Enhanced Chemiluminescence under the Nanoconfinement of Covalent–Organic Frameworks and Its Application in Sensitive Detection of Cancer Biomarkers

Abstract

Chemiluminescence (CL) with intensive emission has been pursued for decades. It is still challenging to find a new mechanism to enhance CL. In this work, confinement-enhanced CL was developed for the first time by the coembedding of N-(aminobutyl)-N-(ethylisoluminol) (ABEI) and Co2+ into gold nanoparticle-modified covalent–organic frameworks (COFs). For the consideration of improving the hydrophilicity of COFs and facilitating subsequent biological modification, gold nanoparticles were first reduced on the COF surface (Au-COF) in situ without other reducing reagents. By virtue of the abundant imine bond and π backbones, ABEI and Co2+ were embedded in Au-COF synergistically through π–π stacking and coordination. The confinement of ABEI and Co2+ into Au-COF brought an over 20-fold enhancement of CL intensity compared to that of adding them to a liquid phase, which benefitted from the three aspects of the confinement effect, including the molecular enrichment effect, the physical constraint effect, and the molecular preorganization effect. As proof of concept, a lipid–protein dual-recognition sandwich strategy based on this CL-functionalized COF was developed for the detection of breast cancer cell line-derived extracellular vesicles (EVs) with four orders of magnitude improvement in the detection limit compared to ELISA. The successful distinction of human epidermal growth factor receptor 2 (HER2)-positive patients from HER2-negative patients indicated the great application potential of the proposed bioassay in HER2-positive breast cancer diagnosis. This work proposed a novel enhancement mechanism for CL based on crystalline porous materials, which provides a new perspective for the development of CL-functionalized materials for biosensors and bioassays.

VS4 Nanodendrites with Narrow Bandgaps in Activating Dissolved Oxygen for Boosted Chemiluminescence and Hemin Detection by Unexpected Quenching

“…It is well known that the sensitivity of chemiluminescent sensors depends remarkably on the quantum efficiency of the generated CL. , To achieve maximum CL emissions for the luminol/DO/VS 4 nanodendrite system, we optimized the pH of the reaction media by investigating the effect of carbonate buffer solution pH in the range of 9.2–12. As shown in Figure S6a, incremental changes in the CL emission were observed with an increase in pH from 9.2 to 10.5.…”

Phosphorous nitride dots induced efficient advanced oxidation with intrinsic chemiluminescence for organic pollutant degradation

“…Chemiluminescence (CL) is an on-line spectral analysis involving the transformation of ROS accompanied, making it significant for exploring the mechanisms of ROS-involved reaction processes. 15–17 However, the low CL efficiency seriously limited its further development. Originating from quantum confinement and tunable properties, a nanomaterial-based CL system proposed immense potential as an indicator to study reaction processes with enhancing efficiency.…”

Ultrasensitive PD-L1-Expressing Exosome Immunosensors Based on a Chemiluminescent Nickel–Cobalt Hydroxide Nanoflower for Diagnosis and Classification of Lung Adenocarcinoma

“…To date, various types of CL-functionalized nanomaterials have been synthesized, including metal nanoparticles, metal nanoclusters, carbon nanomaterials, metal–organic frameworks, magnetic nanomaterials, and hydrogels. − Depending on whether these nanomaterials can catalyze the CL reaction or not, these CL-functionalized nanomaterials can be classified into two categories. The first category of CL-functionalized nanomaterials is using nanomaterials without CL catalytic activity as carriers, such as polydopamine, Fe 3 O 4 magnetic beads, silicon dioxide, and covalent organic frameworks . They usually require further modification of the catalyst on their surface to achieve higher CL intensity, but this may not only affect the stability of the CL-functionalized nanomaterial but also affect the construction of the immunosensor due to the highly occupied surface binding sites.…”