CN119386255B

CN119386255B - Antibacterial cellulose hydrogel dressing and preparation method thereof

Info

Publication number: CN119386255B
Application number: CN202411542465.XA
Authority: CN
Inventors: 曾位位; 甘大莉
Original assignee: Second People's Hospital Of Longgang District Shenzhen City
Current assignee: Second People's Hospital Of Longgang District Shenzhen City
Priority date: 2024-10-31
Filing date: 2024-10-31
Publication date: 2025-06-27
Anticipated expiration: 2044-10-31
Also published as: CN119386255A

Abstract

The present invention belongs to the field of medical supplies, and specifically discloses an antibacterial cellulose hydrogel dressing and a preparation method thereof. The raw materials of the antibacterial cellulose hydrogel dressing include carboxymethyl cellulose and amino hyperbranched polysiloxane-modified porous silicon loaded with carboxyl-containing antibiotics. The present invention utilizes amino hyperbranched polysiloxane-modified porous silicon as an antibiotic carrier applied to CMC hydrogel dressing, greatly improving the drug loading and mechanical strength of the cellulose-based hydrogel dressing, and the prepared hydrogel dressing has good biocompatibility and long-lasting antibacterial effect.

Description

Antibacterial cellulose hydrogel dressing and preparation method thereof

Technical Field

The invention belongs to the field of medical supplies, and particularly relates to an antibacterial cellulose hydrogel dressing and a preparation method thereof.

Background

Cellulose is taken as a raw material of natural hydrogel, belongs to the most abundant renewable resources in nature, has the characteristics of biodegradability, regeneration, recovery and the like, and can meet the environment-friendly requirement of society. Compared with other hydrogel dressings, the cellulose-based hydrogel dressing has proper porosity and good cell compatibility, can provide the required wettability for the surface of a wound, and can also perform gas exchange and exudate absorption. Carboxymethyl cellulose (CMC) is formed by introducing pendant carboxymethyl (-CH ₂ COOH) groups by chemical reaction on the basis of cellulose. CMC has better water solubility due to this structural change. The CMC hydrogel can be conveniently trimmed into any shape, is easy to fully contact with a wound part, and is convenient to wrap and fill the wound, thereby improving the self-healing effect. In addition, CMC molecular structure contains a large amount of carboxyl groups, which can combine with hemoglobin iron ions in blood to activate coagulation factors to promote coagulation, promote the adhesion of platelets in blood and enhance the hemostatic effect.

However, the single carboxymethyl cellulose itself generally has no antibacterial activity to prevent wound infection, so that nano metal ions with antibacterial activity, such as silver ions, copper ions and the like, may be added to impart antibacterial property in general, the added nano antibacterial metal ions have the characteristics of strong antibacterial spectrum, strong antibacterial property and the like, but are easily accumulated in human bodies to cause harm, and the high concentration of metal ions may have toxic effects on surrounding healthy tissues to adversely affect wound healing and tissue repair. In addition, some individuals may be sensitive to metal ions, resulting in allergic reactions or skin irritation. On the other hand, poor interface action of metal ions with CMC dressing can lead to serious decrease of mechanical strength of cellulose dressing. The addition of antibiotics in cellulose hydrogel dressing can give antibacterial property to the dressing, but the cellulose dressing has the defects of low drug loading rate and high drug release speed due to the weak binding capacity of cellulose and micromolecular antibiotic drugs.

Disclosure of Invention

The invention aims to solve the defects of the prior art, and based on the defects, the first aspect of the invention provides an antibacterial cellulose hydrogel dressing, which comprises carboxymethyl cellulose and modified porous silicon loaded with antibiotics, wherein the modified porous silicon is amino hyperbranched polysiloxane modified porous silicon, and the antibiotics contain carboxyl.

According to the invention, the amino hyperbranched polysiloxane is modified to coat the surface of the porous silicon, so that the agglomeration of the porous silicon in a cellulose matrix is effectively reduced, a large number of amino groups are formed on the surface of the carrier, on one hand, hydrogen bonding effect (carboxyl oxygen atoms in carboxyl groups have partial negative charges, and hydrogen atoms in amino groups have partial positive charges) can be generated with antibiotics in CMC-based hydrogel dressing, so that the effect of continuous slow release of antibiotics is realized, the technical problem that conventional cellulose dressing medicines are released too fast is solved, the medicine changing times of wounds are reduced, and the granulation tissues are protected from further infection is solved. In addition, the main components of the porous silicon in the invention are Si and O, and the main components of the hyperbranched polysiloxane are Si, O and C, and the two components have good biocompatibility and no toxicity to cells.

