Synthesis and application of fucoidan biological superabsorbent polymer
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摘要:目的
以富含L−岩藻糖和硫酸基等亲水结构的天然岩藻多糖为原料合成保水剂，以期提高保水剂的降解和可再生能力。
方法以过硫酸铵(Ammonium persulfate, APS)为引发剂，N,N′−亚甲基双丙烯酰胺(N,N'-Methylenebis acrylamide, MBA)为交联剂，采用水溶液聚合技术将天然岩藻多糖接枝在丙烯酸(Arylic acid, AA) 上进行共聚反应合成岩藻多糖生物保水剂。通过单因素试验优化产品制备工艺。采用傅里叶变换红外光谱仪(Fourier-transform infrared spectroscopy, FT-IR)和扫描电子显微镜(Scanning electron microscope, SEM)表征产物；通过盆栽试验检测保水剂对白菜生长的影响。
结果岩藻多糖和AA的最佳质量比为1.0∶7.5，中和度为70%，APS和MBA用量分别为AA质量的3.0%和0.2%。SEM结果表明，产物具有多孔疏松的网状结构；FT-IR分析表明，产物为岩藻多糖与AA的接枝共聚物。保水剂在去离子水、9 g∙L−1NaCl溶液中吸水倍率分别为420.9和63.8 g∙g−1；且在重复吸水、干燥6次后，吸水倍率仍为初始的70.8%。此外，每千克土壤中添加 6 g保水剂的白菜生长状况最佳，植株总生物量显著增加105.5%，土壤含水量提高8.98% (P < 0.05)。
结论岩藻多糖生物保水剂吸水和重复使用性能良好，在土壤中添加该保水剂能够显著促进植物生长。该研究为藻类保水剂的研发及其在农业中的推广应用提供了基础数据。
Abstract:ObjectiveUsing natural fucoidan rich in hydrophilic structures such as L-fucose and sulfated groups as raw material, a superabsorbent polymer (SAP) was synthesized to improve its degradability and renewable capacity.
MethodA fucoidan biological SAP was synthesized via aqueous solution polymerization by grafting natural fucoidan onto acrylic acid (AA) monomers using ammonium persulfate (APS) as the initiator and N, N'-methylenebis acrylamide (MBA) as the crosslinker. The preparation process was optimized through single-factor experiments. The product was characterized using Fourier-transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). A pot experiment was conducted to evaluate the effect of the SAP on cabbage growth.
ResultThe optimal mass ratio of fucoidan to AA was 1.0∶7.5, with a neutralization degree of 70%, and the dosages of APS and MBA were 3.0% and 0.2% of the mass of AA, respectively. The SEM analysis revealed a porous and loose network structure, while FT-IR confirmed the formation of a graft copolymer of fucoidan and AA. The water absorption ratios of the SAP in deionized water and 9 g∙L−1 NaCl solution were 420.9 and 63.8 g∙g−1, respectively. After six cycles of absorption and drying, the water absorption ratio remained 70.8% of its initial value. Additionally, Chinese cabbage grew best when adding 6 g SAP per kilogram of soil, with the total plant biomass significantly increased by 105.5% and soil water content improved by 8.98%.
ConclusionThe fucoidan biological SAP exhibits excellent water absorption and reusability, significantly promoting plant growth when applied to soil. This study provides foundational data for the development and agricultural application of algal-derived SAP.
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图 2 岩藻多糖和岩藻多糖生物保水剂的傅里叶变换红外光谱图
Figure 2. FT-IR spectra of fucoidan and fucoidan biological superabsorbent polymer
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图 3 岩藻多糖生物保水剂颗粒扫描电镜(SEM)图
Figure 3. Scanning electron microscopy (SEM) images of fucoidan biological superabsorbent polymer particle
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图 4 岩藻多糖生物保水剂在吸水进程中形态的时序变化
Figure 4. Temporal variation of the morphology of fucoiden biological superabsorbent polymer during the water absorption process
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图 5 岩藻多糖生物保水剂在ddH2O 和9 g∙L−1NaCl溶液 中的吸水动力学曲线
Figure 5. Kinetic curves of water absorption for fucoidan biological superabsorbent polymer in deionized water and 9 g∙L−1 NaCl solution
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图 6 岩藻多糖生物保水剂的重复吸水性能测试
图柱上的不同小写字母表示差异显著(P<0.05，Duncan’s 法)。
Figure 6. Repeated water swelling performance tests of fucoidan biological superabsorbent polymer
Different lowercase letters on the columns indicate significant differences (P<0.05, Duncan’s method).
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图 7 施用保水剂35 d后白菜的生长情况
CK为土壤对照，T1、T2、T3处理的保水剂与土壤质量比分别为2、4和6 g·kg−1。
Figure 7. Growth of Chinese cabbage after application of superabsorbent polymer for 35 days
CK is the soil control, the mass ratios of superabsorbent polymer to soil in T1, T2 and T3 are 2, 4 and 6 g·kg−1 respectively.
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图 8 保水剂对白菜生长的影响
CK为土壤对照，T1、T2、T3处理的保水剂与土壤质量比分别为2、4和6 g·kg−1；各小图中，同一指标图柱上的不同小写字母表示差异显著(P < 0.05，Duncan’s 法)。
Figure 8. Effect of superabsorbent polymer on the growth of Chinese cabbage
CK is the soil control, the mass ratios of superabsorbent polymer to soil in T1, T2 and T3 are 2, 4 and 6 g·kg−1 respectively. In each figure，different lowercase letters on the columns of the same indicator indicate significant differences (P < 0.05, Duncan’s method ).
表 1 单因素逐步优化合成梯度表1)
Table 1 Single-factor stepwise optimization for synthesizing gradient
梯度序号
Gradient No.S1 中和度 (S2)
Neutralization引发剂(S3)
Initiator交联剂(S4)
Crosslinker1 1.0∶6.0 60 0.020 0.05×10−2 2 1.0∶6.5 65 0.025 0.10×10−2 3 1.0∶7.0 70 0.030 0.15×10−2 4 1.0∶7.5 75 0.035 0.20×10−2 5 1.0∶8.0 80 0.040 0.25×10−2 1) S1、S3和S4分别表示m(岩藻多糖)∶m (AA)、m (APS)∶m (AA)和m (MBA)∶m (AA)。
1) S1, S3 and S4 represent m (fucoidan) ∶ m (AA), m (APS) ∶ m (AA) and m (MBA) ∶ m (AA), respectively.
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