Utilizing Hairy Hollow Conjugated Microporous Polymers and Native Enzymes for Precise Aerobic Photocatalysis Under Near‐Infrared Wavelengths

Abstract

Utilizing photoregenerated cofactors in conjunction with enzymes in a sequential manner presents an effective approach for the synthesis of targeted compounds in gentle reaction conditions. Nevertheless, the integration of enzymes and photocatalysts has faced challenges due to the swift breakdown of biomaterials caused by high‐energy or blue lights and photoinduced reactive oxygen species, leading to the denaturation and deactivation of enzymatic materials. This study details the deliberate development and production of hairy hollow conjugated microporous polymers (S‐hPrTZ‐P HCMPs), achieved via Sonogashira–Hagihara coupling on SiO2 templates, followed by sulfonation, polymer grafting and ultimately eliminating the SiO2 cores. This technique leverages the distinctive characteristics of low‐energy near‐infrared light, such as its superior penetration ability, to effectively regenerate the enzymatic cofactor NAD+ from NADH. It can accomplish this feat even when faced with synthetic or biological barriers that are impermeable to visible light. Simultaneously, photogenerated reactive oxygen species are captured and neutralized by the hydrophilic polymer brushes, safeguarding the integrity of the enzymatic material. The adaptability of S‐hPrTZ‐P with photocatalytic properties is showcased alongside glucose 1‐dehydrogenase and glycerol dehydrogenase. This structure and morphology‐controlled strategy offers a promising pathway for various enzymatic photobiocatalysis employing stable, efficient, and reusable hairy HCMPs.

Enhancing Aqueous Reversible Addition–Fragmentation Chain Transfer Photopolymerization in Continuous Flow Reactors with Hairy Hollow Conjugated Microporous Polymer Nanocomposites

“…The UV–visible diffuse reflectance (UV–vis DR) spectra of all HCMPs and S- c EBDT-P displayed a wide, continuous absorption band spanning the entire visible spectrum and extending into the near-infrared region (Figure d). ,,, The observed red-shifts in the absorption edge, a typical feature commonly associated with benzothiadiazole-anchored HCMPs, indicated an expansion of electronic delocalization and structural connections across the aromatic skeletons. The optical band gap ( E g ) of 1.87 eV is derived from the Kubelka–Munk-transformed reflectance spectrum of S- h EBDT-P (Figure S12).…”

“…From the Fourier-transform infrared (FTIR) spectra, the 3300 cm −1 bands of hEBDT assigned to stretching suggested the effective integration of halosulfonic acid into the internal alkynes within S-hEBDT-P (Figure 2a). 49,51,56 The creation of a hollow cavity in HCMPs contributed to increased Brunauer−Emmett−Teller (BET) surface areas among the different nanocomposites. The hEBDT exhibited a surface area of 452.6 m 2 g −1 , S-hEBDT showed a surface area of 430.3 m 2 g −1 , and S-hEBDT-P displayed a surface area of 318.4 m 2 g −1 , surpassing that of the nonhollow S-cEBDT-P counterparts (Figure 2b).…”

“…Analysis of the conduction band (CB) and valence band (VB) positions suggested that S-hEBDT-P, S-hEBDT, and S-cEBDT-P possessed a similar CB and VB position (Figures S13 and S14). 49,51,55 The order of the photoluminescence (PL) intensity for all samples was as follows: EB > hEBDT > S-hEBDT > S-hEBDT-P ≈ S-cEBDT-P, with the PL intensity of S-hEBDT-P and S-cEBDT-P nearly negligible (Figure S15). The photocurrent intensity of S-hEBDT-P and S-hEBDT was significantly higher compared to that of hEBDT, suggesting that incorporation of sulfonate functionalities into HCMPs can effectively enhance the separation of photogenerated electron− hole pairs (Figure S16).…”

“…As observed from the solid-state 13 C nuclear magnetic resonance ( 13 C NMR) spectra, the resonance signals in the range δ = 110–155 ppm were indicative of aromatic carbons, whereas the resonance signals in the range δ = 10–60 ppm supported the existence of methylene carbons in the PSPMK graft chains (Figure a). Additionally, the lack of signals associated with alkynyl carbons in the δ = 70–90 ppm range suggested the effective integration of halosulfonic acid into the internal alkynes within S- h EBDT-P (Figure a). ,, The creation of a hollow cavity in HCMPs contributed to increased Brunauer–Emmett–Teller (BET) surface areas among the different nanocomposites. The h EBDT exhibited a surface area of 452.6 m 2 g –1 , S- h EBDT showed a surface area of 430.3 m 2 g –1 , and S- h EBDT-P displayed a surface area of 318.4 m 2 g –1 , surpassing that of the nonhollow S- c EBDT-P counterparts (Figure b).…”

“…This attribute facilitates the precise allocation of hydrophilic monomers to active centers for rapid propagation and allows for exceptional dispersibility with trivial alteration of HCMPs. 51,52 This investigation outlines a technique that involves the incorporation of benzylamine into HCMPs and surfaceinitiated atom transfer radical polymerization (SI-ATRP). The process commences with the creation of hairy HCMPs (S-hEBDT-P) on SiO 2 sacrificial templates using Sonogashira− Hagihara coupling, succeeded by sulfonation, polymer grafting, and removal of the SiO 2 cores.…”