苯硼酸衍生物的合成及糖识别性质研究

发布时间：2018-05-25 10:15

本文选题：苯硼酸衍生物 + 荧光识别　；参考：《辽宁大学》2017年硕士论文

【摘要】：自从有机硼酸类化合物在1860年第一次被人工合成后,由于其特殊的原子构型,以及稳定和对环境友好的性质,一直被广泛运用在有机合成、糖类和离子识别以及生物医学等领域。本文将当今有机合成和分子识别的研究热点相结合,设计并获得了两种能够用于果糖识别的苯硼酸类目标产物1和2。本文设计并合成了2种含有磷酸酯取代基的苯硼酸化合物,并对其进行了性质研究和表征以确认其结构组成,并运用荧光光谱法测试了其对糖类化合物的识别作用,计算了相应的结合常数K,并将其应用于蜂蜜中果糖的检测。合成实验采用one pot reaction(一锅法),将2种取代位置不同的甲酰基苯硼酸(4-甲酰基苯硼酸和2-甲酰基苯硼酸)与对氨基苯甲酸反应得到有硼酸基团的Schiff碱类化合物,并把亚磷酸二乙酯加入到反应中,用混合溶剂结晶得到带有膦酸酯取代基的水溶性良好的苯硼酸类化合物1和2。经过合成三大谱图(IR,1H NMR(DMSO-d6),MS)的验证和表征,推测出来了两个化合物的结构,确定为我们预测的产物,并据其结构,设计了荧光实验。荧光定性实验表明,化合物在固态和水溶液状态下都可以发一定的荧光,加入糖类分子后,荧光强度有不同程度的增强,且都对D-果糖有特异性识别作用。液体荧光定量实验表明,化合物1在溶液中与D-果糖有十分良好的结合能力,且这种结合能力明显强于化合物2,产生此现象的原因可能为化合物1中有两个游离的-OH,能更好的与二醇类的果糖作用。用化合物1作为受体检测椴树和槐花蜂蜜中果糖含量,使用混合糖类荧光光谱的工作曲线时,其RSD分别为0.1260%和0.4107%,标准偏差RD分别为-0.71%和-1.8%;使用D-果糖做工作曲线时,其RSD分别为0.1692%和0.5750%,标准偏差RD分别为5.66%和4.5%。说明使用混合糖类荧光光谱的工作曲线时可以排除其他糖类对检测的影响,数据更为准确。固体荧光实验显示了和溶液实验中相似的现象:两种化合物本身发微弱黄绿色荧光,加入果糖后发光有肉眼可见的明显的荧光增强,而加入其他糖类的化合物荧光强度无明显变化,且化合物1的荧光变化增强幅度明显高于2。之后又测试了金属盐类对化合物1与果糖混合体系(摩尔比3:1)的荧光强度的影响,其中加入氯化铁(FeCl3)和氯化钴(CoCl2)的混合物发生了很强的猝灭效应,而测试的其他金属盐(CaCl2,CrCl2,MnCl2,CuCl2,ZnCl2)均无此现象,说明该混合体系可定向识别金属铁盐和钴盐。
[Abstract]:Since organic boric acid compounds were first synthesized in 1860, they have been widely used in organic synthesis because of their special atomic configuration and their stable and environmentally friendly properties. Sugar and ion recognition and biomedicine. In this paper, based on the research focus of organic synthesis and molecular recognition, two phenylboric acid target products, 1 and 2, which can be used for fructose recognition are designed and obtained. In this paper, two kinds of phenylboric acid compounds containing phosphate ester substituents were designed and synthesized, and their properties were studied and characterized to confirm their structural composition. The recognition of carbohydrate compounds was tested by fluorescence spectroscopy. The binding constant K was calculated and applied to the determination of fructose in honey. In this paper, one pot reaction( one-pot method was used to synthesize Schiff base compounds with boric acid groups by reacting two kinds of formyl benzoboric acid with 4-formylbenzboric acid and 2-formyl benzoic acid with p-aminobenzoic acid. Diethyl phosphite was added to the reaction and crystallized in a mixed solvent to obtain water-soluble benzoboric acid compounds 1 and 2 with phosphonate substituents. After the verification and characterization of the synthesis of the three spectra of 1H NMR-DMSO-d6MS-MS, the structures of the two compounds were deduced and determined to be our predicted products. According to the structure of the compounds, fluorescence experiments were designed. The fluorescence qualitative experiment showed that the compounds could emit some fluorescence in the state of solid state and aqueous solution, and the fluorescence intensity of the compounds increased in varying degrees after the addition of carbohydrate molecules, and all of them had a specific recognition effect on D-fructose. Liquid fluorescence quantitative experiments show that compound 1 has a very good binding ability with D-fructose in solution. The binding ability of compound 2 is obviously stronger than that of compound 2. The reason for this phenomenon may be that there are two free -OHs in compound 1, which can act better with fructose of diol. The content of fructose in Linden and Sophora japonica honey was determined by using compound 1 as the receptor. When the working curve of fluorescence spectrum of mixed sugars was used, the RSD of compound 1 was 0.1260% and 0.4107, respectively, and the standard deviation (Rd) was -0.71% and -1.8%, respectively; when using D-fructose as the working curve, the standard deviation was -0.71% and -1.8%, respectively. The RSD was 0.1692% and 0.5750%, and the standard deviation (Rd) was 5.66% and 4.5%, respectively. The results show that the working curve of mixed sugars fluorescence spectrum can exclude the influence of other sugars on the detection, and the data are more accurate. The solid-state fluorescence experiment showed a similar phenomenon to that in the solution experiment: the two compounds themselves emit weak yellow-green fluorescence, and when fructose is added, there is a visible enhancement of fluorescence visible to the naked eye. However, the fluorescence intensity of compounds added with other carbohydrates had no obvious change, and the fluorescence intensity of compound 1 was significantly higher than that of compound 1. The effect of metal salts on the fluorescence intensity of the mixture of compound 1 and fructose (molar ratio 3: 1) was also tested, in which the mixture of FeCl _ 3 and CoCl _ 2 had a strong quenching effect. The other metal salts tested, CaCl2CrCl2CrCl2CrCl2MnCl2CuCl2CuCl2ZnCl2) have no such phenomenon, which indicates that the mixed system can be used to identify metallic ferric salts and cobalt salts.
【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O627.31

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