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反相氣相色譜研究分子印跡聚合物的氣相識(shí)別

發(fā)布時(shí)間:2019-03-30 17:07
【摘要】:本論文分別以甲苯、糠酸、丹皮酚及桃金娘烯醛為目標(biāo)分子,選取不同聚合方法制得分子印跡聚合物,利用不同表征方式測(cè)試其結(jié)構(gòu),并將其作為氣相色譜固定相,采用反相氣相色譜技術(shù)開(kāi)展了一些其對(duì)氣態(tài)模板分子的保留吸附研究。探究了固定相對(duì)氣態(tài)目標(biāo)分子的選擇作用及鍵合能力,測(cè)得了目標(biāo)分子在印跡柱上的吸附等溫線(xiàn),并測(cè)試了分子印跡聚合物對(duì)分析樣品中模板的實(shí)際吸附作用,具體摘要如下:(1)以甲苯為致孔劑(又作為模板分子)結(jié)合沉淀聚合法,以四乙烯基吡啶為功能單體制備了甲苯印跡聚合物均勻微球。采用氮吸附法及光學(xué)顯微鏡測(cè)定了微球的結(jié)構(gòu)特征,利用反相氣相色譜法研究了其對(duì)氣態(tài)甲苯分子及相關(guān)化合物的選擇保留能力,探討了印跡材料及對(duì)照聚合物對(duì)模板的等溫鍵合能力。結(jié)果表明:甲苯印跡(MIP3)氣相色譜柱對(duì)氣態(tài)甲苯分子具有較高的選擇保留能力,在優(yōu)化色譜條件下,其對(duì)甲苯的保留因子和印跡因子分別高達(dá)68.42和7.049,對(duì)甲苯的選擇因子相對(duì)于苯和對(duì)二甲苯分別為4.821和5.370,且能有效分離甲苯、苯及對(duì)二甲苯的模擬混合物(甲苯與對(duì)二甲苯及苯的分辨率分別為5.138和1.762)。甲苯印跡微球?qū)鈶B(tài)甲苯的吸附等溫線(xiàn)類(lèi)型表現(xiàn)為BET吸附的Ⅱ類(lèi)吸附。所得甲苯印跡材料對(duì)室內(nèi)空氣中的甲苯、苯及對(duì)二甲苯均具有較高的脫除能力。(2)以糠酸為模板分子制備了糠酸印跡聚合物,利用紅外光譜和掃描電鏡測(cè)定其結(jié)構(gòu)特征。將其作為氣相色譜固定相,采用反相氣相色譜法對(duì)印跡柱的保留選擇性能進(jìn)行研究,測(cè)試了其對(duì)目標(biāo)分子及結(jié)構(gòu)類(lèi)似物的鍵合能力,探究了其對(duì)樣品模擬液中糠酸的吸附能力。結(jié)果顯示以MIP3對(duì)目標(biāo)分子的保留能力最強(qiáng),且當(dāng)柱溫為443K,印跡柱對(duì)糠酸相對(duì)于糠醛的選擇因子可達(dá)11.55,顯示出較高的選擇性能。確定的色譜條件下,MIP3柱能有效分離糠酸-糠醛模擬混合物,糠酸與糠醛的分辨率可達(dá)為1.544。吸附等溫線(xiàn)結(jié)果顯示MIP3對(duì)糠酸的吸附量遠(yuǎn)高于對(duì)糠醛的吸附量,印跡材料對(duì)樣品模擬液的吸附情況顯示對(duì)糠酸具有較強(qiáng)的吸附能力。(3)丹皮酚為模板分子,制備了丹皮酚分子印跡聚合物,利用掃描電鏡和紅外光譜表征其結(jié)構(gòu),考察了MIP對(duì)目標(biāo)分子的特異識(shí)別性能,探究了其對(duì)目標(biāo)分子及類(lèi)似物的選擇分離能力,測(cè)試了其作為氣相色譜固定相對(duì)氣態(tài)分子的鍵合能力,計(jì)算得到丹皮酚和相關(guān)化合物在固定相上的吸附等溫線(xiàn)。結(jié)果顯示在優(yōu)化的色譜條件下,印跡柱對(duì)丹皮酚的保留因子可達(dá)144.2,對(duì)丹皮酚的選擇因子相對(duì)于丁香酚為6.61,呈現(xiàn)出較高的選擇保留能力,另外,丹皮酚、丁香酚的混合物能夠在分子印跡柱上達(dá)到完全分離。丹皮酚及丁香酚在分子印跡聚合物的吸附等溫線(xiàn)表明:目標(biāo)分子與印跡位點(diǎn)具有較強(qiáng)的結(jié)合作用,且在相同條件下,丹皮酚的吸附量遠(yuǎn)高于丁香酚。這些結(jié)果都表明:印跡材料對(duì)丹皮酚呈現(xiàn)良好吸附選擇性能。(4)桃金娘烯醛為模板分子,納米TiO2為載體,采取表面印跡技術(shù)制備出桃金娘烯醛表面印跡材料,采取SEM及紅外光譜等方法表征結(jié)構(gòu),結(jié)果說(shuō)明經(jīng)過(guò)TiO2表面修飾后的分子印跡聚合物已經(jīng)合成。將制備好的印跡聚合物作為氣相色譜固定相,測(cè)試其對(duì)氣態(tài)分析質(zhì)的各種性能。測(cè)試了印跡材料對(duì)目標(biāo)分子的保留能力及選擇性,在確定的色譜條件下,印跡柱對(duì)桃金娘烯醛的保留因子可達(dá)63.4,遠(yuǎn)遠(yuǎn)大于對(duì)松油醇的保留因子;探究了其表面印跡位點(diǎn)與目標(biāo)分子的鍵合能力,由目標(biāo)分子在不同進(jìn)樣體積下的氣相色譜圖,計(jì)算并繪制出桃金娘烯醛及相似物在固定相上的吸附等溫線(xiàn),表明桃金娘烯醛印跡聚合物表面印跡位點(diǎn)與目標(biāo)分子的鍵合作用要強(qiáng)于松油醇,且對(duì)桃金娘烯醛的吸附量也高于松油醇。
