单宁酸-氯化铁-聚ACG复合水凝胶微针贴片的制备与性能表征

赵喜阳; 康希彤; 刘焕生; 刘涛; 王清文

单宁酸-氯化铁-聚ACG复合水凝胶微针贴片的制备与性能表征

1.
华南农业大学材料与能源学院, 生物质工程研究院, 广州 510642
2.
华南农业大学食品学院, 广州 510642

基金项目: 广东省基础与应用基础面上项目 (2023A1515012167)

详细信息

通讯作者:
刘涛，博士，副教授，硕士生导师，研究方向为生物质基功能材料　E-mail: liutao@scau.edu.cn

中图分类号: O63；TB332
计量
- 文章访问数: 22
- HTML全文浏览量: 15
- 被引次数: 0
出版历程
- 收稿日期: 2024-06-24
- 修回日期: 2024-08-09
- 录用日期: 2024-08-09
- 网络出版日期: 2024-08-31

Preparation and characterization of tannic acid-ferric chloride-polyACG composite hydrogel microneedle patch

1.
College of Materials and Energy, Institute of Biomass Engineering, South China Agricultural University, Guangzhou 510642, China
2.
College of Food Science, South China Agricultural University, Guangzhou 510642, China

Funds: GuangDong Basic and Applied Basic Research Foundation (2023A1515012167)

摘要

摘要: 皮肤是人体最大的器官，皮肤损伤后若不能及时愈合会形成慢性伤口，其中细菌感染是慢性难愈合创面面临的一大难题。水凝胶是一种具有三维网络结构的高分子材料，能够吸收伤口渗出液，保持伤口湿润，有助于加速愈合过程。但实际临床使用中，水凝胶敷料的抗菌性仍有待提升。本文以N-丙烯酰基-2-甘氨酸(ACG)为单体，通过引入单宁酸(TA)、FeCl₃和羟基磷灰石(HAp)，制备具有光热杀菌性能的水凝胶；进一步利用PDMS微针模具，构建具有微针结构的水凝胶，使其能够穿透皮肤角质层达到深层次的杀菌效果，并且不会产生强烈的疼痛感，促进创面愈合。本文研究了TA含量对复合水凝胶的韧性和黏附性能的影响，结果表明，当TA∶ACG为1∶20时，制备出的复合水凝胶具有高力学强度(790 kPa)、高拉伸性(1043%)和良好的黏附性(25.04 kPa)。水凝胶中FeCl₃的含量会影响光热转换温度，当FeCl₃∶TA为1∶25时，水凝胶在808 nm激光照射下2 min可以达到51℃。该研究利用TA与FeCl₃的光热效应，制备临床伤口管理所需要的水凝胶敷料，并做成微针形状，展示出其在促愈合、载药输送、临床检测等领域的应用潜力。
- 水凝胶 /
- 单宁酸 /
- 光热转换 /
- 微针 /
- 伤口敷料
Abstract: Skin is the largest organ of body, and chronic wounds can inevitably form when the skin injuries do not be healed promptly, and bacterial infection is a major challenge for healing chronic wounds. Hydrogel, a three-dimensional network structure, can help accelerate wound healing by absorbing exudate and maintaining moisture of wounds. However, the antibacterial property of hydrogel dressings still need be highly improved. In this study, a photothermal antibacterial hydrogel was prepared by using N-acryloyl-2-glycine (ACG), tannic acid (TA), FeCl₃, and hydroxyapatite (HAp). And subsequently exploiting a PDMS micro-needle mold to construct hydrogel microneedle patch which could penetrate the epidermis for deep-level antibacterial effects without causing strong pain. When TA∶ACG was fixed at 1∶20, the synthetic hydrogel exhibited high mechanical strength (790 kPa), long tensile strain (1043%), and good adhesion (25.04 kPa). Additionally, when FeCl₃∶TA was 1∶25, the hydrogel could reach 51°C under 808-nm laser irradiation for 2 minutes. As the proof of concept, this study demonstrates the hydrogel microneedle patch with photothermal effects can be utilized in clinical wound management, showing great potential for promoting wound healing, drug delivery, and clinical detection.
- hydrogel /
- tannic acid /
- photothermal conversion /
- microneedle /
- wound dressing