Wherein the mass ratio of the carboxymethyl cellulose to the modified porous silicon loaded with the antibiotics is 100 (5-30). The antibiotic can be clindamycin hydrochloride, ciprofloxacin hydrochloride, etc.

The second aspect of the invention provides a preparation method of the antibacterial cellulose hydrogel dressing, which comprises the following steps of uniformly mixing modified porous silicon loaded with antibiotics with carboxymethyl cellulose hydrogel to obtain the antibacterial cellulose hydrogel dressing, wherein the modified porous silicon is amino hyperbranched polysiloxane modified porous silicon, and the antibiotics contain carboxyl. The above-described antimicrobial cellulose hydrogel dressing may also be subsequently poured into a PTFE mold and dried at 50 ℃ for 12 hours.

The preparation process of the carboxymethyl cellulose hydrogel comprises the following steps of uniformly mixing citric acid, glycerol and carboxymethyl cellulose in water to obtain the carboxymethyl cellulose hydrogel. The added citric acid can be used as a cross-linking agent to cross-link CMC, so that the mechanical strength of the cellulose dressing is improved, and the added glycerol can be used for making the cellulose dressing softer, and meanwhile, the added glycerol also helps to keep moisture so as to help wound recovery. The preparation process comprises the steps of dissolving citric acid and glycerol in water, adding CMC, and stirring uniformly to obtain the carboxymethyl cellulose hydrogel, wherein the mass ratio of the citric acid to the glycerol to the CMC is 0.5g to 1g.

The preparation process of the modified porous silicon loaded with the antibiotics comprises the following steps of dispersing the modified porous silicon into an antibiotic solution, immersing the antibiotic solution into pores of the modified porous silicon, separating the modified porous silicon loaded with the antibiotics through centrifugal precipitation, and drying.

The preparation process of the modified porous silicon (namely the amino hyperbranched polysiloxane modified porous silicon) comprises the following steps of mixing porous silicon and amino hyperbranched polysiloxane in an alcohol/water system (alcohol can be one of methanol, ethanol and isopropanol; the volume ratio of the alcohol to the water can be 90mL:10 mL), condensing and refluxing at 60-95 ℃ for 4 hours, and obtaining the modified porous silicon after the reaction is finished. After the reaction is finished, the unreacted amino hyperbranched polysiloxane can be rinsed twice with alcohol and water respectively, washed, centrifuged to obtain precipitate, and dried for 12 hours at 60 ℃. The ratio of porous silicon to the amino hyperbranched polysiloxane is 1g (0.05-1) mL. By controlling the ratio of the amino hyperbranched polysiloxane to the porous silicon, the amount of surface grafting modification can be controlled, so that the number of amino groups on the surface can be controlled, and the slow release rate of the antibiotics can be controlled.

The preparation process of the amino hyperbranched polysiloxane comprises the following steps of dispersing aminosilane in an alcohol/water system (wherein alcohol can be one of methanol, ethanol and isopropanol, the ratio of the aminosilane to the methanol to the water is (1-1.2) mol:1.3), regulating pH to 8-11, and reacting for 4-12 h under the condition of nitrogen atmosphere and 60-95 ℃ to obtain the amino hyperbranched polysiloxane. The amino silane is hydrolyzed and further condensed under the alkaline and water conditions to generate Si-O-Si bonds, so that a dendritic hyperbranched structure is obtained, the hydrolysis rate of the amino silane can be controlled by controlling the pH value, so that the molecular weight of the synthesized hyperbranched polysiloxane is influenced, in addition, the molecular weight of the synthesized amino hyperbranched polysiloxane can be influenced by controlling the reaction time, the reaction temperature and the type of the amino silane, the larger the molecular weight means that the larger the volume of the amino hyperbranched polysiloxane is, the larger the number of polymerized silane monomers is, the larger the number of amino groups on the surface of the modified porous silicon is, and the more the positive charges are.

