Dutta Arnab, Mahapatra Manas, Deb Mousumi, Ghosh Narendra Nath, Chattopadhyay Pijush Kanti, Singha Nayan Ranjan
Advanced Polymer Laboratory, Department of Polymer Science and Technology, Government College of Engineering and Leather Technology (Post Graduate), Maulana Abul Kalam Azad University of Technology, Salt Lake City, Kolkata, West Bengal, 700106, India.
Department of Chemistry, University of Gour Banga, Mokdumpur, Malda, West Bengal, 732103, India.
Macromol Rapid Commun. 2021 Jan;42(2):e2000522. doi: 10.1002/marc.202000522. Epub 2020 Nov 18.
This work reports the design and synthesis of two nonaromatic biocompatible macromolecular luminogens, i.e., 2-(dimethylamino)ethyl methacrylate-co-2-(dimethylamino)ethyl 3-(N-(methylol)acrylamido)-2-methylpropanoate-co-N-(methylol)acrylamide/DMAEMA-co-DMAENMAMP-co-NMA (P1) and methacrylic acid-co-3-(N-(methylol)acrylamido)-2-methylpropanoic acid-co-N-(methylol)acrylamide/MEA-co-NMAMPA-co-NMA (P2), prepared through in situ anchored acrylamido-ester/DMAENMAMP and acrylamido-acid/NMAMPA third comonomers, respectively, in a facile polymerization of two non-luminous monomers in water medium to circumvent the drawbacks related to aggregation-caused quenching of aromatic luminogens. The structures of P1/P2, in situ anchored comonomers, fluorophores, N-branching associated n-π* interactions, and hydrogen bonding assisted aggregation-enhanced emissions are comprehended by nuclear magnetic resonance, Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible, thermogravimetric analysis (TGA), dynamic light scattering (DLS), transmission electron microscopy (TEM), fluorescence lifetime, and fluorescence imaging. P1 and P2 are appropriate for sensitive detections/exclusions of Fe(III)/Cu(II) and cell-imaging. The intrinsic fluorescence, on-off sensing, selective coordinations of Fe(III) and Cu(II) with fluorophores, emission quenching mechanisms, and removals of Fe(III) and Cu(II) are investigated by DFT/NTO analyses of P1/P2 and Fe(III)-P1 and Cu(II)-P2 complexes, XPS, and isotherms and kinetics parameters. The excellent biocompatibilities, comparable limit of detections, i.e., 1.70 × 10 and 1.59 × 10 [m], and higher adsorption capacities, i.e., 77.25 and 154.13 mg g , at low ppm; 303 K; and pH = 7 compel P1/P2 to be acceptable for multipurpose applications.
本工作报道了两种非芳香族生物相容性大分子发光剂的设计与合成，即甲基丙烯酸2-(二甲氨基)乙酯-co-3-(N-(羟甲基)丙烯酰胺基)-2-甲基丙酸2-(二甲氨基)乙酯-co-N-(羟甲基)丙烯酰胺/DMAEMA-co-DMAENMAMP-co-NMA（P1）和甲基丙烯酸-co-3-(N-(羟甲基)丙烯酰胺基)-2-甲基丙酸-co-N-(羟甲基)丙烯酰胺/MEA-co-NMAMPA-co-NMA（P2），它们分别通过原位锚定丙烯酰胺基酯/DMAENMAMP和丙烯酰胺基酸/NMAMPA第三共聚单体，在水介质中使两种非发光单体进行简便聚合反应制备而成，以规避与芳香族发光剂聚集导致猝灭相关的缺点。通过核磁共振、傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）、紫外可见光谱、热重分析（TGA）、动态光散射（DLS）、透射电子显微镜（TEM）、荧光寿命和荧光成像等手段，对P1/P2的结构、原位锚定共聚单体、荧光团、N-支化相关的n-π*相互作用以及氢键辅助的聚集增强发射进行了研究。P1和P2适用于对Fe(III)/Cu(II)的灵敏检测/排除以及细胞成像。通过对P1/P2以及Fe(III)-P1和Cu(II)-P2配合物进行DFT/NTO分析、XPS以及等温线和动力学参数，研究了其固有荧光、开关传感、Fe(III)和Cu(II)与荧光团的选择性配位、发射猝灭机制以及Fe(III)和Cu(II)的去除情况。P1/P2具有出色的生物相容性、相当的检测限，即1.70×10和1.59×10 [m]，以及在低ppm、303 K和pH = 7条件下更高的吸附容量，即77.25和154.13 mg g，使其适用于多种用途。
