摘要
超支化树状修饰方法凭借灵活、可控的结构设计,在聚合物基固定相的疏水改性中发挥着重要作用。该文以聚苯乙烯-二乙烯基苯为基质微球,1,4-丁二醇二缩水甘油醚、四乙烯五胺为环氧-胺接枝原料,以甲胺封端,制备了亲水型离子色谱固定相。利用扫描电子显微镜(SEM)、比表面积分析仪(BET)、傅里叶红外光谱仪(FTIR)、X射线光电子能谱仪(XPS)分析固定相的形貌、结构和表面元素。随后将固定相填充成色谱柱,以无机阴离子、有机弱酸为分离目标评价色谱柱的分离性能和保留机制,计算目标离子的分离度和理论塔板数。通过改变淋洗液浓度、温度和种类,考察自制色谱柱的保留行为和分离性能。结果表明,采用环氧-胺树状支化的修饰方式引入羟基,可有效增加固定相的亲水性。二价离子(SO_(4)^(2-)、HPO_(4)^(2-))受影响较大,表现出弱保留行为,而低价离子为离子交换保留行为。在3.6 mmol/L Na_(2)CO_(3)淋洗液条件下,制备的色谱柱可在20 min内完成12种阴离子(F^(-)、CH_(3)COO^(-)、ClO_(2)^(-)、BrO_(3)^(-)、Cl^(-)、HPO_(4)^(2-)、NO_(2)^(-)、SO_(4)^(2-)、Br^(-)、ClO_(3)^(-)、C_(2)O_(4)^(2-)和NO_(3)^(-))的分离。使用该离子色谱柱对自来水、地表水、工业废水等实际样品中的上述阴离子进行检测,相对标准偏差(RSD,n=3)均小于4.0%,表现出良好的应用前景。
The employment of hyperbranched dendritic modification techniques,recognized for their versatile and precise structural customization,is pivotal in the hydrophobic tailoring of polymerbased stationary phases for chromatographic applications.This investigation utilized polystyrene-divi⁃nylbenzene microspheres as a foundational substrate and engaged 1,4-butanediol diglycidyl ether alongside tetraethylenepentamine as epoxy-amine grafting agents,with methylamine serving as the terminal capping agent,to synthesize a hydrophilic ion chromatography stationary phase.The devel⁃oped phase's morphology,structural attributes,and surface elemental composition were systemati⁃cally characterized employing techniques such as scanning electron microscopy(SEM),Brunauer Emmett Teller(BET),Fourier-transform infrared spectroscopy(FTIR),and X-ray photoelectron spectroscopy(XPS).Subsequent incorporation into a chromatographic column facilitated the assess⁃ment of its separation efficacy and retention dynamics for inorganic anions and weak organic acids.Parameters including separation degree and theoretical plate count for specified ions were quantitative⁃ly established.The retention characteristics and chromatographic resolution of the fabricated column were scrutinized under variable conditions of concentration,temperature,and eluent composition.Outcomes indicated that the integration of hydroxyl functionalities via epoxy-amine dendritic branch⁃ing markedly amplified the stationary phase's hydrophilicity.The retention of divalent anions,specif⁃ically sulfate(SO_(4)^(2-))and hydrogen phosphate(HPO_(4)^(2-)),demonstrated a pronounced decrease,indicating minimal retention,while monovalent anions underwent ion exchange retention.Optimal sepa⁃ration of a suite of 12 anions,including fluoride(F^(-)),acetate(CH_(3)COO^(-)),chlorite(ClO_(2)^(-)),bro⁃mate(BrO_(3)^(-)),chloride(Cl^(-)),hydrogen phosphate(HPO_(4)^(2-)),nitrite(NO_(2)^(-)),sulfate(SO_(4)^(2-)),bro⁃mide(Br^(-)),chlorate(ClO_(3)^(-)),oxalate(C_(2)O_(4)^(2-)),and nitrate(NO_(3)^(-)),was achieved within a 20 mins timeframe using a 3.6 mmol/L sodium carbonate(Na_(2)CO_(3))eluent.Application of the tailored ion chromatography column to the detection of these anions in real samples,such as tap water,surface water,and industrial effluents,yielded a relative standard deviation(RSD,n=3)of less than 4.0%,underscoring its formidable potential for environmental analytical applications.
作者
蒙素仟
刘博
刘伟俊
刘瑞
桑柳波
赖华杰
MENG Su-qian;LIU Bo;LIU Wei-jun;LIU Rui;SANG Liu-bo;LAI Hua-jie(CAS Testing Technical Services(Guangzhou)Co.,Ltd.,Guangzhou 510650,China;CAS Testing Technical Services(Chongqing)Co.,Ltd.,Chongqing 400700,China;Guangzhou Institute of Chemistry,Chinese Academy of Sciences,Guangzhou 510650,China)
出处
《分析测试学报》
CAS
CSCD
北大核心
2023年第12期1565-1572,共8页
Journal of Instrumental Analysis
基金
广州市重点研发计划(2023B03J1365)。
关键词
离子色谱
超支化修饰
亲水型固定相
离子色谱柱
阴离子
ion chromatography
hyperbranched modification
hydrophilic stationary phase
ion chromatographic column
anion
