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    基于群感淬灭的磁性分子印迹聚合物制备及其对信号分子吸附特性研究

    Preparation of Magnetic Molecularly Imprinted Polymers Based on Group Sensing Quenching and Their Adsorption Characteristics on Signaling Molecules

    • 摘要: 在厌氧膜生物反应器(AnMBR)中,微生物的群体感应会加重生物污染,而调控N-酰基高丝氨酸内酯(AHLs)浓度对膜污染控制至关重要。基于表面分子印迹技术,本研究选用呋喃酮(DMHF)作为AHLs的结构类似物,采用纳米磁性Fe3O4颗粒作为载体,以甲基丙烯酸(MAA)为功能单体、偶氮二异丁腈(AIBN)为引发剂,通过表面聚合成功制备了对DMHF具有选择吸附性的磁性分子印迹聚合物(DMHF/SMIP)。利用傅里叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)和振动样品磁强计(VSM)对DMHF/SMIP进行了表征,结果表明,成功包裹印迹层的DMHF/SMIP粒径均匀、晶型稳定,有较好的超顺磁性并且表面含有大量的印迹空腔。随后,进行了DMHF/SMIP吸附性能及其对膜污染控制的模拟研究。结果显示,DMHF/SMIP在50 min基本达到吸附平衡,对DMHF的最大吸附量可达85.97 mg/g,吸附过程符合二级动力学及Langmuir方程,表明其主要以化学吸附和单层吸附为主。DMHF/SMIP表现出优异的稳定性和可回收性,在经过5次吸附-解吸循环后,吸附效率仍可达83.01%。在选择性吸附实验中, DMHF/SMIP对DMHF及其结构类似物表现出高度选择识别能力,对DMHF、4-甲氧基-2,5-二甲基-3(2H)-呋喃酮和5-羟甲基糠醛的吸附量分别为24.09、12.38和5.34 mg/g。利用DMHF/SMIP吸附特征AHLs(C6-HSL),其吸附量可达3.93 ug/g,最后,在针对AnMBR的吸附实验中,DMHF/SMIP对C6-HSL的去除率可达到34.87%。本研究制备了一种可选择性吸附且易于循环利用的AHLs分子印迹聚合物,为其在水处理中的应用提供了理论基础技术指导。

       

      Abstract: In the anaerobic membrane bioreactor (AnMBR), quorum sensing by microorganisms exacerbates biofouling, significantly hindering membrane performance and lifespan. Controlling the concentration of N-acyl homoserine lactones (AHLs) is crucial for membrane fouling control. This study used surface molecular imprinting technology, selecting furanone (DMHF) as a structural analog of AHLs and nano-magnetic Fe3O4 particles as the carriers. Using methacrylic acid (MAA) as a functional monomer, and azobisisobutyronitrile (AIBN) as the initiator, a magnetic molecularly imprinted polymer (DMHF/SMIP) with selective adsorption for DMHF was successfully prepared via surface polymerization. The DMHF/SMIP was characterized by using a Fourier transform infrared spectrometer (FTIR), scanning electron microscope (SEM), and vibrating sample magnetometer (VSM). These analyses indicated that the DMHF/SMIP, with a successfully encapsulated imprinting layer, exhibited a uniform particle size, stable crystal form, good superparamagnetism, and numerous surface imprinting cavities. These features enable the DMHF/SMIP to selectively bind to target molecules. Subsequently, the adsorption performance of DMHF/SMIP and its effect on membrane fouling control were evaluated. The results showed that DMHF/SMIP reached adsorption equilibrium in approximately 50 minutes, with a maximum adsorption capacity of 85.97 mg/g for DMHF. The adsorption process followed second-order kinetics and the Langmuir equation, suggesting primarily chemical and monolayer adsorption. This indicates that DMHF/SMIP has a high affinity for DMHF and can effectively remove it from the system. DMHF/SMIP exhibited excellent stability and recyclability, maintaining an adsorption efficiency of 83.01% even after five consecutive adsorption-desorption cycles. This demonstrates the material′s robustness and potential for long-term use. In selective adsorption experiments, DMHF/SMIP showed a high degree of selective recognition for DMHF and its structural analogs, with adsorption capacities of 24.09, 12.38, and 5.34 mg/g for DMHF, 4-methoxy-2,5-dimethyl-3(2H)-furanone (mesifurane), and 5-hydroxymethylfurfural, respectively. This selectivity is a key advantage of molecularly imprinted polymers, enabling the targeted removal of specific compounds from complex mixtures. Using DMHF/SMIP to adsorb representative AHLs (C6-HSL), the adsorption capacity reached 3.93 μg/g. This suggests that the polymer can effectively capture AHLs, known to contribute to quorum sensing and biofouling. Finally, in the adsorption experiments, the removal rate of C6-HSL by DMHF/SMIP reached 34.87%. This significant result demonstrates the polymer′s ability to reduce the levels of AHLs in AnMBR systems, potentially mitigating quorum sensing and biofouling. This study prepared a readily recyclable, magnetic molecularly imprinted polymer that selectively adsorbs AHLs, providing a theoretical basis and technical guidance for its application in water treatment. The development of such materials could revolutionize biofouling management in AnMBR systems, leading to more efficient and sustainable wastewater treatment.

       

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