Organic thin-film transistors, owing to their intrinsic signal transformation and amplification abilities, have emerged as one of the promising biosensing platforms in health monitoring and environmental detection. Natural materials are considered to be important candidates due to the inherent bioactivity, intrinsic biocompatibility, good solution processability, and prominent flexibility. In this paper, we briefly review the progress of organic transistor-based biosensors developed by natural materials and discuss how the physicochemical properties of these materials govern the sensing performance. First, we summarize the fundamental qualities of the natural origins enabled carrier transport, signal transition, mechanical deformation, biodegradability of organic transistors toward biosensing. Then, we highlight recent advances and strategies of how to integrate bionatural materials into wearable and implantable organic transistor-based biosensors. Finally, we propose the challenges and perspectives for the next-generation evaluation of (bionic-)­natural species and their potential application in early disease diagnose, biomedical investigation, and smart systems.

The direct arylation polycondensation (DArP) has become one of the most important methods to construct conjugated polymers (CPs). However, the homocoupling side-reactions of environmentally-harmful aryl halides and the low regioseletive reactivities of unfunctionalized aryls hinder the development of DArP. Here, we report an efficient Pd and Cu co-catalysis DArP was presented via inert C-S bond cleavage of electron rich aryl thioethers, of which robustness was exemplified by over twenty conjugated polymers (CPs), including copolymers, homopolymers, and random polymers.The capture of oxidative addition intermediate together with experimental and theoretic results suggested the important role of palladium (Pd) and copper (Cu) co-catalysis with a bicyclic mechanism. The studies of NMR, molecular weights, trap densities, X-ray diffraction, and the charge transport mobilities revealed this method is an excellent choice for synthesizing CPs.

The direct arylation polycondensation (DArP) has become one of the most important methods to construct conjugated polymers (CPs). However, the homocoupling side‐reactions of aryl halides and the low regioseletive reactivities of unfunctionalized aryls hinder the development of DArP. Here, an efficient Pd and Cu co‐catalyzed DArP was developed via inert C−S bond cleavage of aryl thioethers, of which robustness was exemplified by over twenty conjugated polymers (CPs), including copolymers, homopolymers, and random polymers. The capture of oxidative addition intermediate together with experimental and theoretic results suggested the important role of palladium (Pd) and copper (Cu) co‐catalysis with a bicyclic mechanism. The studies of NMR, molecular weights, trap densities, two‐dimensional grazing‐incidence wide‐angle X‐ray scattering (2D‐GIWAXS), and the charge transport mobilities revealed that the homocoupling reactions were significantly suppressed with high regioselectivity of unfunctionalized aryls, suggesting this method is an excellent choice for synthesizing high performance CPs.

The direct arylation polycondensation (DArP) has become one of the most important methods to construct conjugated polymers (CPs). However, the homocoupling side‐reactions of aryl halides and the low regioseletive reactivities of unfunctionalized aryls hinder the development of DArP. Here, an efficient Pd and Cu co‐catalyzed DArP was developed via inert C−S bond cleavage of aryl thioethers, of which robustness was exemplified by over twenty conjugated polymers (CPs), including copolymers, homopolymers, and random polymers. The capture of oxidative addition intermediate together with experimental and theoretic results suggested the important role of palladium (Pd) and copper (Cu) co‐catalysis with a bicyclic mechanism. The studies of NMR, molecular weights, trap densities, two‐dimensional grazing‐incidence wide‐angle X‐ray scattering (2D‐GIWAXS), and the charge transport mobilities revealed that the homocoupling reactions were significantly suppressed with high regioselectivity of unfunctionalized aryls, suggesting this method is an excellent choice for synthesizing high performance CPs.

Nano-resolved doping of polymeric semiconductors can overcome scaling limitations toward highly integrated flexible electronics, but remains a fundamental challenge. Here, we report a general methodology for achieving nanoscale ion-implantation-like electrochemical doping of polymeric semiconductors by confining counterion electromigration in an electrolyte. The process is mediated by adjusting the electrolyte glass transition temperature (Tg) and the operating temperature (T), which generates a highly localized electric field distribution and anisotropic ion migration that nearly vertical to the nanotip electrodes. The confined doping produces a record resolution of 56 nm with a lowest lateral diffusion length (LDL) down to 6 nm, which approaches the polaron delocalization limit of the host polymer. Moreover, we demonstrate a universal exponential dependence of the doping resolution on the temperature difference (Tg−T) that can be used to depict the doping resolution for almost infinite polymeric semiconductors. Our results may stimulate the design and nanofabrication of novel polymer devices based on the nanoscale defined doping patterns.