A series of tetraphenylene-acetonitrile AIE compounds with D-A-D' structure for drugs delivery systems of paclitaxel: Synthesis, structure-activity relationship and anti-tumors effect.

Aggregation-induced emission (AIE) materials are attracting great attention in biomedical fields such as sensors, bioimaging, and cancer treatment, et al. due to their strong fluorescence emission in the aggregated state. In this contribution, a series of tetraphenylene-acetonitrile AIE compounds with D-A-D' structures were synthesized by Suzuki coupling reaction and Knoevenagel condensation, and their relationship of chemical structure and fluorescence properties was investigated in detail, among which TPPA compound was selected as the monomer owing to the longest emission wavelength at about 530 nm with low energy band gap ΔE 3.09 eV of neutral TPPA and 1.43 eV of protonated TPPA. Novel amphiphilic AIE PEG-TA copolymers were prepared by RAFT polymerization of TPPA and PEGMA with about 1.44×104 Mw and narrow PDI, and the molar ratio of TPPA in the PEG-TA1 and PEG-TA2 copolymers was about 23.4 % and 29.6 %. The as-prepared PEG-TA copolymers would self-assembled in aqueous solution to form core-shell structures with a diameter of 150-200 nm, and their emission wavelength could reversibly convert from 545 nm to 650 nm with excellent pH sensitivity. The CLSM images showed that the PEG-TA FONs and PTX drugs-loaded PTX-TA FONs could be endocytosed by cells and mainly enriched in the cytoplasm, and CCK-8 results showed that the PEG-TA FONs had excellent biocompatibility but PTX-TA FONs had high inhibition ratio for A549 cells, moreover, the flow cytometry also showed that PTX-TA FONs could result in the apoptosis of A549 cells with some extent anti-tumor effect.

A Comprehensive Review of Nanoparticles: From Classification to Application and Toxicity.

Nanoparticles are structures that possess unique properties with high surface area-to-volume ratio. Their small size, up to 100 nm, and potential for surface modifications have enabled their use in a wide range of applications. Various factors influence the properties and applications of NPs, including the synthesis method and physical attributes such as size and shape. Additionally, the materials used in the synthesis of NPs are primary determinants of their application. Based on the chosen material, NPs are generally classified into three categories: organic, inorganic, and carbon-based. These categories include a variety of materials, such as proteins, polymers, metal ions, lipids and derivatives, magnetic minerals, and so on. Each material possesses unique attributes that influence the activity and application of the NPs. Consequently, certain NPs are typically used in particular areas because they possess higher efficiency along with tenable toxicity. Therefore, the classification and the base material in the NP synthesis hold significant importance in both NP research and application. In this paper, we discuss these classifications, exemplify most of the major materials, and categorize them according to their preferred area of application. This review provides an overall review of the materials, including their application, and toxicity.

Reversible Light-Triggered Stretching of Small-Molecule Photochromic Organic Nanoparticles.

Functional organic nanomaterials are nowadays largely spread in the field of nanomedicine. In situ modulation of their morphology is thus expected to considerably impact their interactions with the surroundings. In this context, photoswitchable nanoparticles that are manufactured, amenable to extensive disassembling upon illumination in the visible, and reversible reshaping under UV exposure. Such reversibility turns to be strongly impaired for photochromic nanoparticles in close contact with a substrate. In situ atomic force microscopy investigations at the nanoscale actually reveal progressive disintegration of the organic nanoparticles under successive UV-vis cycles of irradiation, in the absence of intrinsic elastic forces. These results point out the dramatic interactions exerted by surfaces on the cohesion of non-covalently bonded organic nanoparticles. They invite to harness such systems, often used as biomarkers, to also serve as photoactivatable drug delivery nanocarriers.

Application of Natural Functional Additives for Improving Bioactivity and Structure of Biopolymer-Based Films for Food Packaging: A Review.

The global trend towards conscious consumption plays an important role in consumer preferences regarding both the composition and quality of food and packaging materials, including sustainable ones. The development of biodegradable active packaging materials could reduce both the negative impact on the environment due to a decrease in the use of oil-based plastics and the amount of synthetic preservatives. This review discusses relevant functional additives for improving the bioactivity of biopolymer-based films. Addition of plant, microbial, animal and organic nanoparticles into bio-based films is discussed. Changes in mechanical, transparency, water and oxygen barrier properties are reviewed. Since microbial and oxidative deterioration are the main causes of food spoilage, antimicrobial and antioxidant properties of natural additives are discussed, including perspective ones for the development of biodegradable active packaging.

