Core–Shell Poly (Ionic Liquid)@Mesoporous Silica Chemiluminescent Nanoprobes for Sensitive Intracellular Hydrogen Peroxide Imaging

Abstract

Despite significant developments in spatial distribution imaging of H2O2 as one the most important nonradical reactive oxygen species, novel background‐free, highly sensitive, and selective probes that allow intracellular sensing are still imperative. This is mainly because the fluorescent probes usually suffer some drawbacks such as, fluorescence bleaching and requirement of bulky light sources. In this study, the rational design and fabrication of a nonenzymatic nanoprobe (c‐PIL@mSiO2) with dramatically improved sensitivity for chemiluminescent (CL) imaging of intracellular and in vivo H2O2 at nano molar level is presented. The limit of detection is lower than the endogenous H2O2 concentration, and is significantly better than that of some recently reported fluorescent and CL probes. Structurally, the nanoprobe is composed of a unique amphiphilic poly(ionic liquid) core for preserving H2O2 responsive reagents, and a mesoporous silica shell acts as an “exoskeleton” to provide hydrophilic nature. The multiple alternating hydrophobic and hydrophilic nanodomains of the poly(ionic liquid) core increase mass transfer dynamics, which increase the sensitivity of H2O2 imaging. RAW264.7 macrophages and mice models of inflammations experiment show that the c‐PIL@mSiO2 is capable of imaging H2O2 intracellular and in vivo. This probe for the first time achieves CL detection of endogenous intracellular H2O2 without disruption of cells.

Recent Advances in Nanomaterial-Based Chemiluminescence Probes for Biosensing and Imaging of Reactive Oxygen Species

“…Therefore, various nanomaterial carriers such as micelles and nanocomposites were developed for loading POCL regents [75,76]. Zhou et al prepared a core-shell structured nanocontainer (PIL@mSiO 2 ) consisting of a poly-(ionic liquid) nanoparticle (PIL) core and a hydrophilic mesoporous silica shell to load CPPO and dye molecules [77]. The hydrophilic mesoporous silica shell not only provided the nanoprobe with chemical stability and hydrophilicity, but also permitted quick access of H 2 O 2 to the CPPO in the hydrophobic PIL core (Figure 4b).…”

Sensors, Imaging Agents, and Theranostics to Help Understand and Treat Reactive Oxygen Species Related Diseases

“…The fluorescence of the nanoparticles was quenched with AuNPs due to electrostatic attraction, and the presence of H 2 O 2 recovered the fluorescence through the oxidation of the AgNPs to Ag(I). Moreover, Xia and co-workers [129] constructed a core-shell nanoparticle based on polymer and mesoporous silica for the intracellular and in vivo imaging of H 2 O 2 . Fluorogenic probes were loaded into the nanoparticle container with organic chains, and the fluorescence recovered inside the container in the presence of H 2 O 2 .…”

“…In vivo imaging of exogenous H 2 O 2 using the nanoprobe c-PIL@mSiO 2 : I) negative control; II) nanoprobe with 1 × 10 −9 m H 2 O 2 ; III) nanoprobe alone; IV) nanoprobe with 10 × 10 −9 m H 2 O 2 (right). Reproduced with permission [129]. Copyright 2018, Wiley-VCH.…”

Microenvironment‐Tailored Catalytic Nanoprobe for Ratiometric NIR‐II Fluorescence/Photoacoustic Imaging of H2O2 in Tumor and Lymphatic Metastasis

“…[ 4–8 ] In situ and real‐time monitoring of H 2 O 2 has important clinical implications not only for disease diagnosis but also for better understanding of the mechanisms underlying disease initiation and progression. [ 9–15 ] Therefore, it is of fundamental importance to develop sensing methods with excellent sensitivity and accuracy for quantitative visualization of H 2 O 2 in vivo.…”