Abstract
The newly designed polythiophene chemosensors (PT1 and PT2) were synthesized via the Suzuki–Miyaura polymerization with appropriate yields. The photophysical properties of PTs thus obtained were examined by means of UV/vis, fluorescence, excitation spectroscopy, and time-correlated single-photon-counting method. The π–π* transitions around 400–600 nm and the emissions in the range of 400–650 nm were observed. The binding behavior of PTs was also investigated upon the interaction of tetrabutylammonium or tetrabutylphosphonium isophthalate, affording the binding constants (K) of 5790–8310 M−1, which were quite smaller than those observed in the corresponding repeating unit. The comprehensive analyses of the UV/vis data and theoretical calculation supports revealed the origins of scope and limitation toward signal-amplification sensing. The present results obtained herein will guide the development of new amplification chemosensors.
Highlights
A smarter sensing method seems to be a signal ampli cation, e.g., polymerase chain reaction (PCR)[26] and enzyme-linked immunosorbent assay (ELISA),[27] the former of which has been well-known owing to the Covid-19 disaster in recent years
The signal-ampli cation sensing” (SASS) approach consists of the following three steps: (1) supramolecular complexation of a target analyte with a recognition site in a chemosensor skeleton, (2) allosteric propagation of binding information upon the complexation of the analyte through a polymer chain, and (3) signal ampli cation caused by an enhanced complexation stability of the analyte into an induced- t site
In order to clearly estimate the scope and limitations of the PTbased SASS, we carefully designed monothiophene- and bithiophene-spaced PT1 and PT2, respectively, enabling us to understand the effects on the SASS mechanism that may be different from those observed in the direct triad monomer unit (TM)-connected PT0
Summary
Chemical sensing of target molecules with chemosensors has become a recent trend in the elds of chemistry due to some applications in the precise detection of hazardous explosives and toxic vapors (VOCs)[1,2,3] and biomarkers relating to serious diseases or cancers.[4,5,6] The previous chemosensors have been achieved based on the “lock-and-key” model, which was proposed as activations of enzymes by Emil Fischer since the late 1800's,7 and many sophisticated reports have been exempli ed so far.[8,9,10,11,12,13,14,15,16,17,18,19] unluckily, such a model is not as almighty since target analytes have become complicated structurally and conformationally, e.g., peptides, proteins, and carbohydrates.[20,21,22,23,24] This current research implies the necessity of an alternative to the conventional lock-and-key principlebased chemosensor construction.[25]A smarter sensing method seems to be a signal ampli cation, e.g., polymerase chain reaction (PCR)[26] and enzyme-linked immunosorbent assay (ELISA),[27] the former of which has been well-known owing to the Covid-19 disaster in recent years.
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