] As a preferred embodiment of the present invention, the HP-β-CD crosslinked polymer prepared in step 1 has a weight-average molecular weight Mw of 8000–20000 Da, and is a crosslinked polymer containing carboxyl / carboxylate groups.

[0017] As a preferred embodiment of the present invention, step 1 is specifically as follows: 10.0 g of hydroxypropyl-β-cyclodextrin and 8.0 g of 1,2,3,4-butanetetracarboxylic acid are dissolved in 30 mL of deionized water, and 0.5 g of sodium hypophosphite is added as a catalyst. The reaction is carried out at 120 °C for 1 h using a vacuum distillation apparatus. After the reaction is completed, deionized water is added to dissolve the viscous product, followed by the addition of acetone to precipitate the product. The precipitate is collected by centrifugation, and after redissolving the precipitate, it is placed in a dialysis bag for dialyzing. Then, the product is freeze-dried to obtain the target polymer HCP.

[0018] As a preferred embodiment of the present invention, the polyphenolic active molecules in step 1 are selected from one or more of curcumin, luteolin, or quercetin; the prepared HCP and polyphenolic active molecules are weighed, and the HCP is dissolved in water at 45°C to obtain an aqueous solution; the polyphenolic active molecules are dissolved in ethanol to prepare an alcoholic solution; the alcoholic solution is slowly added to the aqueous solution under stirring, controlling the volume ratio of the aqueous solution to the alcoholic solution to be 2:1, and stirring is continued for 30 min; the reaction is carried out under constant temperature and shaking at 45°C and 150 rpm for 12 h in the dark; after the reaction is completed, the ethanol is removed by rotary evaporation under reduced pressure at 45°C to obtain an aqueous concentrate; the concentrate is dialyzed in a dialysis bag, and the solution in the bag is pre-frozen at -40°C for 6 h and then freeze-dried under vacuum to obtain a pale yellow powder product.

[0019] As a preferred embodiment of the present invention, step 2 is specifically as follows: immerse the cellulose-based textile substrate in an aqueous solution containing 30 g / L 3-chloro-2-hydroxypropyltrimethylammonium chloride and 15 g / L NaOH, stack it at room temperature for 18 h, wash it with water until neutral, and then dry it.

[0020] As a preferred embodiment of the present invention, the concentration of the dispersion is 30 mg / mL during electrostatic assembly in step 3, and the modified cellulose-based textile substrate is immersed in the dispersion and adsorbed by shaking at room temperature for 30 min.

[0021] As a preferred embodiment of the present invention, the divalent metal ion in step 4 is Ca. 2+ Contains Ca 2+ The concentration of the aqueous solution was 20–150 mM, and the treatment time was 5–60 min. When the solution contained Ca... 2+ When the aqueous solution concentration is 20–50 mM, the material exhibits rapid release characteristics; when it contains Ca... 2+ When the aqueous solution concentration is 80–150 mM, the material exhibits pH-responsive sustained-release characteristics.

[0022] The construction mechanism of this invention can be summarized as a dual fixation of "electrostatic assembly - ion / coordination locking": electrostatic assembly (first fixation): utilizing the electrostatic interaction between the quaternary ammonium salt cationic groups and the ionizable groups (e.g., carboxyl groups / carboxylates) in the cyclodextrin polymer, the cyclodextrin polymer is deposited on the fiber surface and forms a structural layer; in-situ locking (second fixation): introducing divalent metal ions (preferably Ca2+). 2+ It interacts with coordinable groups in the structural layer through coordination / ion bridging, improving the stability and durability of the structural layer. Furthermore, the coordination crosslinking strength initiated by divalent metal ions is tunable, enabling the regulation of drug release behavior: by adjusting the Ca content... 2+ By adjusting the concentration of the aqueous solution after treatment, rapid-release or pH-responsive slow-release materials can be obtained; when the material comes into contact with an aqueous medium containing trisodium citrate, trisodium citrate can complex the Ca in the structural layer. 2+ This causes dissociation or a reduction in the degree of crosslinking of coordination crosslinks, thereby triggering a structural response, which includes enhanced swelling and / or accelerated drug release.