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图 1 搭接剪切测试水凝胶黏附性能示意图

Figure 1. Schematic representation of the adhesion properties of hydrogels under lap shear test

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图 2 DMSO-d6中聚合单体ACG的核磁氢谱图

Figure 2. ¹H NMR spectrum of N-acryloyl 2-glycine in DMSO-d6

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图 3 不同TA含量水凝胶的力学性能和PATH-3水凝胶的抗疲劳性： (a) 应力-应变拉伸曲线；(b) 韧性； (c) PATH-3分步拉伸曲线； (d) PATH – 3分步压缩曲线； (e) PATH-3分步循环压缩曲线； (f) 50 %应变循环压缩100次。

Figure 3. Mechanical properties of composited hydrogels with different mass ratio of TA and ACG, fatigue resistance of hydrogel PATH-3: (a) stress-strain tensile curve; (b) Resilience; (c) PATH-3 step-by-step tensile curve; (d) PATH-3 step-by-step compression curve; (e) PATH-3 step-by-step cyclic compression curve; (f) 50% strain cyclic compression 100 times.

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图 4 不同FeCl₃含量水凝胶的温度随光照时间变化过程

Figure 4. The temperature change process of hydrogels with different FeCl₃ content with laser irradiation time

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图 5 (a) 不同FeCl3含量水凝胶的温度-时间变化趋势图；(b) PATH-Fe-2水凝胶不同光照距离温度-时间变化趋势图

Figure 5. (a) Temperature-time trend diagram of hydrogels with different FeCl₃ contents ; (b) Temperature-time trend diagram of PATH-Fe-2 hydrogel with different light distances

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图 6 PATH-Fe-2水凝胶对不同基材的黏附性能

Figure 6. Adhesion of PATH-Fe-2 hydrogels to different substrates

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图 7 不同TA含量和加入FeCl₃后水凝胶的黏附性能：(a) 180°搭接剪切测试曲线；(b) 黏附强度。

Figure 7. Adhesion properties of hydrogels with different TA content and adding FeCl₃: (a). 180 ° lap shear test curve; (b). Adhesion strength.

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图 8 PATH-Fe-MNs水凝胶形貌图

Figure 8. The morphology of PATH-Fe-MNs hydrogel

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图 9 PATH-Fe-2水凝胶对大肠杆菌和金黄色葡萄球菌的光热杀菌效果：(a) 大肠杆菌空白对照组；(b) 大肠杆菌实验组；(c) 金黄色葡萄球菌空白对照组；(d) 金黄色葡萄球菌实验组。

Figure 9. Photothermal sterilization effect of PATH-Fe-2 hydrogel on Escherichia coli and Staphylococcus aureus: (a). Escherichia coli blank control group; (b). Escherichia coli experimental group; (c). Staphylococcus aureus blank control group; (d) Staphylococcus aureus experimental group.

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表 1 PATH水凝胶配方表

Table 1. The formulation of PATH composited hydrogel

Sample	ACG/g	TA/g	H₂O/mL	HAp/g	I₂₉₅₉/g
PATH-0	1	0	2.27	0.06	0.01
PATH-1	1	0.01	2.26	0.06	0.01
PATH-2	1	0.03	2.24	0.06	0.01
PATH-3	1	0.05	2.22	0.06	0.01
PATH-4	1	0.10	2.17	0.06	0.01
PAT	1	0.05	2.28	0	0.01
Notes：PATH: P, polymer; A, N-acryloyl-2-glycine (ACG); T, tannic acid (TA); H, hydroxyapatite (HAp).

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表 2 PATH-Fe水凝胶配方表

Table 2. The formulation of PATH-Fe composited hydrogel

Sample	ACG/g	TA/g	FeCl₃·6H₂O/g	H₂O/mL	HAp/g	I₂₉₅₉/g
PATH-Fe-1	1	0.05	0.0025	2.22	0.06	0.01
PATH-Fe-2	1	0.05	0.0033	2.22	0.06	0.01
PATH-Fe-3	1	0.05	0.0042	2.22	0.06	0.01

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