The amino silane is 3-aminopropyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl methyl diethoxy silane, 3-aminopropyl methyl dimethoxy silane aminoethylaminopropyl trimethoxysilane, aminoethylaminopropyl triethoxysilane amino ethyl amino propyl methyl dimethoxy silane aminoethylaminomethyl triethoxysilane, diethylenetriamine propyl trimethoxysilane diethylenetriamine propyl triethoxy silane at least one of diethylenetriamine propyl methyl dimethoxy silane and diethylenetriamine methyl diethoxy silane.

The preparation process of the porous silicon comprises the following steps of dissolving a surfactant in water, regulating the pH value to 9-12, adding a silicon source, uniformly mixing, performing hydrothermal reaction at 60-120 ℃ for 12-48 h, centrifuging to obtain a precipitate, and burning at 500-800 ℃ for 1-4 h to obtain the porous silicon.

Wherein the ratio of the surfactant to the silicon source is (0.3 g-0.8 g) 4mL, the surfactant is at least one of n-hexadecyltrimethyl ammonium bromide (CTAB), dodecyltrimethyl ammonium bromide (DTAB), polyether P123, polyether F127 and Sodium Dodecyl Sulfate (SDS), and the silicon source is Tetraethoxysilane (TEOS) or tetramethoxysilane.

The pore diameter of the prepared porous silicon can be controlled by controlling the type and the dosage of the surfactant (if two or more surfactants are selected, the obtained pore diameter is smaller), the pH value and the temperature and time of the hydrothermal reaction, and the larger the pore diameter is, the larger the drug loading is, but if the pore diameter is too large, the larger the macromolecule of the amino hyperbranched polysiloxane can enter the pore to be modified, occupy the space in the pore, and cause the reduction of the final drug loading.

Therefore, the control of the pore size of the porous silicon and the molecular weight of the amino hyperbranched polysiloxane are comprehensively considered, so that the maximum drug loading is realized. In this case, the porous silicon may be prepared by dissolving CTAB in water, adjusting pH to 10.5, adding tetraethoxysilane, stirring, performing hydrothermal reaction at 100deg.C for 24 hr, centrifuging (10000 rpm,15 min) to obtain precipitate, and burning at 600deg.C for 2 hr to obtain the porous silicon, wherein the ratio of CTAB to tetraethoxysilane is 0.6 g/4 mL. The preparation process of the amino hyperbranched polysiloxane comprises the steps of dispersing amino silane in a methanol/water system, adjusting the pH to 10, reacting for 6 hours in a nitrogen atmosphere at 60 ℃, and removing methanol and water by rotary evaporation to obtain the amino hyperbranched polysiloxane, wherein the molar ratio of the amino silane to the methanol to the water is 1mol:1.3 mol.

The preparation method has the beneficial effects that the amino hyperbranched polysiloxane modified porous silicon is used as an antibiotic carrier to be applied to CMC hydrogel dressing, the drug loading capacity and the mechanical strength of the cellulose-based hydrogel dressing are greatly improved, and the prepared hydrogel dressing has good biocompatibility and long-acting antibacterial effect.

Drawings

FIG. 1 is a scanning electron microscope image of porous silicon synthesized in example 1;

FIG. 2 is a transmission electron microscope image of the porous silicon synthesized in example 1;

FIG. 3 shows XRD patterns of porous silicon synthesized in example 1;

FIG. 4 is an infrared spectrum of porous silicon synthesized in example 1;

FIG. 5 is a schematic representation of the synthesis of an amino hyperbranched polysiloxane according to example 1;

FIG. 6 is a GPC chart of amino hyperbranched polysiloxanes of example 1;

FIG. 7 is a GPC chart of amino hyperbranched polysiloxanes of example 4;

FIG. 8 is a GPC chart of amino hyperbranched polysiloxanes of example 5;

FIG. 9 is a transmission electron microscope image of the amino hyperbranched polysiloxane modified porous silicon of example 1 and a corresponding EDX element distribution diagram;

FIG. 10 is a graph showing thermogravimetric curves of the modified porous silicon synthesized in the process of example 1 and the porous silicon synthesized in the process of comparative example 1 after loading with antibiotics;

FIG. 11 is a Zeta potential diagram of modified porous silicon or porous silicon synthesized in the processes of examples 1-5 and comparative examples 1-2;

FIG. 12 is a graph showing the tensile properties of the hydrogel dressings prepared in examples 1-4 and comparative examples 1-2;

FIG. 13 is a digital photograph showing the antibacterial cellulose hydrogel dressing prepared in example 1.