[0023] Advantages and beneficial effects of the present invention:

[0024] (1) Good washability and adhesion: through "electrostatic adsorption + Ca 2+ The structure layer exhibits good stability under washing conditions due to the "coordination crosslinking" dual fixation mechanism; when the material is used as a washable textile, the retention rate of polyphenolic active molecules can reach ≥80% after 5 washing cycles.

[0025] (2) Release behavior is adjustable and switchable: only by adjusting Ca 2+Post-treatment concentrations can achieve different release characteristics in the same system: at lower Ca... 2+ At concentrations (e.g., 20–50 mM), rapid release characteristics are obtained (24-hour cumulative release rate >70%, and the difference between pH 5.5 and pH 7.4 is <15%); at higher Ca... 2+ At concentrations (e.g., 80–150 mM), pH-responsive sustained-release characteristics can be obtained (the cumulative release over 24 hours at pH 5.5 is at least twice that at pH 7.4).

[0026] (3) It has the ability to moderately trigger response modulation: In a medium containing trisodium citrate, the material structure layer may dissociate or the degree of cross-linking may be reduced, thereby resulting in enhanced swelling and / or accelerated release; this response modulation helps to reduce interfacial adhesion and improve the ease of removal in dressing applications.

[0027] (4) Balancing bioactivity and wearing comfort: The material can simultaneously exhibit antibacterial and antioxidant capabilities (e.g., antibacterial rate against Staphylococcus aureus ≥85%, antibacterial rate against Escherichia coli ≥70%, DPPH free radical scavenging rate ≥80%), and the water vapor permeability of the treated material is not less than 85% of that of the untreated control sample of the same substrate, which is beneficial to maintaining the breathability and comfort of the fabric. Attached Figure Description

[0028] Figure 1 The HP-β-CD and cyclodextrin polymer in Example 1 of this invention 13 C spectrum;

[0029] Figure 2 The solubility curves of HP-β-CD and cyclodextrin polymer in Example 3 of this invention are shown.

[0030] Figure 3 The figures are the cumulative release curves of Examples 4 and 5 of the present invention; wherein, (a) is the cumulative release curve of Example 4 in PBS buffer at pH 7.4 and pH 5.5; and (b) is the cumulative release curve of Example 5 in PBS buffer at pH 7.4 and pH 5.5. Detailed Implementation

[0031] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0032] Example 1: Synthesis of BTCA crosslinked hydroxypropyl-β-cyclodextrin polymer (HCP)

[0033] 10.0 g of HP-β-CD (hydroxypropyl-β-cyclodextrin) and 8.0 g of BTCA (1,2,3,4-butanetetracarboxylic acid) were dissolved in 30 mL of deionized water. 0.5 g of sodium hypophosphite (SHP) was added as a catalyst, and the reaction was carried out at 120 °C for 1 h using a vacuum distillation apparatus (-0.09 MPa). After the reaction was complete, a small amount of deionized water was added to dissolve the viscous product, followed by the addition of excess acetone to precipitate the product. The precipitate was collected by centrifugation, reconstituted, and placed in a dialysis bag (3500 Da MWCO). Dialysis with pure water at room temperature for 3 days was performed to remove small molecules. The final product was freeze-dried to obtain the target polymer HCP (a cross-linked polymer containing carboxyl / carboxylate groups).

[0034] Results: The weight-average molecular weight (Mw) was determined to be 12000 (PDI = 1.85) using GPC (0.1 NaNO3, pullulan). Furthermore, 13C-NMR (with attached...) Figure 1 Ester bond carbonyl (–COO–) and residual carboxyl (–COOH) signals appeared in the carbonyl region of 170–180 ppm, and BTCA skeleton carbon signals appeared in the region of 30–45 ppm, indicating that BTCA undergoes esterification crosslinking with HP-β-CD and retains some carboxyl sites.

[0035] Example 2: Preparation of polymer functional powder loaded with luteolin

[0036] Weigh the HCP and luteolin (a polyphenolic active molecule) prepared in Example 1, with a mass ratio of m(HCP):m(luteolin) = 8:1. Dissolve HCP in water at 45°C to obtain an aqueous solution; dissolve luteolin in ethanol to prepare an alcoholic solution. Slowly add the alcoholic solution to the aqueous solution while stirring, controlling the volume ratio of the aqueous solution to the alcoholic solution to be 2:1 (V / L). 水 :V 乙醇 =2:1), continue stirring for 30 min. React at a constant temperature and vibration of 45℃ and 150 rpm for 12 h in the dark. After the reaction is complete, remove ethanol by rotary evaporation under reduced pressure at 45℃ to obtain a concentrated aqueous phase. Place the concentrated solution in a dialysis bag (3500 Da MWCO) and dialyze against pure water at room temperature for 12 h (changing the external dialysis medium 3 times). Pre-freeze the solution in the bag at -40℃ for 6 h and then freeze-dry under vacuum to obtain a pale yellow powder product.

