本文選題：苯硼酸衍生物 + 熒光識別　； 參考：《遼寧大學(xué)》2017年碩士論文

【摘要】：自從有機(jī)硼酸類化合物在1860年第一次被人工合成后,由于其特殊的原子構(gòu)型,以及穩(wěn)定和對環(huán)境友好的性質(zhì),一直被廣泛運(yùn)用在有機(jī)合成、糖類和離子識別以及生物醫(yī)學(xué)等領(lǐng)域。本文將當(dāng)今有機(jī)合成和分子識別的研究熱點(diǎn)相結(jié)合,設(shè)計(jì)并獲得了兩種能夠用于果糖識別的苯硼酸類目標(biāo)產(chǎn)物1和2。本文設(shè)計(jì)并合成了2種含有磷酸酯取代基的苯硼酸化合物,并對其進(jìn)行了性質(zhì)研究和表征以確認(rèn)其結(jié)構(gòu)組成,并運(yùn)用熒光光譜法測試了其對糖類化合物的識別作用,計(jì)算了相應(yīng)的結(jié)合常數(shù)K,并將其應(yīng)用于蜂蜜中果糖的檢測。合成實(shí)驗(yàn)采用one pot reaction(一鍋法),將2種取代位置不同的甲�；脚鹚�(4-甲酰基苯硼酸和2-甲�；脚鹚�)與對氨基苯甲酸反應(yīng)得到有硼酸基團(tuán)的Schiff堿類化合物,并把亞磷酸二乙酯加入到反應(yīng)中,用混合溶劑結(jié)晶得到帶有膦酸酯取代基的水溶性良好的苯硼酸類化合物1和2。經(jīng)過合成三大譜圖(IR,1H NMR(DMSO-d6),MS)的驗(yàn)證和表征,推測出來了兩個化合物的結(jié)構(gòu),確定為我們預(yù)測的產(chǎn)物,并據(jù)其結(jié)構(gòu),設(shè)計(jì)了熒光實(shí)驗(yàn)。熒光定性實(shí)驗(yàn)表明,化合物在固態(tài)和水溶液狀態(tài)下都可以發(fā)一定的熒光,加入糖類分子后,熒光強(qiáng)度有不同程度的增強(qiáng),且都對D-果糖有特異性識別作用。液體熒光定量實(shí)驗(yàn)表明,化合物1在溶液中與D-果糖有十分良好的結(jié)合能力,且這種結(jié)合能力明顯強(qiáng)于化合物2,產(chǎn)生此現(xiàn)象的原因可能為化合物1中有兩個游離的-OH,能更好的與二醇類的果糖作用。用化合物1作為受體檢測椴樹和槐花蜂蜜中果糖含量,使用混合糖類熒光光譜的工作曲線時,其RSD分別為0.1260%和0.4107%,標(biāo)準(zhǔn)偏差RD分別為-0.71%和-1.8%;使用D-果糖做工作曲線時,其RSD分別為0.1692%和0.5750%,標(biāo)準(zhǔn)偏差RD分別為5.66%和4.5%。說明使用混合糖類熒光光譜的工作曲線時可以排除其他糖類對檢測的影響,數(shù)據(jù)更為準(zhǔn)確。固體熒光實(shí)驗(yàn)顯示了和溶液實(shí)驗(yàn)中相似的現(xiàn)象:兩種化合物本身發(fā)微弱黃綠色熒光,加入果糖后發(fā)光有肉眼可見的明顯的熒光增強(qiáng),而加入其他糖類的化合物熒光強(qiáng)度無明顯變化,且化合物1的熒光變化增強(qiáng)幅度明顯高于2。之后又測試了金屬鹽類對化合物1與果糖混合體系(摩爾比3:1)的熒光強(qiáng)度的影響,其中加入氯化鐵(FeCl3)和氯化鈷(CoCl2)的混合物發(fā)生了很強(qiáng)的猝滅效應(yīng),而測試的其他金屬鹽(CaCl2,CrCl2,MnCl2,CuCl2,ZnCl2)均無此現(xiàn)象,說明該混合體系可定向識別金屬鐵鹽和鈷鹽。
[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.
【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O627.31

【參考文獻(xiàn)】

相關(guān)碩士學(xué)位論文 前1條

1 張美音;3-酰胺基苯硼酸類化合物的合成及對D-果糖識別的研究[D];遼寧大學(xué);2011年

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本文編號：1933059