Detailed Description

The conception and the technical effects produced by the present invention will be clearly and completely described below with reference to the embodiments and the drawings to fully understand the objects, aspects and effects of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.

Example 1

An antimicrobial cellulose hydrogel dressing, the preparation method of which comprises the following steps:

(1) Synthesis of porous silicon 0.6g CTAB (surfactant) was dissolved in 100mL of water, then NaOH was added to adjust the pH to 10.5, then 4mL Tetraethoxysilane (TEOS) was added, and after stirring thoroughly for 2 hours, it was transferred to a PTFE-lined hydrothermal reactor and reacted at 100℃for 24 hours. Then obtaining white precipitate by centrifugation at 10000rpm for 15min, placing the obtained white precipitate in a tube furnace, burning at 600 ℃ for 2 hours in air atmosphere to obtain porous silicon, wherein a scanning electron microscope image is shown as a graph 1, a transmission electron microscope image is shown as a graph 2, which shows that the porous silicon contains ordered pore structures, an XRD image is shown as a graph 3, the crystal forms of the porous silicon are confirmed, and the synthetic porous silicon has stable structure and is mainly Si-O bonds as proved by comprehensive analysis of FTIR data of FIG. 4, and the material is harmless to human bodies, and an infrared spectrogram is shown as a graph 4;

(2) The synthesis of amino hyperbranched polysiloxane comprises the steps of uniformly mixing 1mol of 3-aminoethylaminopropyl trimethoxysilane with 1.3mol of methanol and 1.3mol of water in a flask, adding ammonia water to adjust the pH value to 10, and reacting for 6 hours under the condition of 60 ℃ in nitrogen atmosphere, transferring reactants into a rotary evaporator, and evaporating alcohol and water to obtain the amino hyperbranched polysiloxane, wherein the synthesis schematic diagram is shown in figure 5, and the GPC chart is shown in figure 6;

(3) Dispersing 1g of porous silicon prepared in the step (1) in a mixed solution of 90 ml of methanol/10 ml of water, carrying out ultrasonic treatment for 5 minutes, adding 0.5ml of amino hyperbranched polysiloxane prepared in the step (2), condensing and refluxing for 4 hours under the heating condition of 70 ℃, rinsing with alcohol and water respectively for two times after the reaction is finished, washing unreacted hyperbranched polysiloxane, centrifuging at a high speed of 10000rpm for 10 minutes to obtain white precipitate, and placing in a vacuum oven for drying at 60 ℃ for 12 hours to prepare the modified porous silicon, namely the amino hyperbranched polysiloxane modified porous silicon, wherein a transmission electron microscope image and a corresponding EDX element distribution diagram of the amino hyperbranched polysiloxane modified porous silicon are shown in fig. 9, the porous silicon does not contain nitrogen, the nitrogen is derived from the amino hyperbranched polysiloxane, and the nitrogen is uniformly distributed on the surface of the porous silicon as shown in the figure, so that the amino hyperbranched polysiloxane is uniformly modified on the surface of the porous silicon;

(4) The synthesis of the clindamycin-loaded modified porous silicon comprises the steps of dispersing the modified porous silicon prepared in the step (3) into clindamycin hydrochloride aqueous solution (50 mg/mL;50mg/mL is the maximum solubility of clindamycin hydrochloride in the aqueous solution), enabling the concentration of the modified porous silicon to be 10mg/mL, carrying out ultrasonic dispersion for 10min, vigorously stirring for 24 h, enabling the clindamycin hydrochloride aqueous solution to permeate into the inner pores of the modified porous silicon, then carrying out high-speed centrifugation at 10000rpm for 10min to obtain white precipitate, then placing the white precipitate in a vacuum oven at 50 ℃, and continuously drying for 12 h to obtain the clindamycin-loaded modified porous silicon;

(5) The antibacterial cellulose hydrogel dressing is synthesized by dissolving 0.5g of lemon and 0.5g of glycerol in 100mL of water, adding 1g of CMC, fully stirring to obtain uniform CMC hydrogel, adding 0.1g of clindamycin-loaded modified porous silicon prepared in the step (4), fully stirring to obtain uniform cellulose/drug-loaded modified porous silicon mixed hydrogel, namely the antibacterial cellulose hydrogel, pouring the hydrogel into a PTFE mold, vacuumizing to remove bubbles, and drying for 10 hours at 50 ℃ to obtain the antibacterial cellulose hydrogel dressing, wherein the photo of the antibacterial cellulose hydrogel dressing is shown in figure 13.

