本文選題：剛果紅 + �；撬���； 參考：《華東師范大學(xué)》2017年博士論文

【摘要】：隨著色譜學(xué)科的發(fā)展,色譜工作者更加注重于復(fù)雜樣品的分離及分析。這就要求同一根色譜柱能同時(shí)分離極性和非極性混合物,離子形式的和中性的混合物或有機(jī)和無機(jī)混合物。通常,針對(duì)于復(fù)雜混合物的分離,高效液相色譜法中的梯度分析方法常常被人們首先使用。然而,一旦完成單次樣品分析,系統(tǒng)必須返回到初始狀態(tài),這大大降低了多試樣分析的吞吐量�；旌夏Ｊ缴V方法是基于改變流動(dòng)相的選擇而開發(fā)的一種色譜方法,它至少同時(shí)存在兩種相互作用的機(jī)制,能對(duì)極性和非極性分子具有很強(qiáng)的保留。相比于反相或離子交換方法,該色譜方法由于使用了一個(gè)具有多個(gè)相互作用機(jī)制固定相,使其具有更大的應(yīng)用范圍。混合色譜法的一個(gè)主要優(yōu)勢(shì)是同一色譜柱可以使用一個(gè)單一的模式(如離子交換或反相)下使用或在組合的模式下使用。多維分離作為混合色譜方法中的一種,它是通過耦合兩個(gè)或兩個(gè)以上的具有相同或不同的分離機(jī)制類似柱或獨(dú)立柱,使特殊的分析峰從第一個(gè)維度轉(zhuǎn)移到第二個(gè)維度或更多維度。相比于簡(jiǎn)單的一維分離,這種簡(jiǎn)單的方法提供了更高的分辨率和靈敏度以及足夠的吞吐量和再現(xiàn)性。因此,本論文主要采用化學(xué)改性或是物理封裝技術(shù)制備了一系列混合色譜柱并對(duì)其色譜性能進(jìn)行研究探討。具體研究?jī)?nèi)容如下:第一章緒論首先介紹了毛細(xì)管液相色譜(CLC)的基本概念包括CLC的發(fā)展史、色譜柱的類型以及常見色譜固定相的應(yīng)用領(lǐng)域;其次對(duì)親水作用色譜(HILIC)進(jìn)行了介紹;再次對(duì)混合模式色譜(MMC)固定相及其應(yīng)用進(jìn)行綜述。最后提出本論文的研究目的和意義。第二章是剛果紅衍生硅膠(Sil-CR)固定相的制備及其在毛細(xì)管液相色譜中的應(yīng)用。剛果紅(CR)作為磺酸偶氮苯酸堿指示劑,當(dāng)環(huán)境pH值為3.0-5.2時(shí),兩個(gè)偶氮基團(tuán)發(fā)生質(zhì)子化,表現(xiàn)出兩性離子特征,染料顏色變化從藍(lán)色到紅色。離子化的磺酸基團(tuán)、質(zhì)子化的偶氮基團(tuán)和pi-pi-stacking行為使CR固定相具有多重作用機(jī)制。因此,我們將CR衍生硅膠用作固定相填充制備了 Sil-CR毛細(xì)管MMC柱,探討其在不同模式下的分離機(jī)制。實(shí)驗(yàn)結(jié)果表明,CR毛細(xì)管MMC柱在反相液相色譜(RPLC),HILIC和富水色譜(PALC)三種模式下均能使用的多模色譜分離能力。苯甲酸衍生物和磺胺類藥物的有效分離揭示出CR衍生硅膠具有混合模式保留行為。與ODS單模保留行為不同,該色譜柱除了親疏水保留機(jī)理外還有離子交換作用機(jī)理。另外,醇羥基及殘氨基的存在使得該色譜柱具有多個(gè)作用位點(diǎn),能增強(qiáng)與分析物間相互作用,擴(kuò)大了被分析物的測(cè)試范圍。同時(shí)該材料制備的色譜柱對(duì)被分析物有很好保留,而且作為色譜柱具有良好重現(xiàn)性和穩(wěn)定性。由于多個(gè)功能基團(tuán)的存在,可預(yù)見的是這種材料不僅可以用作通用的色譜固定相而且在其他化學(xué)領(lǐng)域可作為一個(gè)固體萃取吸附劑。第三章是剛果紅衍生硅膠與十八烷基硅膠混合模式色譜柱的制備和性能評(píng)價(jià)。十八烷基硅膠(ODS)作為經(jīng)典的反相色譜材料針對(duì)于離非極性化合物和弱極性化合物具有優(yōu)異的分離能力。因此,為了提升CR柱在非極性化合物的分離能力,本章分別通過化學(xué)方法和物理方法制備了四種經(jīng)ODS改性的CR柱,它們分別是 Sil-CR-con-ODS 接枝柱、Sil-CR-bis-ODS 鍵合柱、Sil-CR-mix-ODS 混合柱和Sil-CR-tan-ODS兩相柱。通過對(duì)苯系物的分離分析得到Sil-CR-tan-ODS兩相柱不但在制備上能精確可控其固定相組成比例還具有與一次填充色譜柱柱效相當(dāng)。通過對(duì)異構(gòu)體,極性與非極性化合物組成的混合物的分離分析得出Sil-CR-tan-ODS兩相柱的制備是非常成功的。第四章是牛磺酸衍生硅膠與十八烷基硅膠混合模式色譜柱的制備與性能評(píng)價(jià)。牛磺酸衍生硅膠(TDS)固定相用于HILIC分離各種極性和弱極性化合物表現(xiàn)出極強(qiáng)的保留。結(jié)合ODS和牛磺酸的兩大優(yōu)點(diǎn),很容易實(shí)現(xiàn)分離極性和弱極性化合物的混合物。相比單一的固定相柱,該柱可以擴(kuò)大范圍的樣本選擇和減少樣品預(yù)處理。更重要的是,多個(gè)作用機(jī)制能大大延長(zhǎng)被分析物的保留時(shí)間,提高對(duì)樣品的選擇性和分離度。與一般的二維系統(tǒng)相比,這種毛細(xì)管連續(xù)裝填色譜操作簡(jiǎn)單、穩(wěn)定,具有較好的適用性。因此,在本章中,我們制備了一種TDS-ODS MMC兩相柱,苯同系物、多環(huán)芳烴、核苷酸和生物胺分別在該色譜柱上進(jìn)行分離測(cè)試。實(shí)驗(yàn)結(jié)果表明,該兩相柱結(jié)合ODS和TDS的各自優(yōu)勢(shì),不僅展示了對(duì)核苷酸具有良好的選擇性,也展示對(duì)高疏水性和高親水混合物的同時(shí)保留特性。該系統(tǒng)結(jié)合了多維分離的諸多優(yōu)勢(shì)和固定相組成的靈活調(diào)配優(yōu)勢(shì),能更好增強(qiáng)對(duì)被分析物的選擇性,適合于復(fù)雜樣品的分析。第五章是氨丙基衍生硅膠和�；撬嵫苌枘z混合模式色譜柱的制備和性能評(píng)價(jià)。氨丙基衍生硅膠(APS)被用于HILIC,特別是針對(duì)于碳水化合物的分離起到優(yōu)越的分離性能,它對(duì)于分析芳香族化合物、有機(jī)酸及無機(jī)陰離子分離也具有較好選擇效果。然而,它對(duì)于某些化合物特別是陽離子化合物則表現(xiàn)不佳或不具有選擇保留特性。TDS為強(qiáng)陽離子交換材料在HILIC模式對(duì)核苷核堿以及生物胺表現(xiàn)出良好的分離特性。由于它們都能被運(yùn)用于HILIC,故而選用TDS作為APS改性材料來彌補(bǔ)其在分離陽離子化合物上的不足。在本章中,我們制備了一種APS-TDSMMC兩相柱,經(jīng)其對(duì)生物胺類物質(zhì),有機(jī)酸類物質(zhì),核苷核堿和磺胺藥物的分離試驗(yàn),我們發(fā)現(xiàn)TDS對(duì)APS的改性是非常成功的。APS-TDS柱不僅兼具有單一 APS柱和單一 TDS柱的全部功能,同時(shí)兩種固定相的共同作用使得分析物進(jìn)行了一次等度的2D-LC(HILIC×HILIC)分離,其直接的結(jié)果是出現(xiàn)了超過于單一APS柱或單一TDS柱的分離性能。滿意的結(jié)果表明,該連續(xù)填充柱能簡(jiǎn)單且完美實(shí)現(xiàn)APS和TDS的相互改性,這為任意多個(gè)色譜固定相的物理改性提供了一種依據(jù)和方法。第六章是磺基甜菜堿衍生硅膠和十八烷基硅膠混合模式色譜柱的制備及性能評(píng)價(jià)�；腔鸩藟A兩性離子固定相(ZIC)是一種含有APS與TDS功能基團(tuán)的化學(xué)改性衍生材料。它不但可以分離反相中保留很弱,或是根本沒有保留的化合物甚至是高極性的水溶性化合物,而且由于存在陰陽離子基團(tuán),它能隨著pH的改變而改變自身的電荷類型達(dá)到陰陽離子的交換。但是對(duì)于未能電離的化合物和LogP值較大的物質(zhì)則出現(xiàn)弱的選擇性保留或是幾乎無選擇性保留。然而,該類化合物在反相(RP)柱上卻是極其容易被保留并被選擇性分離。一旦能夠?qū)烧呓Y(jié)合在一起,發(fā)揮各自的性能,那么這將大大擴(kuò)大了分析樣品的適用范圍。因此,在本章中我們采用了商品化的ZIC制備了一種ZIC-ODS MMC兩相柱,該色譜柱對(duì)由核苷、核堿和苯同系物組成的跨極性混合物具有同時(shí)保留分離的能力。此外,對(duì)于具有極性相近的磺胺類藥物,ODS所具有的RP機(jī)制彌補(bǔ)了 ZIC分離上的不足。在對(duì)位置異構(gòu)體的分離上,由于RP機(jī)制的引入,使得ZIC-ODS具有了很好的空間識(shí)別能力。
