Study on Recognition Mechanism of Al3+ by Cyanuric Chloride Molecules of Dual-Probe Group (DPG)
NING Xiao-yu1, WEI Gang2, GUANG Shan-yi1*, ZHAO Gang2, XU Hong-yao2,3
1. College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, China
2. College of Materials Sciences and Engineering and State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620, China
3.Research Center for Analysis and Measurement of Donghua University, Shanghai 201620, China
Abstract：The metabolism of aluminum in the human body is extremely slow, the ingested aluminum will accumulate in the body gradually, and the Al3+ of abnormal concentration will damage the central nervous system, leading to serious neurological diseases, so the detection of Al3+ efficiently and sensitively is very important. Fluorescent probes are widely used for analysis and detection of metal ion because of their advantages of convenient carrying, quick and easy detection, low price, good selectivity, etc., and a large number of literature for the detection of Al3+ are based on being complexed with Single-Probe Group (SPG) molecules at 1∶1, 2∶1, 3∶1, etc. In this paper, an active cyanuric chloride as a bridging group, a rhodamine B amide and a Schiff base derivative, p-amino benzoyl salicylic acid, as a cyanuric chloride molecule (RBCS) of a dual-probe group (DPG) was studied. It is prepared in one step by an easily controlled thermodynamic method. The total concentration of immobilized RBCS+Al3+ was 20 μmol·L-1, and the experimental results of Job-plot show that the fluorescence intensity at 578 nm reaches the highest value when the ratio of ions to total concentration is 0.68, by adjusting the concentration ration of the two, the result indicates that RBCS and Al3+ are mainly coordinated by 1∶2. The MALDI-TOF-MASS study found that the new peak of RBCS-Al3+ at 900.07 compared to the spectrum without Al3+, further verified that the DPG cyanuric chloride (RBCS) and Al3+ are complexed at 1∶2. The recognition mechanism of RBCS to Al3+ was studied in detail by the 1H NMR titration experiment with 0, 0.5, 1, 2, 3 equivalents of Al3+ added to the probe RBCS (10 mg) to compare the change of the characteristic H position. The results indicate that when Al3+ is present, the complexation of Al3+ with the carbonyl O, amino N and cyanuric chloride N on the rhodamine part of RBCS leads to the ring opening of rhodamine, at the same time, the imino group N of Schiff base and two O of carboxylic acid radical and phenol radical also bind with Al3+ respectively which solidifies the C═N bond and increases the overall conjugation resulting in fluorescence. In conclusion, the cyanuric chloride molecule (RBCS) can be used as a Double-probe group molecule for the recognition of Al3+ ions. RBCS-Al3+ showed orange-red fluorescence under 365 nm ultraviolet lamp irradiation, and the fluorescence increased gradually with the increase of Al3+ concentration. After optimizing the testing conditions of RBCS optical properties, the optical properties of RBCS were studied in ethanol/water (99/1, V/V) solution. The RBCS (10 μmol·L-1) in the ethanol/water (99/1, V/V) solution was carried out by fluorescence titration experiments at an excitation wavelength of 557 nm and an emission wavelength of 578 nm finally. The fluorescence intensity changes of RBCS (10 μmol·L-1) for different concentrations of Al3+ (0.01～8 eq) were tested, and the data was linearly regressed. The equation was y=32.336 0+65.364 1x, R2=0.993 3, and the linear range was 1～10 μmol·L-1. The detection limit of RBCS for Al3+ calculated by 3σ/k is 15.0 nmol·L-1. The research in this study can provide a reference for the design of double probe group (DPG) molecules for the detection of metal ions.
Key words：Al3+; Dual-probe group; Recognition mechanism; Rhodamine-schiff base derivative
宁晓钰，魏 刚，光善仪，赵 岗，徐洪耀. 双探针基团(DPG)聚氰分子对Al3+识别机理研究[J]. 光谱学与光谱分析, 2020, 40(01): 80-84.
NING Xiao-yu, WEI Gang, GUANG Shan-yi, ZHAO Gang, XU Hong-yao. Study on Recognition Mechanism of Al3+ by Cyanuric Chloride Molecules of Dual-Probe Group (DPG). SPECTROSCOPY AND SPECTRAL ANALYSIS, 2020, 40(01): 80-84.
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