Enhanced chemiluminescence resonance energy transfer using surfactant-modified AIE carbon dots.

Chemiluminescence resonance energy transfer (CRET) efficiency can be enhanced by confining CRET donors and acceptors within nanoscale spaces. However, this enhanced efficiency is often affected by uncertainties stemming from the random distribution of CRET donors and acceptors in such confined environments. In this study, a novel confined nanospace was created through the surfactant modification of carbon dots (CDs) exhibiting aggregation-induced emission (AIE) characteristics. Hydrophobic CRET donors could be effectively confined within this nanospace. The distance between the CRET donors and acceptors could be controlled by anchoring the AIE-CDs as the CRET acceptors, resulting in significantly improved CRET efficiency. Furthermore, this AIE-CDs-based CRET system was successfully applied to the detection of hydrogen peroxide (H2O2) in rainwater, showcasing its potential for practical applications.

Aggregation-induced emission-active micelles: synthesis, characterization, and applications.

Aggregation-induced emission (AIE)-active micelles are a type of fluorescent functional materials that exhibit enhanced emissions in the aggregated surfactant state. They have received significant interest due to their excellent fluorescence efficiency in the aggregated state, remarkable processability, and solubility. AIE-active micelles can be designed through the self-assembly of amphipathic AIE luminogens (AIEgens) and the encapsulation of non-emissive amphipathic molecules in AIEgens. Currently, a wide range of AIE-active micelles have been constructed, with a significant increase in research interest in this area. A series of advanced techniques has been used to characterize AIE-active micelles, such as cryogenic-electron microscopy (Cryo-EM) and confocal laser scanning microscopy (CLSM). This review provides an overview of the synthesis, characterization, and applications of AIE-active micelles, especially their applications in cell and in vivo imaging, biological and organic compound sensors, anticancer drugs, gene delivery, chemotherapy, photodynamic therapy, and photocatalytic reactions, with a focus on the most recent developments. Based on the synergistic effect of micelles and AIE, it is anticipated that this review will guide the development of innovative and fascinating AIE-active micelle materials with exciting architectures and functions in the future.

Recent Advances in Fluorescent Probes for Cancer Biomarker Detection.

Many important biological species have been identified as cancer biomarkers and are gradually becoming reliable targets for early diagnosis and late therapeutic evaluation of cancer. However, accurate quantitative detection of cancer biomarkers remains challenging due to the complexity of biological systems and the diversity of cancer development. Fluorescent probes have been extensively utilized for identifying biological substances due to their notable benefits of being non-invasive, quickly responsive, highly sensitive and selective, allowing real-time visualization, and easily modifiable. This review critiques fluorescent probes used for detecting and imaging cancer biomarkers over the last five years. Focuses are made on the design strategies of small-molecule and nano-sized fluorescent probes, the construction methods of fluorescence sensing and imaging platforms, and their further applications in detection of multiple biomarkers, including enzymes, reactive oxygen species, reactive sulfur species, and microenvironments. This review aims to guide the design and development of excellent cancer diagnostic fluorescent probes, and promote the broad application of fluorescence analysis in early cancer diagnosis.

Probing Coordination Number of Single-Atom Catalysts by d-Band Center-Regulated Luminescence.

It is essential to probe the coordination number (CN) because it is a crucial factor to ensure the catalytic capability of single-atom catalysts (SACs). Currently, synchrotron X-ray absorption spectroscopy (XAS) is widely used to measure the CN. However, the scarcity of synchrotron X-ray source and complicated data analysis restrict its wide applications in determining the CN of SACs. In this contribution, we have developed a d-band center-regulated acetone cataluminescence (CTL) probe for a rapid screening of the CN of Pt-SACs. It is disclosed that the CN-triggered CTL is attributed to the fact that the increased CN could induce the downward shift of d-band center position, which assists the acetone adsorption and promotes the subsequent catalytic reaction. In addition, the universality of the proposed acetone-CTL probe is verified by determining the CN of Fe-SACs. This work has opened a new avenue for exploring an alternative to synchrotron XAS for the determination of CN of SACs and even conventional metal catalysts through d-band center-regulated CTL.

Vesicles as a Multifunctional Microenvironment for Electrochemiluminescence Signal Amplification.