[Abstract]:With the development of the chromatography discipline, chromatograph workers pay more attention to the separation and analysis of complex samples. This requires the simultaneous separation of polar and nonpolar mixtures, ionic and neutral mixtures or organic and inorganic mixtures on the same chromatographic column. Generally, the ladder in the separation of complex mixtures, the ladder in high performance liquid chromatography The degree analysis method is often used first. However, once the single sample analysis is completed, the system must return to the initial state, which greatly reduces the throughput of the multi sample analysis. The mixed mode chromatography is a chromatographic method based on the choice of changing the mobile phase. At least two mechanisms of interaction exist at the same time, One of the main advantages of the mixed chromatography method is that the same chromatographic column can use a single mode (such as ion exchange). Use or use under a combined mode. Multidimensional separation is one of the mixed chromatography methods, which transfers special analysis peaks from the first dimension to second dimensions or more dimensions by coupling two or more of the same or different separation mechanisms that have the same or different separation mechanisms to second dimensions or more dimensions. One dimensional separation, this simple method provides higher resolution and sensitivity as well as sufficient throughput and reproducibility. Therefore, a series of mixed chromatographic columns are prepared by chemical modification or physical encapsulation technology. The content of the study is as follows: first introduction is introduced. The basic concepts of capillary liquid chromatography (CLC) include the history of the development of CLC, the type of chromatographic column and the application of common chromatographic stationary phase. Secondly, the hydrophilic interaction chromatography (HILIC) is introduced, and the fixed phase of the mixed mode chromatography (MMC) and its application are reviewed. Finally, the purpose and significance of this paper are put forward. Second chapters It is the preparation of Congo red derived silica gel (Sil-CR) fixed phase and its application in capillary liquid chromatography. Congo red (CR) is a sulfonated azobenzene acid base indicator. When the environmental pH value is 3.0-5.2, the two azo groups are protonated, showing the characteristics of the amphoteric ions, the color changes of the dye from blue to red. The sulfonated sulfonic group and the mass of the ions. The azo group and the pi-pi-stacking behavior of the azo groups make the CR stationary phase multiple mechanism. Therefore, we use CR derived silica gel as a stationary phase to prepare the Sil-CR capillary MMC column and discuss the separation mechanism under different modes. The experimental