RESUMEN
The metal-free porphyrins protonation has gained interest over five decades because its structure modification and hardly monoacid intermediate isolation. Here, upon the hydrogen atom abstraction processes, one step diproptonated H3STTP(BF4)2 (STTP = 5,10,15,20-tetraphenyl-21-thiaporphyrin) (3) and stepwise protonated HS2TTPSbCl6 (5) and diprotonated H2S2TTP(BF4)2 (6) (S2TTP = 5,10,15,20-tetraphenyl-21,23-thiaporphyrin) compounds were obtained using HSTTP and S2TTP with oxidants. The closed-shell protonated compounds were fully characterized using XRD, UV-vis, IR and NMR spectra. In addition, the reduced 19π compounds [K(2,2,2)]HSTTP (2) and [K(2,2,2)]S2TTP (7) were synthesized by the ligands with reductant KC8 in THF solution. These two open-shell compounds were characterized with UV-vis, IR and EPR spectroscopies. The semiempirical ZINDO/S method was employed to analyze the HOMO/LUMO gap lever and identify the electronic transitions of the UV-vis spectra of the closed- and open-shell porphyrin compounds.
RESUMEN
A smart home sleep respiratory monitoring system based on a breath-responsive covalent organic framework (COF) was developed and utilized to monitor the sleep respiratory behavior of real sleep apnea patients in this work. The capacitance of the interdigital electrode chip coated with COFTPDA-TFPy exhibits thousands-level reversible responses to breath humidity gases, with subsecond response time and robustness against environmental humidity. A miniaturized printed circuit board, an open-face-mask-based respiratory sensor, and a smartphone app were constructed for the wearable wireless smart home sleep respiratory monitoring system. Leveraging the sensitive and rapid reversible response of COFs, the COF-based respiratory monitoring system can effectively record normal breath, rapid breath, and breath apnea, enabling over a thousand cycles of hour-level continuous monitoring during daily wear. Next, we took the groundbreaking step of advancing the humidity sensor to the clinical trial stage. In clinical experiments on real sleep apnea patients, the COF-based respiratory monitoring system successfully recorded hour-level sleep respiratory data and differentiated the breathing behavior characteristics and severity of sleep apnea patients and subjects with normal sleep function and primary snoring patients. This work successfully advanced humidity sensors into clinical research for real patients and demonstrated the enormous application potential of COF materials in clinical diagnosis.