Vesicles as a typical interface-rich microenvironment can promote the reaction rate and the intermediate stability, which are promising for introduction in electrochemiluminescence (ECL) signal amplification. In this work, a kind of multilamellar vesicle obtained from sodium bis(2-ethylhexyl) sulfosuccinate (AOT) was used to modify the electrode surface. The AOT vesicle-modified microenvironment could significantly enhance the ECL performances for the luminol/O2 system in a neutral medium. The mechanism study demonstrated that the nanoscale multilamellar vesicles could maintain the vesicle structure on the electrode surface, which substantially improved the electron transfer and reaction rate, luminescence efficiency of the excited-state 3-aminophthalate anion, and stability of the superoxide anion radical. Alternatively, such a multifunctional microenvironment was also able to enhance the ECL signals from the tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)32+)/tripropylamine (TPrA) system. Moreover, another dodecyl dimethyl(3-sulfopropyl) ammonium hydroxide inner salt (DSB)-based vesicle was constructed to further verify the versatility of the vesicle-modified microenvironment for ECL signal amplification. Our work not only provides a versatile microenvironment for improving the efficiency of various ECL systems but also offers new insights for the microenvironment construction using the ordered assemblies in ECL fields.

Quantitative Measurement of Drug Release Dynamics within Targeted Organelles Using Förster Resonance Energy Transfer.

Measuring the release dynamics of drug molecules after their delivery to the target organelle is critical to improve therapeutic efficacy and reduce side effects. However, it remains challenging to quantitatively monitor subcellular drug release in real time. To address the knowledge gap, a novel gemini fluorescent surfactant capable of forming mitochondria-targeted and redox-responsive nanocarriers is designed. A quantitative Förster resonance energy transfer (FRET) platform is fabricated using this mitochondria-anchored fluorescent nanocarrier as a FRET donor and fluorescent drugs as a FRET acceptor. The FRET platform enables real-time measurement of drug release from organelle-targeted nanocarriers. Moreover, the obtained drug release dynamics can evaluate the duration of drug release at the subcellular level, which established a new quantitative method for organelle-targeted drug release. This quantitative FRET platform can compensate for the absent assessment of the targeted release performances of nanocarriers, offering in-depth understanding of the drug release behaviors at the subcellular targets.

Real-Time Imaging of Stress in Single Spherulites and Its Relaxation at the Single-Particle Level in Semicrystalline Polymers.

Crystallization-induced microscopic stress and its relaxation play a vital role in understanding crystallization behavior and mechanism. However, the real-time measurements for stress and its relaxation seem to be an unachievable task due to difficulties in simultaneous labeling, spatiotemporal discrimination, and continuous quantification. We designed a micron-sized fluorescent probe, whose fluorescence can respond to stress-induced environmental rigidity and whose three-dimensional (3D) flow can respond to stress relaxation. Using the as-prepared fluorescent probe, we established a versatile strategy to realize the real-time 3D imaging of stress and its relaxation in the crystallization process. The rigidity-responsive fluorescence clearly indicated the stress, while the 3D flow movement could quantify the stress relaxation. It is revealed that stress in spherulites increased dramatically as a result of the suppression of stress relaxation in polymer melts. The developed method provides a novel avenue to simultaneously detect stress and its relaxation in various semicrystalline polymers at the single-particle level. This success would achieve the microscopic ways to guide the development of advanced crystallization-dependent materials.

Rapid Discrimination of Adsorbed Oxygen and Lattice Oxygen in Catalysts by the Cataluminescence Method.

Adsorbed oxygen and lattice oxygen are crucial parameters for catalyst characterization and catalytic oxidation mechanism. Therefore, rapid discrimination of adsorbed oxygen and lattice oxygen is highly desired. Herein, a direct correlation between cataluminescence (CTL) kinetic curve and oxygen species was discovered. The adsorbed oxygen-catalyzed CTL only lasted for a few minutes, whereas the lattice oxygen-catalyzed CTL could exhibit hours of continuous luminescence. The long-term CTL was attributed to the slow migration of lattice oxygen in a slow and continuous catalytic oxidation reaction. In addition to the discrimination between the adsorbed oxygen and lattice oxygen by the CTL kinetic processes, the corresponding CTL intensity was positively proportional to their amounts. Accordingly, the developed catalytic oxidation-related CTL can be used as an indicator for rapid discrimination and determination of adsorbed oxygen and lattice oxygen in catalysts. Oxygen species detected by the proposed CTL method not only matched well with those obtained by conventional X-ray photoelectron spectroscopy and O2-temperature programmed methods but also offered some distinguished advantages, such as convenient operation, fast response, and low cost. It can be expected that the established oxygen-responsive CTL probe has great potential in distinguishing adsorbed oxygen and lattice oxygen in various catalysts.