[0037] Inclusion rate determination: A certain amount of product powder was dispersed in ethanol, the inclusion structure was destroyed by ultrasonication and the drug was extracted, the supernatant was collected by centrifugation, and the absorbance was measured at 353 nm. The inclusion rate was calculated to be 84.36% according to the standard curve.

[0038] Example 3: Phase solubility experiment (evaluation of solubilization effect)

[0039] To verify the solubilizing effect of cyclodextrin polymers on poorly soluble drugs, a phase solubility experiment was conducted: a series of concentrations of HP-β-CD monomer solutions and HCP polymer solutions were prepared, where the polymer concentration was expressed as the effective cyclodextrin unit concentration ([CDunit]). Excess luteolin solid was added to each solution, and the solutions were placed in a constant-temperature shaker at 37°C and shaken in the dark for 48 hours to reach equilibrium. The supernatant was filtered through a 0.45 μm microporous membrane, and its absorbance at 353 nm was measured.

[0040] Results: See attached. Figure 2 As shown, the solubility of luteolin and the carrier concentration exhibit an approximately linear relationship within the investigated range. Based on the effective cyclodextrin unit concentration [CD unit], the slope of the solubility-concentration curve for the HCP system is higher than that for the HP-β-CD system, indicating that HCP has a superior solubilizing effect under the experimental conditions.

[0041] Example 4: Fast-release drug-loaded cellulose-based textile material (Ca 2+ (Post-treatment concentration: 30 mM)

[0042] Step 1. Substrate Modification: Pure cotton fabric was immersed in an aqueous solution containing 30 g / L CHPTAC (3-chloro-2-hydroxypropyltrimethylammonium chloride) and 15 g / L NaOH, and the mixture was piled up at room temperature for 18 hours. The fabric was then washed with water until neutral and dried. After modification, the cotton fabric surface was positively charged, and the nitrogen content was 0.45%.

[0043] Step 2. Electrostatic Assembly: Weigh the loaded powder obtained in Example 2 and disperse it in deionized water to prepare a dispersion with a concentration of 30 mg / mL. Immerse the modified cotton cloth in the dispersion (liquor ratio 1:10) and shake at room temperature for 30 min for adsorption.

[0044] Step 3. Low calcium locking: Take out the adsorbed fabric and immerse it directly in a 30mM CaCl2 aqueous solution for 15 minutes without drying.

[0045] Step 4. Post-treatment: Remove the fabric, wash it twice with deionized water, and dry it at 60℃.

[0046] Example 5: pH-responsive sustained-release drug-loaded cellulose-based textile material (Ca 2+ (Post-treatment concentration: 100 mM)

[0047] Step 1. The substrate modification steps are the same as in Example 4;

[0048] Step 2. The electrostatic assembly process is the same as in Example 4;

[0049] Step 3. High calcium locking: Take out the adsorbed fabric and immerse it directly in a 100mM CaCl2 aqueous solution for 15 minutes without drying.

[0050] Step 4. The post-processing steps are the same as in Example 4.

[0051] Example 6: Simulation of Structural Reconfigurability and Painless Removal

[0052] The sample prepared in Example 5 was used to verify the structural reversibility by performing the following operations:

[0053] (1) Simulated dressing change (decrosslinking): The sample was immersed in 50mM trisodium citrate solution for 5min (simulating clinical application of dissociation agent). Significant swelling of the polymer gel layer on the fabric surface was observed. The Ca content on the surface was reduced from 1.25% to below 0.1% by EDS test, indicating that the crosslinking network was dissociated.

[0054] (2) Structural reconstruction (re-crosslinking): After washing the citrate-treated sample, it was immersed again in 100 mM CaCl2 solution for 15 min. The test showed that its drug release behavior and wash resistance were restored to the same level as in Example 5.

