Papageorgiou Myrsini, Nanaki Stavroula G, Kyzas George Z, Koulouktsi Christina, Bikiaris Dimitrios N, Lambropoulou Dimitra A
Laboratory of Environmental Pollution Control, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Greece.
Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Greece.
Polymers (Basel). 2017 Nov 10;9(11):595. doi: 10.3390/polym9110595.
The present study focused on the synthesis and application of novel isocyanate-modified carrageenan polymers as sorbent materials for pre-concentration and removal of diclofenac (DCF) and carbamazepine (CBZ) in different aqueous matrices (surface waters and wastewaters). The polymer materials were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Thermal Gravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). The effects on the adsorption behavior were studied, and the equilibrium data were fitted by the Langmuir and Freundlich models. The maximum adsorption capacity () was determined by Langmuir⁻Freundlich model and was ranged for iota-carrageenan (iCAR) from 7.44 to 8.51 mg/g for CBZ and 23.41 to 35.78 mg/g for DCF and for kappa-carrageenan (kCAR) from 7.07 to 13.78 mg/g for CBZ and 22.66 to 49.29 mg/g for DCF. In the next step, dispersive solid phase extraction (D-SPE) methodology followed by liquid desorption and liquid chromatography mass spectrometry (LC/MS) has been developed and validated. The factors, which affect the performance of D-SPE, were investigated. Then, the optimization of extraction time, sorbent mass and eluent's volume was carried out using a central composite design (CCD) and response surface methodology (RSM). Under the optimized conditions, good linear relationships have been achieved with the correlation coefficient (²) varying from 0.9901 to 0.995. The limits of detections (LODs) and limits of quantifications (LOQs) ranged 0.042⁻0.090 μg/L and 0.137⁻0.298 μg/L, respectively. The results of the recoveries were 70⁻108% for both analytes, while the precisions were 2.8⁻17.5% were obtained, which indicated that the method was suitable for the analysis of both compounds in aqueous matrices.
本研究聚焦于新型异氰酸酯改性卡拉胶聚合物的合成与应用，该聚合物可作为吸附剂材料，用于预富集和去除不同水性基质（地表水和废水）中的双氯芬酸（DCF）和卡马西平（CBZ）。采用傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、热重分析（TGA）和扫描电子显微镜（SEM）对聚合物材料进行了表征。研究了其对吸附行为的影响，并采用朗缪尔和弗伦德里希模型对平衡数据进行拟合。通过朗缪尔-弗伦德里希模型确定了最大吸附容量（），对于ι-卡拉胶（iCAR），CBZ的最大吸附容量为7.44至8.51 mg/g，DCF为23.41至35.78 mg/g；对于κ-卡拉胶（kCAR），CBZ为7.07至13.78 mg/g，DCF为22.66至49.29 mg/g。下一步，开发并验证了分散固相萃取（D-SPE）方法，随后进行液体解吸和液相色谱-质谱联用（LC/MS）分析。研究了影响D-SPE性能的因素。然后，采用中心复合设计（CCD）和响应面方法（RSM）对萃取时间、吸附剂质量和洗脱剂体积进行了优化。在优化条件下，获得了良好的线性关系，相关系数（²）在0.9901至0.995之间。检测限（LOD）和定量限（LOQ）分别为0.042⁻0.090 μg/L和0.137⁻0.298 μg/L。两种分析物的回收率为70⁻108%，精密度为2.8⁻17.5%，表明该方法适用于分析水性基质中的两种化合物。
