Deb Mousumi, Hassan Nadira, Chowdhury Deepak, Sanfui Md Hussain, Roy Shrestha, Bhattacharjee Chiranjib, Majumdar Swapan, 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 Chemical Engineering, Jadavpur University, Kolkata, India.
Macromol Rapid Commun. 2022 Oct;43(19):e2200317. doi: 10.1002/marc.202200317. Epub 2022 Jul 7.
Here, redox active aliphatic luminescent polymers (ALPs) are synthesized via polymerization of N,N-dimethyl-2-propenamide (DMPA) and 2-methyl-2-propenoic acid (MPA). The structures and properties of the optimum ALP3, ALP3-aggregate and Cu(I)-ALP3, ratiometric pH sensing, redox activity, aggregation enhanced emission (AEE), Stokes shift, and oxygen-donor selective coordination-reduction of Cu(II) to Cu(I) are explored via spectroscopic, microscopic, density functional theory-reduced density gradient (DFT-RDG), fluorescence quenching, adsorption isotherm-thermodynamics, and electrochemical methods. The intense blue and green fluorescence of ALP3 emerges at pH = 7.0 and 9.0, respectively, due to alteration of fluorophores from -C(═O)N(CH ) / -C(═O)OH to -C(O )═N (CH ) / -C(═O)O , inferred from binding energies at 401.32 eV (-C(O )═N (CH ) ) and 533.08 eV (-C(═O)O ), significant red shifting in absorption and emission spectra, and peak at 2154 cm . The n-π* communications in ALP3-aggregate, hydrogen bondings within 2.34-2.93 Å (intramolecular) in ALP3 and within 1.66-2.89 Å (intermolecular) in ALP3-aggregate, respectively, contribute significantly in fluorescence, confirmed from NMR titration, ratiometric pH sensing, AEE, excitation dependent emission, and Stokes shift and DFT-RDG analyses. For ALP3, Stokes shift, excellent limit of detection, adsorption capacity, and redox potentials are 13561 cm /1.68 eV, 0.137 ppb, 122.93 mg g , and 0.33/-1.04 V at pH 7.0, respectively.
在此，通过N，N-二甲基-2-丙烯酰胺（DMPA）和2-甲基-2-丙烯酸（MPA）的聚合反应合成了氧化还原活性脂肪族发光聚合物（ALPs）。通过光谱、显微镜、密度泛函理论-约化密度梯度（DFT-RDG）、荧光猝灭、吸附等温线-热力学和电化学方法，研究了最佳ALP3、ALP3聚集体和Cu（I）-ALP3的结构和性质、比率pH传感、氧化还原活性、聚集诱导发光（AEE）、斯托克斯位移以及Cu（II）向Cu（I）的氧供体选择性配位还原。由于荧光团从-C（═O）N（CH）/-C（═O）OH转变为-C（O）═N（CH）/-C（═O）O，ALP3分别在pH = 7.0和9.0时出现强烈的蓝色和绿色荧光，这是根据401.32 eV（-C（O）═N（CH））和533.08 eV（-C（═O）O）处的结合能、吸收和发射光谱中的显著红移以及2154 cm处的峰推断得出的。ALP3聚集体中的n-π*相互作用、ALP3中2.34-2.93 Å（分子内）以及ALP3聚集体中1.66-2.89 Å（分子间）内的氢键分别对荧光有显著贡献，这通过NMR滴定、比率pH传感、AEE、激发依赖发射以及斯托克斯位移和DFT-RDG分析得到证实。对于ALP3，在pH 7.0时，斯托克斯位移、出色的检测限、吸附容量和氧化还原电位分别为13561 cm /1.68 eV、0.137 ppb、122.93 mg g和0.33/-1.04 V。