Example 2

An antibacterial cellulose hydrogel dressing was prepared in the same manner as in example 1 except that "ciprofloxacin hydrochloride" was used instead of "clindamycin".

Example 3

An antibacterial cellulose hydrogel dressing was prepared in the same manner as in example 1 except that "0.8g CTAB" was used instead of "0.6g CTAB".

Since example 3 has more surfactant added than example 1, the internal pore size produced during the preparation of porous silicon is smaller, and the mass of the antibiotic-containing drug entering the pores is less, so that less antibiotic remains in the pores after the solvent for the antibiotic is removed.

Example 4

An antibacterial cellulose hydrogel dressing was prepared in the same manner as in example 1 except that "diethylenetriamine propyl trimethoxysilane" was used instead of "3-aminoethylaminopropyl trimethoxysilane", and "2 hours of reaction" was used instead of "6 hours of reaction" in step (2).

In this example, the GPC chart of the amino hyperbranched polysiloxane synthesized in the process is shown in FIG. 7.

Example 5

An antibacterial cellulose hydrogel dressing was prepared in the same manner as in example 1 except that "1.2mol of 3-aminopropyl trimethoxysilane" was used instead of "1mol of 3-aminoethylaminopropyl trimethoxysilane", and "reaction under 75℃for 6 hours in a nitrogen atmosphere" was used instead of "reaction under 60℃for 6 hours in a nitrogen atmosphere" in step (2).

In this example, the GPC chart of the in-process synthetic amino hyperbranched polysiloxanes is shown in FIG. 8, mw (equivalent to M W) represents the weight average molecular weight, and it can be seen from FIGS. 6, 7 and 8 that the molecular weight of the amino hyperbranched polysiloxanes synthesized in examples 1, 4 and 5 is much higher than that of the silane monomers, indicating that the amino hyperbranched polysiloxanes polymerized from different aminosilane monomers were successfully prepared. On the other hand, just because the molecular weight of the amino hyperbranched polysiloxane is much higher, as shown in fig. 5, it takes on a dendritic-like molecular structure, and the amino hyperbranched polysiloxane is not easy to enter the inside of the pores of the porous silicon by the pore-size adjustment of the porous silicon.

Comparative example 1

Compared with the hydrogel dressing prepared in the embodiment 1 without modifying porous silicon, the porous silicon is directly loaded with antibiotics, and the preparation process is as follows:

(1) Synthesis of porous silicon 0.6g CTAB (surfactant) was dissolved in 100mL of water, then NaOH was added to adjust the pH to 10.5, then 4mL Tetraethoxysilane (TEOS) was added, and after stirring thoroughly for 2 hours, it was transferred to a PTFE-lined hydrothermal reactor and reacted at 100℃for 24 hours. Then obtaining white precipitate by centrifugation at 10000rpm for 15min, placing the obtained white precipitate in a tube furnace, and firing at 600 ℃ for 2 hours under air atmosphere to obtain porous silicon;

(2) The synthesis of the clindamycin-loaded porous silicon comprises the steps of dispersing the porous silicon prepared in the step (1) into clindamycin hydrochloride aqueous solution (50 mg/mL), dispersing the porous silicon with ultrasound for 10min, vigorously stirring for 24 hours to enable the clindamycin hydrochloride aqueous solution to permeate into the inner pores of the porous silicon, centrifuging at 10000rpm for 10min to obtain a precipitate, placing the white precipitate in a vacuum oven at 50 ℃, and continuously drying for 12 hours to obtain the clindamycin-loaded porous silicon;

(3) The preparation method of the hydrogel dressing comprises the steps of dissolving 0.5g of lemon and 0.5g of glycerol in 100mL of water, adding 1g of CMC, fully stirring to obtain uniform CMC hydrogel, adding 0.1g of clindamycin-loaded porous silicon prepared in the step (2), fully stirring to obtain uniform cellulose/drug-loaded porous silicon mixed hydrogel, pouring the hydrogel into a PTFE mold, vacuumizing to remove bubbles, and drying at 50 ℃ for 10 hours to obtain the hydrogel dressing.