[Abstract]:In this paper, the molecular imprinting polymer was prepared by using toluene, furfuryl acid, paeonol and myrcaldehyde as the target molecule, and the structure of the molecularly imprinted polymer was tested by different methods, and the structure was used as the stationary phase of gas chromatography. The retention and adsorption of gaseous template molecules were studied by reverse-phase gas chromatography. The selective effect and bonding ability of fixed relative gaseous target molecules were investigated, the adsorption isotherms of the target molecules on the blots were measured, and the actual adsorption of the molecularly imprinted polymer to the template in the sample was tested. The specific abstract is as follows: And (1) using toluene as a pore-forming agent (as a template molecule) in combination with a photopolymerization method, and preparing a toluene-imprinted polymer uniform microsphere by using a tetravinyl benzene-based monomer as a functional monomer. The structural characteristics of the microspheres were determined by a nitrogen adsorption method and an optical microscope. The selective retention of the gaseous toluene molecules and related compounds was studied by reversed-phase gas chromatography, and the isothermal bonding ability of the imprinted material and the control polymer to the template was discussed. The results show that the toluene-imprinted (MIP3) gas chromatographic column has a high selectivity to the gaseous toluene molecule, and the retention factor and the imprint factor of toluene are as high as 68.42 and 7.049, respectively, under the optimized chromatographic conditions. The selection factors for toluene were 4.821 and 5.370, respectively, and the simulated mixture of toluene, benzene and p-xylene was effectively separated (the resolution of toluene to para-xylene and benzene was 5.138 and 1.762, respectively). The adsorption isotherms of the toluene-imprinted microspheres on the gaseous toluene showed a type 鈪,

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