Imine-Linked 2D Conjugated Porous Organic Polymer Films for Tunable Acid Vapor Sensing.

Two-dimensional (2D) films of conjugated porous organic polymers (C-POPs) can translate the rich in-plane functionalities of conjugated frameworks into diverse optical and electronic applications while addressing the processability issues of their crystalline analogs for adaptable device architectures. However, the lack of facile single-step synthetic routes to obtain large-area high-quality films of 2D-C-POPs has limited their application possibilities so far. Here, we report the synthesis of four mechanically robust imine-linked 2D-C-POP free-standing films using a single-step fast condensation route that is scalable and tunable. The rigid covalently bonded 2D structures of the C-POP films offer high stability for volatile gas sensing in harsh environments while simultaneously enhancing site accessibility for gas molecules due to mesoporosity by structural design. Structurally, all films were composed of exfoliable layers of 2D polymeric nanosheets (NSs) that displayed anisotropy from disordered stacking, evinced by out-of-plane birefringent properties. The tunable in-plane conjugation, different nitrogen centers, and porous structures allow the films to act as ultraresponsive colorimetric sensors for acid sensing via reversible imine bond protonation. All the films could detect hydrogen chloride (HCl) gas down to 0.05 ppm, far exceeding the Occupational Safety and Health Administration's permissible exposure limit of 5 ppm with fast response time and good recyclability. Computational insights elucidated the effect of conjugation and tertiary nitrogen in the structures on the sensitivity and response time of the films. Furthermore, we exploited the exfoliated large 2D NSs and anisotropic optoelectronic properties of the films to adapt them into micro-optical and triboelectric devices to demonstrate their real-time sensing capabilities.

Real-Time In Vivo Sensing of Nitric Oxide Using Photonic Microring Resonators.

Real-time in vivo detection of biomarkers, particularly nitric oxide (NO), is of utmost importance for critical healthcare monitoring, therapeutic dosing, and fundamental understanding of NO's role in regulating many physiological processes. However, detection of NO in a biological medium is challenging due to its short lifetime and low concentration. Here, we demonstrate for the first time that photonic microring resonators (MRRs) can provide real-time, direct, and in vivo detection of NO in a mouse wound model. The MRR encodes the NO concentration information into its transfer function in the form of a resonance wavelength shift. We show that these functionalized MRRs, fabricated using complementary metal oxide semiconductor (CMOS) compatible processes, can achieve sensitive detection of NO (sub-µM) with excellent specificity and no apparent performance degradation for more than 24 h of operation in biological medium. With alternative functionalizations, this compact lab-on-chip optical sensing platform could support real-time in vivo detection of myriad of biochemical species.