Ag-O-Co Interface Modulation-Amplified Luminol Cathodic Electrogenerated Chemiluminescence.

It remains a great challenge to develop effective strategies for improving the weak cathodic electrogenerated chemiluminescence (ECL) of the luminol-dissolved O2 system. Interface modulation between metal and supports is an attractive strategy to improve oxygen reduction reaction (ORR) activity. Therefore, the design of electrocatalysts via interface modulation would provide new opportunities for the ECL amplification involving reactive oxygen species (ROSs). Herein, we have fabricated an Ag single-atom catalyst with an oxygen-bridged interface (Ag-O-Co) through the electrodeposition of Ag on a CoAl layered double hydroxide (LDH) modified indium tin oxide (ITO) electrode (Ags/LDH/ITO). Interestingly, it was found that the cathodic ECL intensity of the luminol-dissolved O2 system at the Ags/LDH/ITO electrode was extraordinarily enhanced in comparison with those at bare ITO and other Ag nanoparticle-based electrodes. The enhanced ECL performances of the Ags/LDH/ITO electrode were attributed to the increasing amounts of ROSs by electrocatalytic ORR in the Ag-O-Co interface. The electron redistribution of Ag and Co bimetallic sites could accelerate electron transfer, promote the adsorption of O2, and sufficiently activate O2 through a four-electron reaction pathway. Finally, the luminol cathodic ECL intensity was greatly improved. Our findings can provide inspiration for revealing the interface effects between metal and supports, and open up a new avenue to improve the luminol cathodic ECL.

Advances in intelligent-responsive nanocarriers for cancer therapy.

With the rapid development of nanotechnology, strategies related to nanomedicine have been used to overcome the shortcomings of traditional chemotherapy drugs, thereby demonstrating significant potential for innovative drug delivery. Nanomaterials play an increasingly important role in cancer immunotherapy. Stimuli-responsive nanomaterials enable the precise control of drug release through exposure to specific stimuli and exhibit excellent specificity in response to various stimuli. Immunomodulators carried by nanomaterials can also effectively regulate the immune system and significantly improve their therapeutic effect on cancer. In recent years, stimuli-responsive nanomaterials have evolved rapidly from single stimuli-responsive systems to multi-stimuli-responsive systems. This review focuses on recent advances in the design and applications of stimuli-responsive nanomaterials, including exogenous and endogenous responsive nanoscale drug delivery systems, which show extraordinary potential in intelligent drug delivery for multimodal cancer diagnosis and treatment. Ultimately, the opportunities and challenges in the development of intelligent responsive nanomaterials are briefly discussed according to recent advances in multi-stimuli-responsive systems.

Determination of the critical micelle concentration of surfactants using fluorescence strategies.

The increasing importance of surfactants in various fields has led to growing interest in the comprehensive characterization of surfactants. The critical micelle concentration (CMC), the most fundamental property of surfactants, is a parameter that must be measured. In particular, with the continuous expansion of the molecular structure of surfactants, numerous novel amphiphilic molecules have been developed that are capable of forming ordered aggregates in various solvent systems. Fluorescence spectroscopy, based on the differences in fluorescence intensity and wavelength of the fluorescent probe in the solvent phase and micellar phase, can sensitively detect the CMC of surfactants. This review aims to summarize the various fluorescence methods used to determine the CMC, including aggregation-induced emission (AIE), excimer formation, intramolecular charge transfer (ICT), and other miscellaneous strategies. The difficulties and limitations in the CMC determination process are also described. Further suggestions are provided to guide the existing fluorescence probes and the corresponding fluorescence methods to detect critical aggregation concentrations of amphiphilic molecules.

Disordered Assembly of Donors and Acceptors on Layered Double Hydroxides for High-Efficiency Chemiluminescence Resonance Energy Transfer.

