载药聚合物原位改性竹材的尺寸稳定性与pH值响应释药特性

张浩良; 陈吉鑫; Nan Ohnmar Kyaw; 王慧; 武新星; 张艳; 韩帅波; 谢小兵; 马同华; 孙芳利

doi:10.12326/j.2096-9694.2026025

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载药聚合物原位改性竹材的尺寸稳定性与pH值响应释药特性
In-Situ Formation of Drug-Loaded Polymers in Bamboo for Dimensional Stabilization and pH Value Responsive Drug Release Performance
1.浙江农林大学化学与材料工程学院，浙江杭州 311300
2.浙江农林大学生物基材料菌虫防治研究所，浙江杭州 311300
3.千年舟新材科技集团股份有限公司，浙江杭州 311112
2026年40卷第4期页码：22-36
DOI： 10.12326/j.2096-9694.2026025
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张浩良,陈吉鑫,Nan Ohnmar Kyaw等.载药聚合物原位改性竹材的尺寸稳定性与pH值响应释药特性[J].木材科学与技术,2026,40(04):22-36. DOI： 10.12326/j.2096-9694.2026025.

Zhang Haoliang,Chen Jixin,Kyaw Nan Ohnmar,et al.In-Situ Formation of Drug-Loaded Polymers in Bamboo for Dimensional Stabilization and pH Value Responsive Drug Release Performance[J].Chinese Journal of Wood Science and Technology,2026,40(04):22-36. DOI： 10.12326/j.2096-9694.2026025.

摘要

首先以壳聚糖（chitosan，CS）、甲基丙烯酸羟乙酯（2-Hydroxyethyl methacrylate，HEMA）和马来酸（maleic acid，MA）构建三元聚合物体系CS/p（HEMA-co-MA）（简称为CHM），然后将防腐剂四水合八硼酸二钠（disodium octaborate tetrahydrate，DOT）负载于CHM中得到载药聚合物CHMD，采用CHMD浸渍毛竹（

Phyllostachys edulis

）试样得到CHMD-B，以解决竹材尺寸稳定性差和DOT易流失等问题。采用响应面法优化聚合物CHM合成工艺，确定最佳条件为：反应温度160 ℃、HEMA与MA物质的量比为2∶1、反应时间2 h，所得CHM的凝胶率为98.9%，溶胀率为20.2%。多种表征方法表明CHM以氢键、酯键和酰胺键等键形成致密的三维网络结构，加入的壳聚糖提高了聚合物的热稳定性和力学强度。载药聚合物CHMD表现出明显的pH值响应释药行为，药物释放速率随pH值降低而增大，符合一级动力学模型，以扩散机制为主。CHMD可有效渗透进入毛竹的细胞腔和细胞壁中，在竹材内部原位固化。改性后竹材

表面水接触角由未处理材的22.8°提高至66.5°，吸水体积湿胀率为4.3%，在3次吸水-干燥循环后抗湿胀率仍保持在57.1%。处理竹材中DOT呈现“突释”后“缓释”的双阶段释放规律，且具有pH值响应释药特性，在酸性条件下释放加快，在中性条件下释放受到抑制。与DOT单独处理材相比，CHMD-B中DOT的72 h流失率降至59.1%，抗流失率提高32.0%。CS/p（HEMA-co-MA）载药体系通过物理填充、疏水交联与响应释药三重协同作用，为竹材尺寸稳定性提升与DOT长效固着和响应释放提供一体化的解决方案。

Abstract

In this paper

a ternary polymer system

CS/p (HEMA-co-MA) (CHM)

was prepared from chitosan (CS)

2-hydroxyethyl methacrylate (HEMA)

and maleic acid (MA)

and subsequently loaded with disodium octaborate tetrahydrate (DOT) to obtain a preservative-loaded polymer (CHMD). CHMD was then formed in situ within bamboo to improve its dimensional stability and reduce DOT leaching. Response surface methodology identified the optimal conditions as a reaction temperature of 160 ℃

an HEMA/MA molar ratio of 2∶1

and reaction time of 2 h

under which the resulting polymer exhibited a gel content of 98.9% and a swelling rate of 20.2%. Structural and physicochemical characterizations revealed that CHM formed a dense three-dimensional network structure via hydrogen bonds

ester bonds

and amide bonds. The incorporation of CS improved the thermal stability and mechanical strength of the polymer network. CHMD showed significant pH-responsive release behavior in vitro

with the release rate increasing as pH value decreased

following the first-order kinetic model and dominated by a diffusion mechanism. CHMD effectively penetrated into the bamboo cell lumens

cell walls

and intercellular spaces and was cured in situ. The modified bamboo showed enhanced surface hydrophobicity

with water contact angle increasing from 22.8° for untreated bamboo to 66.5°. The water absorption swelling rate of the treated bamboo remained below 4.3%

and the anti-swelling efficiency remained above 57.1% after three water absorption-drying cycles. The DOT release from the treated bamboo exhibited a “burst release” followed by a “sustained release” pattern

with pH-responsive behavior: release was suppressed under neutral conditions but accelerated under acidic conditions. Compared with DOT-only treated

the 72  h leaching rate of DOT in the treated bamboo decreased to 59.1%

and the anti-loss rate increased by 32.0%. In summary

the CS/p(HEMA-co-MA)-based system integrates physical filling

formation of a hydrophobic crosslinked network

and pH-responsive preservative release

providing an effective strategy for simultaneously improving the dimensional stability of bamboo

enhancing DOT retention

and enabling environmentally responsive release.

关键词

Keywords

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