Comparative example 2

A hydrogel dressing, compared with the preparation of the porous silicon in the embodiment 1, adopts non-hyperbranched conventional aminosilane (3-glycidoxypropyl trimethoxysilane) to modify, namely, the preparation of the porous silicon in the embodiment 1 is replaced by dispersing 1g of porous silicon prepared in the embodiment 1 in a mixture of 90 ml of methanol and 10 ml of water, carrying out ultrasonic treatment for 5 minutes, adding 0.5 ml of 3-glycidoxypropyl trimethoxysilane, condensing and refluxing for 4 hours under the heating condition of 70 ℃, rinsing twice with alcohol and water after the reaction is finished, centrifuging at a high speed of 10000rpm for 10 minutes to obtain precipitate, and placing in a vacuum oven for drying at 60 ℃ for 12 hours.

The hydrogel dressings prepared in examples and comparative examples were subjected to performance testing as follows:

1. Tensile property test samples of the hydrogel dressings prepared in examples 1 to 5 and comparative examples 1 to 2 were cut into rectangles of 80mm by 10mm, respectively, and the thickness was measured with a thickness gauge, and the tensile strength of the samples was measured with a universal electronic tester. The samples were placed in ambient conditions of 70% relative humidity and 23 ℃ for 24 hours of saturation and further tested. The sample was held at a distance of 40mm and stretched at a speed of 15mm/min. Each set of samples was tested at least 5 times and the data obtained was the average of 5 sets of valid data.

2. Drug loading test samples of modified porous silicon synthesized in the process of examples 1-5, porous silicon synthesized in the process of comparative example 1 (unmodified) and non-hyperbranched modified porous silicon synthesized in the process of comparative example 2 were continuously baked in a 60 ℃ oven for 24 hours, respectively, then the same mass (recorded as m ₀) of the baked modified porous silicon, porous silicon and non-hyperbranched modified porous silicon was immersed in an aqueous solution of clindamycin (50 mg/mL), sonicated for 30 minutes, and then continuously stirred for 12 hours. The samples were centrifuged out and then transferred to an oven at 60 ℃ for continuous baking for 24 hours, with the weight recorded as m _t. The drug loading was calculated according to the following formula, drug loading rate= ((m _t-m₀)/m₀) ×100%.

The results of the mechanical properties and drug loading properties are shown in table 1, and the tensile property diagram of the dressing is shown in fig. 12, which shows that the porous silicon of the modified amino hyperbranched polysiloxane contains a large amount of amino groups, can form hydrogen bonds with carboxymethyl groups on cellulose, further has better compatibility with a cellulose matrix, and shows better tensile property.

TABLE 1

3. In vitro drug release experiments:

the drug standard curve equation is that PBS buffer solution with pH=7.4 is prepared, then clindamycin is dissolved in the PBS buffer solution to obtain 1mg/mL antibiotic solution, and then different amounts of PBS buffer solution are used for dilution to obtain solutions with different concentrations. And taking the antibiotic solutions with different concentrations, and performing high performance liquid chromatography to determine the concentration, and fitting to obtain a standard curve.

The hydrogel dressings prepared in example 1, examples 3 to 5 and comparative examples 1 to 2 were cut into squares of 20mm. Times.20 mm, respectively, immersed in 50mL of PBS buffer, extracted for a prescribed period of time with 0.01mL of release solution, and supplemented with 0.01mL of fresh PBS buffer. The concentration of antibiotics was determined by high performance liquid chromatography and similar release of drug was calculated, with 3 parallel samples per group. The results are shown in Table 2.