results show that the CR capillary MMC column is in the reverse phase liquid chromatography (RPLC), HILIC and water rich chromatography (PALC). The effective separation of multimode chromatography that can be used in the three modes. The effective separation of benzoic acid derivatives and sulfonamides reveals that the CR derived silica gel has a mixed mode retention behavior. Unlike the ODS single mode retention behavior, the chromatographic column has the mechanism of ion exchange in addition to the hydrophobic retention mechanism. At the same time, the chromatographic column can enhance the interaction between the analyte and expand the test range of the analyte. The chromatographic column prepared by this material is well preserved for the analyte and has good reproducibility and stability as a chromatographic column. The material can not only be used as a general chromatographic stationary phase but also as a solid extractive adsorbent in other chemical fields. The third chapter is the preparation and performance evaluation of the mixed mode chromatography column of Congo red derived silica gel and eighteen alkyl silica gel. The eighteen alkyl silica gel (ODS) is used as a classic anti phase chromatography material for the separation of non polar compounds and The weak polar compounds have excellent separation ability. Therefore, in order to improve the separation ability of CR columns in non polar compounds, four kinds of ODS modified CR columns were prepared by chemical and physical methods, respectively, Sil-CR-con-ODS grafting column, Sil-CR-bis-ODS bonding column, Sil-CR-mix-ODS column and Sil-CR-tan-ODS two respectively. Phase column. Through the separation and analysis of the benzene series, it is found that the Sil-CR-tan-ODS two phase column is not only able to accurately control the composition of its stationary phase, but also is equivalent to the column effect of a packed column. The preparation of the Sil-CR-tan-ODS two phase column is obtained by the separation and analysis of the mixture of isomers, polar and non polar compounds. Successful. The fourth chapter is the preparation and performance evaluation of the mixed mode chromatography column of taurine derived silica gel and eighteen alkyl silica gel. The immobilized phase of taurine derived silica gel (TDS) is used in HILIC separation of various polar and weak polar compounds with very strong retention. It is easy to achieve separation polarity and weak polarity by combining the two advantages of ODS and taurine. A mixture of compounds. Compared to a single stationary phase column, the column can expand the range of sample selection and reduce sample pretreatment. More importantly, multiple mechanisms can greatly prolong the retention time of the analyte, improve the selectivity and separation of the sample. Compared with the general two-dimensional system, this capillary continuous loading chromatography operation Therefore, in this chapter, we have prepared a TDS-ODS MMC two-phase column, benzene homologue, polycyclic aromatic hydrocarbons, nucleotides and biogenic amines separately on the column. The experimental results show that the two phase column combines the advantages of ODS and TDS, which not only shows the good selection of nucleotides. The fifth chapter is a mixture of ammonia and taurine derived silica gel and taurine