[0055] Results: The material was confirmed to have ion-responsive structural switching properties, supporting potential applications of "painless removal".

[0056] Comparative Example 1: No calcium ion locking (verification of wash resistance mechanism)

[0057] The preparation process is the same as in Example 4, except that in step 3, the adsorbed fabric is not treated with CaCl2, but is directly washed and dried.

[0058] Comparative Example 2: No cationization modification (verification of loading mechanism)

[0059] Using unmodified raw cotton fabric, the remaining steps are the same as in Example 5 (treated with 100mM CaCl2).

[0060] This embodiment tests the fabric materials prepared in Examples 4 and 5, Comparative Example 1, and Comparative Example 2 to verify the performance of each fabric material. The tests include wash resistance, antibacterial properties, antioxidant properties, in vitro drug release, water vapor permeability, and cytotoxicity. The specific details are as follows:

[0061] (1) Washability test:

[0062] The evaluation was conducted using a laboratory-simulated mild washing procedure: functional fabrics were cut into 5cm × 5cm pieces and immersed in an aqueous solution containing 0.1% (w / v) neutral soap flakes (liquor ratio 1:50), and washed with agitation at 30℃ and 60 rpm for 15 min. After removal, the samples were rinsed twice with deionized water and air-dried at room temperature, completing one washing cycle. Samples before and after washing were subjected to ultrasonic extraction with ethanol, and the drug loading was determined by ultraviolet spectrophotometry (353 nm). The drug retention rate after 5 cycles was calculated (R = C5 / C0 × 100%; where C5 represents the drug loading after 5 cycles, and C0 represents the drug loading before any cycles).

[0063] (2) Antibacterial performance test:

[0064] The test was conducted according to the shaking method in GB / T 20944.3-2008, using Staphylococcus aureus and Escherichia coli as experimental strains. The sample from Example 4 was cut into 2cm × 2cm pieces and placed in 50mL of bacterial suspension (1×10⁻⁶). 5 The sample was incubated in a buffer solution containing CFU / mL at 37°C and 150 rpm for 24 hours with shaking. The colony count was determined by agar plate counting, and the inhibition rate was calculated as (Y = (AB) / A × 100%, where A and B are the colony counts of the control and test samples, respectively).

[0065] (3) Antioxidant performance test:

[0066] The DPPH free radical scavenging method was used for testing. The sample from Example 4 was cut into 1cm × 1cm pieces and immersed in 5mL of 0.1mM DPPH ethanol solution, reacting at room temperature in the dark for 30min. The absorbance of the supernatant was measured at 517nm. Using the DPPH stock solution as a control, the scavenging rate was calculated (I = (Acontrol – Asample) / Acontrol × 100%; where Acontrol represents the absorbance of the control group and Asample represents the absorbance of the sample).

[0067] (4) In vitro drug release

[0068] Functional fabrics were cut into 1cm × 1cm pieces and placed in 100mL of PBS buffer at pH 7.4 (simulating a physiological environment) and pH 5.5 (simulating an acidic infection environment), respectively, and shaken in a constant temperature shaker at 37℃ and 100rpm. Samples were taken at predetermined time points (0–24h), and an equal volume of fresh medium was added. Drug concentration was determined by ultraviolet spectrophotometry (353nm), and cumulative release curves were plotted.

[0069] (5) Water vapor transmission rate (WVT) test

[0070] The determination was performed according to GB / T 12704.2-2009 (evaporation method). The functional fabric was placed over the mouth of a moisture permeability cup filled with distilled water and then placed in a fabric moisture permeability meter at 37℃ and 40% RH. The weight loss due to water evaporation within 12 hours was measured, and the 24-hour water vapor transmission rate (WVT=△m / (S×t)×24; where △m represents the mass change of the sample during the test time, S represents the effective test area of ​​the sample, and t represents the actual test duration) was calculated.

[0071] (6) Cytotoxicity

[0072] The test was conducted according to ISO 10993-5 using the CCK-8 method. An extract was prepared from the sample in complete culture medium (extraction ratio 3 cm⁻¹). 2 / mL, 37℃, 24h). After co-culturing the extract with mouse fibroblasts (L929) for 24h, CCK-8 reagent was added and incubated for 2h. The absorbance at 450nm was measured and the cell viability was calculated.