High-efficiency chemiluminescence (CL) resonance energy transfer (CRET) can be obtained by shortening the donor-acceptor distance and/or improving the luminescence efficiency of CRET acceptors. However, careful design and stringent experimental conditions are usually required for the ordered assembly of CRET acceptors on support materials to avoid aggregation-caused quenching problems. In this work, an aggregation-induced emission (AIE)-active fluorophore was disorderly adsorbed on the surface of layered double hydroxides (LDHs), which could exhibit high-efficiency luminescence. On the other hand, the positively charged LDHs can further adsorb peroxynitrite (ONOO-) on the surface of LDHs. Therefore, the LDH-supported AIE fluorophore could dramatically amplify weak CL signals from ONOO- donors as a result of ultra-high CRET efficiency by coupling the shorter donor-acceptor distance with efficient CRET acceptors. The proposed CL system has been successfully applied for the detection of NaNO2 in the concentration range from 1.0 to 100 µM with a detection limit as low as 0.5 µM. Satisfactory recoveries (98-106%) and good accuracy were achieved for sausage samples. Our success will open new avenues for the convenient design of high-efficiency CRET systems.

Charge Neutralization Strategy to Construct Salt-Tolerant and Cell-Permeable Nanoprobes: Application in Ratiometric Sensing and Imaging of Intracellular pH.

Intracellular pH homeostasis is essential for the survival and function of biological cells. Negatively charged molecular probes, such as pyranine (HPTS), tend to exhibit poor salt tolerance and unsatisfactory cell permeability, limiting their widespread use in intracellular assays. Herein, we explored a charge neutralization strategy using multicharged cationic nanocarriers for an efficient and stable assembly with the pH-sensitive HPTS. Through immobilization and neutralization with poly(allylamine hydrochloride)-stabilized red-emitting gold nanoclusters (PAH-AuNCs), the resulting nanoprobes (HPTS-PAH-AuNCs) offered improved salt tolerance, satisfactory cell permeability, and dual-emission properties. The fluorescence ratio exhibited a linear response over the pH range of 3.0-9.0. Moreover, the proposed HPTS-PAH-AuNCs were successfully applied to determine and visualize lysosomal pH variations in living cells, which indicated great potential for biosensing and bioimaging applications in living systems. Benefiting from the charge neutralization strategy, various types of probes can be expected to achieve broader analytical applications.

Chemiluminescence Resonance Energy Transfer Efficiency and Donor-Acceptor Distance: from Qualitative to Quantitative.

Since its birth in 1967, the utilization of chemiluminescence resonance energy transfer (CRET) has made substantial progress in a variety of fields for its unique features. However, the quantitative relationship between CRET efficiency and donor-acceptor distance has not yet been determined owing to the difficulty in designing the variable lengths between chemiluminescent donors and acceptors. Herein, we synthesized three kinds of tetraphenylethene (TPE)-anchored cationic surfactants with aggregation-induced emission (AIE) characteristics. For the first time, it is quantitatively demonstrated that the CRET efficiency is inversely proportional to the sixth power of distance between luminol donors and TPE acceptors. The details disclosed in this contribute have provided the solid evidence that CRET follows Förster resonance theory. Our strategy would build a promising platform to control donor-acceptor distance, allowing to the interdisciplinary applications of CRET.

Superoxide-Triggered Luminol Electrochemiluminescence for Detection of Oxygen Vacancy in Oxides.

Oxygen vacancy is known to act as a reactive center in oxides to produce radicals. Currently, X-ray photoelectron spectra (XPS) become a unique spectral tool for analyzing oxygen vacancy based on the differences in atomic number ratios between metal ions and lattice oxygen. In this work, it was found that the superoxide radical (O2•-)-luminol electrochemiluminescence (ECL) intensity linearly increases with increasing the oxygen vacancy concentrations of TiO2 samples coated on the electrodes. An experimental study of the mechanism demonstrates that an increase in oxygen vacancy concentrations could lead to an increase in the generation of O2•-, resulting in an increase in the O2•--related luminol ECL signals. Accordingly, we have developed a rapid and simple O2•--luminol ECL platform to detect oxygen vacancy in TiO2 samples, based on the relationship between O2•- generation and oxygen vacancy. The proposed ECL platform exhibits good reproducibility and stability through the parallel ECL measurements. Moreover, the feasibility is verified by analyzing the oxygen vacancy concentrations in different TiO2 samples with varying the Co, Cr, Fe, and N doping concentrations. The oxygen vacancy concentrations obtained by the proposed ECL method could match well with those obtained by conventional XPS measurements. Our successful construction of the ECL platform will significantly promote the development of the oxygen vacancy detection in oxides and deepen the understanding of the relationship between oxygen vacancy and radicals.

Measurement of Solubilization Location in Micelles Using Anchored Aggregation-Induced Emission Donors.