derived silica gel. The system combines the advantages of multidimensional separation and the flexibility of the fixed phase, which can better enhance the selectivity of the analyte and be suitable for the analysis of complex samples. Preparation and performance evaluation of chromatographic columns. Ammonia propyl derived silica gel (APS) has been used in HILIC, especially for separation of carbohydrates. It has a better choice for the analysis of aromatic compounds, organic acids and inorganic anions. .TDS is a strong cationic exchange material that shows good separation characteristics for nucleoside nucleobase and biogenic amines in HILIC mode. Because they can all be used in HILIC, TDS is used as a APS modified material to make up for its deficiency in separation of cationic compounds. In this chapter, we A APS-TDSMMC two phase column was prepared by the separation test of biogenic amines, organic acids, nucleoside nucleobases and sulfonamides. We found that the modification of TDS to APS is a very successful.APS-TDS column not only with a single APS column and a single TDS column, but also the combined action of two stationary phases to make the analyte in the same time. The separation of an equal degree of 2D-LC (HILIC x HILIC) has been performed. The direct result is that the separation performance exceeds the single APS column or single TDS column. The satisfactory results show that the continuous filling column can easily and perfectly realize the mutual modification of APS and TDS, which provides a basis and method for the physical modification of any fixed phase fixed phase. The sixth chapter is the preparation and performance evaluation of the mixed mode chromatographic column with sulfonated betaine derived silica gel and eighteen alkyl silica gel. The sulfonated betaine amphoteric ion fixed phase (ZIC) is a chemically modified derivative containing APS and TDS functional groups. It can not only separate the compounds that are very weak in the reverse phase or are not retained at all or even the compounds that are not retained. The high polarity water soluble compound, and because of the existence of the anion group, it can change its charge type to exchange of yin and Yang with the change of pH, but there is a weak selective retention or few selective retention for the compounds which are not ionized and the material with larger LogP value. However, this kind of compound is in the opposite direction. The phase (RP) column is extremely easy to be retained and selectively separated. Once the two can be combined to perform their respective performance, this will greatly enlarge the scope of application of the analytical samples. Therefore, in this chapter, we use a commercialized ZIC to prepare a ZIC-ODS MMC two-phase column, which is composed of nucleosides, nuclear bases and benzene. The cross polar mixture composed of homologues has the ability to retain the separation at the same time. In addition, for the sulfonamides with very similar sulfonamides, the RP mechanism of ODS has made up for the shortage of ZIC separation. In the separation of the location isomers, the ZIC-ODS has a good spatial recognition ability due to the introduction of the RP mechanism.

【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O657.72

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本文編號(hào)：1839418