[0073] In this embodiment, the performance test results of each fabric material are shown in Table 1, and the drug release behavior is as follows: Figure 3 As shown in Table 2.

[0074] Table 1. Physicochemical properties data of each embodiment and comparative example.

[0075]

[0076]

[0077] As shown in Table 1, Examples 4 and 5 (after Ca) 2+ The drug retention rate of the modified material exceeded 80% after 5 washes, demonstrating good adhesion and wash resistance, significantly superior to Comparative Example 1. This proves that the "ion-locking" strategy can effectively solve the problem of functional molecule loss during textile washing, which is crucial for reusable functional clothing and medical textiles. The low loading of Comparative Example 2 confirms that the cationic sites on the substrate surface are key to achieving active polymer deposition. The modified material of this invention maintains excellent antibacterial rate (>88%) and biosafety (cell viability ≥95%) while retaining a water vapor transmission rate (WVT) of 2200 g / m². 2 • More than 24 hours. This indicates that the introduction of the functional layer did not significantly affect the breathability and comfort of the substrate, making it not only suitable for medical dressings, but also for close-fitting clothing, hygiene products, and other fields where breathability is highly required. It has excellent overall performance and a wide range of applications.

[0078] Table 2. Differences in drug release behavior (cumulative release rate over 24 hours)

[0079]

[0080] Depend on Figure 3 As shown in Table 2, in this embodiment, divalent metal ions (Ca) are introduced. 2+ The physical crosslinking points are formed by coordination with the carboxyl / carboxylate groups in the crosslinked polymer. This not only enables the functional layer to be locked and fixed, but also allows for the acquisition of functional textile materials with different release rates or pH response release characteristics by adjusting the concentration of divalent metal ions and / or treatment conditions, making the materials suitable for different application scenarios.

[0081] In summary, the material provided in this embodiment combines the comprehensive performance of "stable adhesion, washability and durability, breathability and comfort" with "adjustable or switchable release mode"; and the functional layer can undergo reversible structural changes under mild conditions, which helps to reduce interface adhesion and improve removal operability in dressing applications, meeting the application needs of medical dressings and functional sanitary textiles.

[0082] The above description is a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An ion-locked, cyclodextrin crosslinked polymer-functionalized cellulose-based textile material, comprising a cellulose-based textile substrate and a drug-controlled release structure layer fixed to the surface of the cellulose-based textile substrate; characterized in that, The cellulose-based textile substrate is cationized to have quaternary ammonium salt cationic groups on its surface; the drug-controlled release structural layer comprises a hydroxypropyl-β-cyclodextrin crosslinked polymer formed by crosslinking 1,2,3,4-butanetetracarboxylic acid, and polyphenolic active molecules encapsulated and / or loaded by the cyclodextrin polymer; the drug-controlled release structural layer is fixed to the surface of the cellulose-based textile substrate through a dual mechanism of electrostatic adsorption and coordination crosslinking initiated by divalent metal ions.

2. The ion-locked, cyclodextrin crosslinked polymer-functionalized cellulose-based textile material according to claim 1, characterized in that, The cellulose-based textile substrate is selected from cotton, linen, viscose, lyocell, modal fabrics, and their blends; the cationization modification uses 3-chloro-2-hydroxypropyltrimethylammonium chloride as a modifier, and the nitrogen content of the modified cellulose-based textile substrate is 0.1–1.0 wt%; the polyphenolic active molecules are selected from one or more of curcumin, luteolin, or quercetin; the divalent metal ion is Ca. 2+ .

3. The ion-locked, cyclodextrin crosslinked polymer functionalized cellulose-based textile material according to claim 2, characterized in that, Provide Ca 2+ The calcium salts are selected from calcium chloride and / or calcium acetate, and the surface loading of polyphenolic active molecules on the material is 0.05–1.0 mg / cm². 2 .