Solubilization locations play a critical role in developing advanced surfactants and improving solubilization power in micelle-based applications. However, the current polarity-based techniques for measuring solubilization locations could come to conflicting conclusions. The key challenge is the unpredictable polarities in the micellar microenvironment. Now, an approach that is independent of micellar polarities is used to measure solubilization locations by covalently linking tetraphenylethylene (TPE) to the alkyl chain end of cationic surfactants. The solubilization locations of solubilized acceptors in the TPE-cored spherical micelles were accurately measured by calculating the Förster resonance energy transfer distance between anchored TPE donors and solubilized acceptors. Solubilization locations of solubilized substances in the micellar interior and at the micellar surface depend on their size and hydrophobicity, respectively.

Micelle-Mediated Chemiluminescence as an Indicator for Micellar Transitions.

The structural phase of micelles plays an important role in controlling the micellar performance. Despite the great developments of some advanced characterization techniques, it remains challenging to achieve fast and sensitive determination of micellar transitions in solution. Herein, a novel indicator system for micellar transitions was developed based on the micelle-mediated peroxyoxalate chemiluminescence that showed a sensitive response toward the changes of micellar morphologies. A peroxyoxalate derivative and a fluorophore were first coassembled into the hydrophobic cavities of micelles of the typical cationic surfactant cetyltrimethylammonium bromide (CTAB). A strong and rapidly falling chemiluminescence response was exhibited in spherical micelles as a result of the loose arrangement of CTAB molecules. By contrast, rodlike or wormlike micelles transformed from spherical micelles could induce a compact arrangement of CTAB molecules, leading to a weak chemiluminescence emission with a slow decay rate. The practicability and universality of the chemiluminescent indicator were demonstrated by determining the micellar transitions in a variety of surfactant solutions (ionic, nonionic, and polymeric). These findings open attractive perspectives for the practice of chemiluminescence technique in micelle characterization.

A novel homolateral and dicationic AIEgen for the sensitive detection of casein.

The exploitation of highly soluble and responsive AIEgens is essential for further expansion of their practical applications. In this study, dipropyltrimethylammonium bromide-substituted TPE (denoted as o-TPEDTA), a homolateral and dicationic AIEgen, was synthesized and applied for the turn-on detection of casein via hydrophobic interactions. The rapid and sensitive detection of casein was achieved using the designed o-TPEDTA probe with the limit of detection of 0.05 µg mL-1. The satisfying selectivity of over 1000-fold concentration of other probably existing chemicals, including amino acids, sugars and salts, was achieved due to the strong binding affinity between o-TPEDTA and casein. The evaluation of casein in milk powder samples with small relative standard deviations was realized using the o-TPEDTA probe. The accuracy of the o-TPEDTA probe-based detection method was validated by the consistency of the casein detection results with those obtained via a national standard casein evaluation approach.

Three-dimensional direct visualization of silica dispersion in polymer-based composites.

The uniform dispersion of silica fillers or other neutral fillers in the polymer matrix is significant for fabricating high-performance polymer-based composites. However, there is a long-standing challenge to provide a comprehensive, wide-area and real 3D distribution map to achieve direct visualization for the dispersion state of neutral silica. Herein, we propose a novel strategy for modifying silica fillers with commercial fluorophores to form fluorescent fillers in a standard manner. Through fluorescence imaging technology, we successfully observed the 2D-planar and 3D-spatial dispersion states of silica fillers in the polymer matrix. This success not only provides a visualized evaluation method for the spatial dispersion of an oxide filler, but also offers great potential in the further establishment of industrialized standards for the polymer-based composite industry.

Cation-π Interaction Triggered-Fluorescence of Clay Fillers in Polymer Composites for Quantification of Three-Dimensional Macrodispersion.

It is a considerable challenge to realize 3D fluorescence quantification of macrodispersion of clay fillers in a polymer matrix mainly owing to quenching of light emission in the solid state. Herein, a strong light emission is generated within the interlaminated clay as a result of a cation-π interaction between cationic surfactant and fluorescent polycyclic aromatic hydrocarbon when they are cointercalated into clay. Confocal laser scanning microscopy (CLSM) is applied for 3D imaging of macrodispersion of the fluorescence-labeled clay fillers in a silicone rubber matrix. More importantly, the quantification of macrodispersion of clay fillers in the overall polymer composite is established by a statistical model. The proposed method fills in an important gap in the standard for macrodispersion quantification of inorganic fillers in polymer composites.