【摘要】：基于羅丹明的‘'OFF-ON"效應(yīng),本論文選取羅丹明B為熒光基團(tuán),通過與水合肼的取代反應(yīng),合成羅丹明B-酰肼作為反應(yīng)原料,設(shè)計(jì)并合成出了4種羅丹明B衍生物,利用質(zhì)譜、核磁對目標(biāo)化合物的結(jié)構(gòu)進(jìn)行了確認(rèn)。通過紫外吸收光譜和熒光光譜研究了不同識別基團(tuán)的引入對羅丹明B衍生物離子識別性能的影響。主要內(nèi)容如下：①R1是羅丹明B-酰肼與對溴苯甲醛直接相連,對金屬陽離子沒有識別能力。但對pH敏感,在酸堿條件下,出現(xiàn)開關(guān)環(huán)的顯色反應(yīng),且具有快速、穩(wěn)定、可逆的識別特點(diǎn)。②R2為直接引入對甲氧基苯甲醛,本身無色,無熒光,在加入Hg2+后熒光強(qiáng)度增加了15倍左右,并且顏色從無色變?yōu)樽霞t色。利用Job-Plot光度滴定法得到絡(luò)合比為1：1,結(jié)合常數(shù)為1.43×105L/mol,最低檢測限為12.5×10-mol/L,預(yù)測其可作為Hg2+熒光探針應(yīng)用的可能性。③R3以鄰苯二胺為識別基團(tuán),對Ag+和Cu2+都有一定的選擇性,同時(shí)伴隨著顏色從無色到粉色的變化,故在實(shí)際檢測應(yīng)用中兩者會存在干擾。在單獨(dú)對Ag+的識別實(shí)驗(yàn)中,所得體系的紫外最大吸光度和熒光發(fā)射強(qiáng)度都出現(xiàn)明顯增強(qiáng)的現(xiàn)象,熒光強(qiáng)度增加了25倍葒右,得到絡(luò)合比為1：1,結(jié)合常數(shù)為4.16×104 L/mol,最低檢測限為4.3×10-6mol/L。④R4以2-氨基-5-巰基-1,3,4-噻二唑?yàn)樽R別基團(tuán),能對Cu2+專一選擇識別,且不受其它離子十?dāng)_。作用時(shí)體系的的紫外最大吸光度出現(xiàn)明顯增強(qiáng)的現(xiàn)象,并能夠裸眼識別從無色到桃紅色的變化。得到絡(luò)合比為1：1,結(jié)合常數(shù)為4.45×1 04L/mol,最低檢測限為8.4×10-6mol/L,預(yù)測其可作為Cu2+熒光分子探針,應(yīng)用于環(huán)境檢測的可能性。
[Abstract]:Based on the Rhodamine OFF-ON effect, four Rhodamine B derivatives were designed and synthesized by the substitution reaction of hydrazine hydrate with Rhodamine B as the fluorescence group. Four Rhodamine B derivatives were designed and synthesized by mass spectrometry. The structure of the target compound was confirmed by NMR. The effects of different recognition groups on the ion recognition properties of Rhodamine B derivatives were studied by UV and fluorescence spectra. The main contents are as follows: 1: 1R1 is a direct link between rhodamine B-hydrazide and p-bromobenzaldehyde and has no ability to recognize metal cations. But sensitive to pH, the color reaction of switch ring appears under the condition of acid and base, and it has fast, stable and reversible recognition characteristic. 2R2 is the direct introduction of p-methoxybenzaldehyde, which is colorless and fluorescence free. After adding Hg 2, the fluorescence intensity increased about 15 times, and the color changed from colorless to purplish red. By means of Job-Plot spectrophotometric titration, the complexation ratio is 1: 1, the binding constant is 1.43 脳 10 ~ (-5) L / mol, and the lowest detection limit is 12.5 脳 10 ~ (-mol / L). The possibility of its application as a fluorescent probe for Hg2 is predicted. At the same time, with the change of color from colorless to pink, there will be interference between them in practical application. In the recognition experiment of Ag alone, the UV maximum absorbance and fluorescence emission intensity of the obtained system were obviously enhanced, and the fluorescence intensity increased by 25 times to the right. The complexation ratio is 1: 1, the binding constant is 4.16 脳 10 ~ 4 L / mol, the lowest detection limit is 4.3 脳 10 ~ (-6) mol / L 路L ~ (4) R _ (4) with 2-amino-5-mercapto-3-thiadiazole as the recognition group, the Cu _ (2) can be specifically selected and recognized without the interference of other ions. The UV maximum absorbance of the system increases obviously and can recognize the change from colorless to peach red by naked eyes. The complexation ratio is 1: 1, the binding constant is 4.45 脳 10 ~ (-4) L / mol, and the lowest detection limit is 8.4 脳 10 ~ (-6) mol / L. It is predicted that it can be used as a fluorescent molecular probe of Cu _ 2 for environmental detection.
【學(xué)位授予單位】：上海應(yīng)用技術(shù)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O657.3
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本文編號：2127253