Nitric Oxide Releasing Nanomaterials for Cardiovascular Applications.

A central paradigm of cardiovascular homeostasis is that impaired nitric oxide (NO) bioavailability results in a wide array of cardiovascular dysfunction including incompetent endothelium-dependent vasodilatation, thrombosis, vascular inflammation, and proliferation of the intima. Over the course of more than a century, NO donating formulations such as organic nitrates and nitrites have remained a cornerstone of treatment for patients with cardiovascular diseases. These donors primarily produce NO in the circulation and are not targeted to specific (sub)cellular sites of action. However, safe, and therapeutic levels of NO require delivery of the right amount to a precise location at the right time. To achieve these aims, several recent strategies aimed at therapeutically generating or releasing NO in living systems have shown that polymeric and inorganic (silica, gold) nanoparticles and nanoscale metal-organic frameworks could either generate NO endogenously by the catalytic decomposition of endogenous NO substrates or can store and release therapeutically relevant amounts of NO gas. NO-releasing nanomaterials have been developed for vascular implants (such as stents and grafts) to target atherosclerosis, hypertension, myocardial ischemia-reperfusion injury, and cardiac tissue engineering. In this review, we discuss the advances in design and development of novel NO-releasing nanomaterials for cardiovascular therapeutics and critically examine the therapeutic potential of these nanoplatforms to modulate cellular metabolism, to regulate vascular tone, inhibit platelet aggregation, and limit proliferation of vascular smooth muscle with minimal toxic effects.

Organic Nanoparticles in Progressing Cardiovascular Disease Treatment and Diagnosis.

Cardiovascular diseases (CVDs), the world's most prominent cause of mortality, continue to be challenging conditions for patients, physicians, and researchers alike. CVDs comprise a wide range of illnesses affecting the heart, blood vessels, and the blood that flows through and between them. Advances in nanomedicine, a discipline focused on improving patient outcomes through revolutionary treatments, imaging agents, and ex vivo diagnostics, have created enthusiasm for overcoming limitations in CVDs' therapeutic and diagnostic landscapes. Nanomedicine can be involved in clinical purposes for CVD through the augmentation of cardiac or heart-related biomaterials, which can be functionally, mechanically, immunologically, and electrically improved by incorporating nanomaterials; vasculature applications, which involve systemically injected nanotherapeutics and imaging nanodiagnostics, nano-enabled biomaterials, or tissue-nanoengineered solutions; and enhancement of sensitivity and/or specificity of ex vivo diagnostic devices for patient samples. Therefore, this review discusses the latest studies based on applying organic nanoparticles in cardiovascular illness, including drug-conjugated polymers, lipid nanoparticles, and micelles. Following the revised information, it can be concluded that organic nanoparticles may be the most appropriate type of treatment for cardiovascular diseases due to their biocompatibility and capacity to integrate various drugs.

Research Progress in Nanoparticle Inhibitors for Crude Oil Asphaltene Deposition.

Currently, the alteration of external factors during crude oil extraction easily disrupts the thermodynamic equilibrium of asphaltene, resulting in the continuous flocculation and deposition of asphaltene molecules in crude oil. This accumulation within the pores of reservoir rocks obstructs the pore throat, hindering the efficient extraction of oil and gas, and consequently, affecting the recovery of oil and gas resources. Therefore, it is crucial to investigate the principles of asphaltene deposition inhibition and the synthesis of asphaltene inhibitors. In recent years, the development of nanotechnology has garnered significant attention due to its unique surface and volume effects. Nanoparticles possess a large specific surface area, high adsorption capacity, and excellent suspension and catalytic abilities, exhibiting unparalleled advantages compared with traditional organic asphaltene inhibitors, such as sodium dodecyl benzene sulfonate and salicylic acid. At present, there are three primary types of nanoparticle inhibitors: metal oxide nanoparticles, organic nanoparticles, and inorganic nonmetal nanoparticles. This paper reviews the recent advancements and application challenges of nanoparticle asphaltene deposition inhibition technology based on the mechanism of asphaltene deposition and nano-inhibitors. The aim was to provide insights for ongoing research in this field and to identify potential future research directions.