4. A method for preparing an ion-locked, cyclodextrin crosslinked polymer-functionalized cellulose-based textile material, characterized in that, The method includes the following steps: Step 1. Synthesis and loading of cyclodextrin polymer: HP-β-CD crosslinked polymer was prepared by esterification and crosslinking of hydroxypropyl-β-cyclodextrin with 1,2,3,4-butanetetracarboxylic acid in an aqueous phase; polyphenolic active molecules were introduced to be included and / or loaded onto the HP-β-CD crosslinked polymer to obtain a dispersion; Step 2. Substrate modification: Quaternization modification of cellulose-based textile substrate to make its surface positively charged; Step 3. Electrostatic assembly: The modified substrate from step 2 is immersed in the dispersion from step 1, and the cyclodextrin polymer is deposited on the surface of the cellulose-based textile substrate by electrostatic adsorption. Step 4. In-situ locking: The substrate treated in step 3 is brought into contact with an aqueous solution containing divalent metal ions to initiate a coordination crosslinking reaction. After cleaning and drying, the product is obtained.

5. The method for preparing an ion-locked, cyclodextrin crosslinked polymer-functionalized cellulose-based textile material according to claim 4, characterized in that, The HP-β-CD crosslinked polymer prepared in step 1 has a weight-average molecular weight (Mw) of 8000–20000 Da, and it is a crosslinked polymer containing carboxyl / carboxylate groups.

6. The method for preparing an ion-locked, cyclodextrin crosslinked polymer-functionalized cellulose-based textile material according to claim 5, characterized in that, The specific steps of step 1 are as follows: 10.0 g of hydroxypropyl-β-cyclodextrin and 8.0 g of 1,2,3,4-butanetetracarboxylic acid are dissolved in 30 mL of deionized water, and 0.5 g of sodium hypophosphite is added as a catalyst. The reaction is carried out at 120 °C for 1 h using a vacuum distillation apparatus. After the reaction is completed, deionized water is added to dissolve the viscous product, followed by the addition of acetone to precipitate the product. The precipitate is collected by centrifugation, and after redissolving the precipitate, it is placed in a dialysis bag for dialyzing. Then, the product is freeze-dried to obtain the target polymer HCP.

7. The method for preparing an ion-locked, cyclodextrin crosslinked polymer-functionalized cellulose-based textile material according to claim 6, characterized in that, The polyphenolic active molecules mentioned in step 1 are selected from one or more of curcumin, luteolin, or quercetin; weigh the prepared HCP and polyphenolic active molecules, dissolve the HCP in water at 45℃ to obtain an aqueous solution; dissolve the polyphenolic active molecules in ethanol to prepare an alcoholic solution; slowly add the alcoholic solution to the aqueous solution while stirring, controlling the volume ratio of the aqueous solution to the alcoholic solution to be 2:1, and continue stirring for 30 min; react at a constant temperature of 45℃ and 150 rpm for 12 h in the dark; after the reaction is completed, remove the ethanol by rotary evaporation under reduced pressure at 45℃ to obtain an aqueous concentrate; place the concentrate in a dialysis bag for dialyzing, and freeze-dry the solution in the bag under vacuum after pre-freezing at -40℃ for 6 h to obtain a pale yellow powder product.

8. The method for preparing an ion-locked, cyclodextrin crosslinked polymer-functionalized cellulose-based textile material according to claim 7, characterized in that, The specific steps of step 2 are as follows: Immerse the cellulose-based textile substrate in an aqueous solution containing 30 g / L 3-chloro-2-hydroxypropyltrimethylammonium chloride and 15 g / L NaOH, stack it at room temperature for 18 hours, wash it with water until it is neutral and then dry it.

9. The method for preparing an ion-locked, cyclodextrin crosslinked polymer-functionalized cellulose-based textile material according to claim 8, characterized in that, In step 3, the concentration of the dispersion was 30 mg / mL during electrostatic assembly. The modified cellulose-based textile substrate was immersed in the dispersion and adsorbed by shaking at room temperature for 30 min.

10. The method for preparing an ion-locked, cyclodextrin crosslinked polymer functionalized cellulose-based textile material according to claim 9, characterized in that, In step 4, the divalent metal ion is Ca. 2+ Contains Ca 2+ The concentration of the aqueous solution was 20–150 mM, and the treatment time was 5–60 min. When the solution contained Ca... 2+ When the aqueous solution concentration is 20–50 mM, the material exhibits rapid release characteristics; when it contains Ca... 2+ When the aqueous solution concentration is 80–150 mM, the material exhibits pH-responsive sustained-release characteristics.

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