TABLE 2

Cumulative release rate of clindamycin (%)	Comparative example 1	Comparative example 2	Example 1	Example 3	Example 4	Example 5
							0	0	0	0	0	0	0
For 2 hours	40.9	30.3	15.8	20.4	17.7	18.3
							4 Hours	55.7	45.3	24.7	27.3	26.5	28.0
8 Hours	62.1	56.7	39.6	37.4	36.0	37.5
							For 12 hours	65.7	61.4	53.2	51.8	48.9	50.4
24 Hours	67.8	64.4	59.5	61.1	60.6	58.9
							48 Hours	67.7	64.7	68.4	69.4	68.7	66.2
72 Hours	68.1	64.9	77.9	75.3	73.2	72.6
							96 Hours	68.3	65.4	85.3	81.7	79.8	77.5

4. Other tests:

The thermal weight curves of the amino hyperbranched polysiloxane modified porous silicon of example 1 and the porous silicon of comparative example 1 after loading with antibiotics are shown in fig. 10, and it is understood from fig. 10 that hyperbranched modification can load more antibiotics, so that weight loss is more. The porous silicon is silicon, has stable property, can not lose weight in the heating process, and the antibiotics are small molecules and are decomposed by heating.

The Zeta potential diagrams of the modified porous silicon or porous silicon synthesized in the processes of examples 1-5 and comparative examples 1-2 are shown in fig. 11, illustrating that the modified amino hyperbranched polysiloxane can effectively change the surface electronegativity of the porous silicon.

The present invention is not limited to the above embodiments, but is merely preferred embodiments of the present invention, and the present invention should be construed as being limited to the above embodiments as long as the technical effects of the present invention are achieved by the same means. Various modifications and variations are possible in the technical solution and/or in the embodiments within the scope of the invention.

Claims

1. An antibacterial cellulose hydrogel dressing, characterized in that its raw materials include carboxymethyl cellulose and modified porous silicon loaded with antibiotics; the modified porous silicon is amino hyperbranched polysiloxane modified porous silicon; the antibiotic contains a carboxyl group.

2. The antibacterial cellulose hydrogel dressing according to claim 1, characterized in that the mass ratio of carboxymethyl cellulose to the modified porous silicon loaded with antibiotics is 100:(5-30).

3. A method for preparing an antibacterial cellulose hydrogel dressing, characterized in that it comprises the following steps: mixing modified porous silicon loaded with antibiotics with carboxymethyl cellulose hydrogel to obtain the antibacterial cellulose hydrogel dressing; the modified porous silicon is amino-hyperbranched polysiloxane-modified porous silicon; and the antibiotic contains a carboxyl group.

4. The preparation method according to claim 3 is characterized in that the preparation process of the modified porous silicon comprises the following steps: mixing porous silicon and amino hyperbranched polysiloxane in an alcohol/water system, condensing and refluxing at 60° C.-95° C., and obtaining the modified porous silicon after the reaction is completed.

5 . The preparation method according to claim 4 , characterized in that the ratio of the porous silicon to the amino-hyperbranched polysiloxane is 1 g: (0.05-1) mL.

6. The preparation method according to claim 4 is characterized in that the preparation process of the amino-hyperbranched polysiloxane comprises the following steps: dispersing aminosilane in an alcohol/water system, adjusting the pH to 8-11, and reacting for 4h-12h under a nitrogen atmosphere and 60°C-95°C to obtain the amino-hyperbranched polysiloxane.

7. The preparation method according to claim 6, wherein the aminosilane is at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminomethyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, diethylenetriaminopropyltriethoxysilane, diethylenetriaminopropylmethyldimethoxysilane and diethylenetriaminomethyldiethoxysilane.

8. The preparation method according to claim 4 is characterized in that the preparation process of the porous silicon comprises the following steps: dissolving the surfactant in water and adjusting the pH to 9-12, then adding the silicon source and mixing, then hydrothermally reacting at 60°C-120°C for 12h-48h, centrifuging to obtain a precipitate, and then calcining at 500°C-800°C for 1h-4h to obtain the porous silicon.

9. The preparation method according to claim 8, characterized in that the ratio of the surfactant to the silicon source is (0.3g-0.8g):4mL; and/or the surfactant is at least one of n-hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, polyether P123, polyether F127 and sodium dodecyl sulfate; and/or the silicon source is tetraethoxysilane or tetramethoxysilane.

10. The preparation method according to claim 3, characterized in that the preparation process of the carboxymethyl cellulose hydrogel comprises the following steps: mixing citric acid, glycerol and carboxymethyl cellulose in water to obtain the carboxymethyl cellulose hydrogel.