【摘要】：核磁共振中色譜技術(shù)無需經(jīng)過物理分離便可實現(xiàn)混合物中分析物的信號分離,已在混合物組分分離分析方面顯示出良好的應(yīng)用潛能。目前關(guān)于提升核磁共振色譜分析效果的研究還是相對較少,因此本文首先較系統(tǒng)考察有機(jī)溶劑對核磁共振中色譜分離效果的影響;接著,以十二烷基磺酸鈉為虛擬固定相,拓展適用于該技術(shù)的分析物體系;最后,將核磁共振色譜分離技術(shù)應(yīng)用于生物質(zhì)轉(zhuǎn)化實際應(yīng)用體系中,展現(xiàn)出優(yōu)于傳統(tǒng)分析方法的特點。首先,本文選用氘代甲醇、氘代二甲基亞砜、氘代丙酮和氘代乙腈四種有機(jī)改性劑,以醇、酸和氨基酸等不同類型的化合物作為分析物模型體系,考察水相中不同體積分?jǐn)?shù)的有機(jī)改性劑對核磁共振中色譜分離技術(shù)的影響。實驗結(jié)果表明:前三種氘代試劑對分析物分離效果的影響具有共性,隨著水相中加入氘代試劑體積分?jǐn)?shù)的增加,分析物的擴(kuò)散系數(shù)先減小后增大;而隨著氘代乙腈體積分?jǐn)?shù)的增加,分析物的擴(kuò)散系數(shù)一直增加。氘代試劑的加入,在某種程度上改善了混合物之間的分離效果。其次,本文考察了十二烷基磺酸鈉作為虛擬固定相,分離以下6組芳香族有機(jī)酸混合物的分離能力:(1)鄰羥基苯甲酸、間羥基苯甲酸和對羥基苯甲酸;(2)苯甲酸、鄰苯二甲酸和均苯三甲酸;(3)水楊酸、鄰苯二甲酸和對甲苯磺酸;(4)對溴苯甲酸、水楊酸和對甲苯磺酸;(5)苯甲酸、鄰苯二甲酸和對甲苯磺酸;(6)對溴苯甲酸、苯甲酸和對甲苯磺酸。實驗結(jié)果表明:上述六組混合物均能在虛擬固定相的作用下實現(xiàn)信號分離,其信號分離原因為分析物與虛擬固定相的作用強(qiáng)度不同。最后,本文將核磁共振色譜技術(shù)應(yīng)用到丁二酸實際發(fā)酵液中,通過測定發(fā)酵液中不同組分的擴(kuò)散系數(shù),并結(jié)合模型化合物的核磁信號,測定出發(fā)酵液中含有的主要物質(zhì)為葡萄糖、丁二酸和乙酸。進(jìn)一步對丁二酸實際發(fā)酵液進(jìn)行qHNMR定量實驗,實驗結(jié)果得出,發(fā)酵液中目的產(chǎn)物丁二酸的含量為14 g/L,副產(chǎn)物乙酸的含量為11 g/L,計算結(jié)果與HPLC定量結(jié)果一致。
[Abstract]:The chromatographic technique in NMR can realize the signal separation of the analyte in the mixture without physical separation. It has shown good application potential in the separation and analysis of mixture components. At present, there is relatively little research on improving the analytical effect of NMR chromatography, so the effect of organic solvents on chromatographic separation in NMR is studied systematically, and then sodium dodecyl sulfonate is used as virtual stationary phase. Finally, the nuclear magnetic resonance chromatographic separation technology was applied to the practical application system of biomass conversion, which showed better characteristics than the traditional analytical methods. Firstly, four organic modifiers, such as deuterated methanol, deuterated dimethyl sulfoxide, deuterated acetone and deuterated acetonitrile, were used as the analytical model system. The effect of organic modifiers with different volume fraction in water phase on chromatographic separation in NMR was investigated. The experimental results show that the first three deuterium reagents have a common effect on the separation of analytes. With the increase of the volume fraction of deuterium reagents in the water phase, the diffusion coefficient of the analytes decreases first and then increases. However, with the increase of deuterated acetonitrile volume fraction, the diffusion coefficient of the analyte increases. The addition of deuterium reagents improves the separation of mixtures to some extent. Secondly, the separation ability of sodium dodecyl sulfonate as a virtual stationary phase for the separation of six groups of aromatic organic acid mixtures was investigated: (1) o-hydroxybenzoic acid, m-hydroxybenzoic acid and p-hydroxybenzoic acid, (2) benzoic acid, Phthalic acid and terephthalic acid; (3) salicylic acid, phthalic acid and p-toluenesulfonic acid; (4) p-bromobenzoic acid, salicylic acid and p-toluenesulfonic acid; (5) benzoic acid, phthalic acid and p-toluenesulfonic acid; (6) p-bromobenzoic acid, benzoic acid and p-toluenesulfonic acid. The experimental results show that the above six groups of mixtures can achieve signal separation under the action of the virtual stationary phase, and the reason for the signal separation is that the interaction intensity between the analyte and the virtual stationary phase is different. Finally, nuclear magnetic resonance chromatography was applied to the actual fermentation broth of succinic acid. The diffusion coefficient of different components in the fermentation broth was determined, and the nuclear magnetic signal of the model compound was combined. The main substances in fermentation broth are glucose, succinic acid and acetic acid. Further qHNMR quantitative experiments were carried out on the fermentation broth of succinic acid. The results showed that the content of succinic acid and acetic acid were 14 g / L and 11 g / L, respectively. The calculated results were in agreement with the quantitative results of HPLC.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O652.6

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