Nanothermometer Based on Polychlorinated Trityl Radicals Showing Two-Photon Excitation and Emission in the Biological Transparency Window: Temperature Monitoring of Biological Tissues.

Nanothermometers are emerging probes as biomedical diagnostic tools. Especially appealing are nanoprobes using NIR light in the range of biological transparency window (BTW) since they have the advantages of a deeper penetration into biological tissues, better contrast, reduced phototoxicity and photobleaching. This article reports the preparation and characterization of organic nanoparticles (ONPs) doped with two polychlorinated trityl radicals (TTM and PTM), as well as studies of their electronic and optical properties. Such ONPs having inside isolated radical molecules and dimeric excimers, can be two-photon excited showing optimal properties for temperature sensing. Remarkably, in TTM-based ONPs the emission intensity of the isolated radical species is unaltered increasing temperature, while the excimer emission intensity decreases strongly being thereby able to monitor temperature changes with an excellent thermal absolute sensitivity of 0.6-3.7% K-1 in the temperature range of 278-328 K. The temperature dependence of the excimeric bands of ONPs are theoretically simulated by using electronic structure calculations and a vibronic Hamiltonian model. Finally, TTM-doped ONPs as ratiometric NIR-nanothermometers are tested with two-photon excitationwith enucleated pig eye sclera, as a real tissue model, obtaining a similar temperature sensitivity as in aqueous suspensions, demonstrating their potential as NIR nanothermometers for bio applications.

Enzymatic Dimerization-Induced Self-Assembly of Alanine-Tyramine Conjugates into Versatile, Uniform, Enzyme-Loaded Organic Nanoparticles.

Herein, we report a novel enzymatic dimerization-induced self-assembly (e-DISA) procedure that converts alanine-tyramine conjugates into highly uniform enzyme-loaded nanoparticles (NPs) or nanocontainers by the action of horseradish peroxidase (HRP) in an aqueous medium under ambient conditions. The NP formation was possible with both enantiomers of alanine, and the average diameter could be varied from 150 nm to 250 nm (with a 5-12 % standard deviation of as-prepared samples) depending on the precursor concentration. About 60 % of the added HRP enzyme was entrapped within the NPs and was subsequently utilized for post-synthetic modification of the NPs with phenolic compounds such as tyramine or tannic acid. One-pot multi-enzyme entrapment of glucose oxidase (GOx) and peroxidase (HRP) within the NPs was also achieved. These GOx-HRP loaded NPs allowed multimodal detection of glucose, including that present in human saliva, with a limit of detection (LoD) of 740 nM through fluorimetry. The NPs exhibited good cytocompatibility and were stable to changes in pH (acidic to basic), temperature, ultrasonication, and even the presence of organic solvent (EtOH) to a certain extent, since they are stabilized by intermolecular hydrogen bonding, π-π, and CH-π interactions. The proposed e-DISA procedure can be widely expanded through the design of diverse enzyme-responsive precursors.

Novel small molecule-based organic nanoparticles for second near-infrared photothermal tumor ablation.

Second near-infrared (NIR-II,1000 âˆ¼ 1700 nm) therapeutic window presents an increased tissue penetration and elevated maximal permissible exposure in the application of photothermal therapy (PTT). However, the lack of NIR-II photothermal conversion agents (PCAs) limit their further development. In this work, we rationally designed and successfully developed three novel indolium-like heptamethine cyanine dyes (NFs) by installing N,N-diethylamino on the terminal ends of a conjugated polyene backbone and replacing the middle chlorine atom with o-mercapto benzoic acid and p-mercapto benzoic acid. Notably, NF2 with stronger rotating group encapsulated in organic nanoparticles (NF2 NPs) exhibited high photothermal conversion efficiency (PCE), which could come up to (61.3 %). Then we conducted serial experiments to further investigate PTT capability of NF2 NPs 4 T1 cell line and nude mice bearing 4 T1 tumor. As expected, the resulting NF2 NPs presented the excellent photothermal conversion ability and superb PTT effect both in vivo and in vitro. This study will inspire more work for future design and clinical applications of NIR-II therapeutic agents.

Furan-Dihydroquinazolinone Based Fluorescent Nanoprobe for Selective Recognition of 4-Nitrophenol: A Spectofluorimetric Approach.

Fluorescent organic nanoparticles (FONPs) have attracted much attention as a practicable and effective platform for detection applications. The present article describes the preparation of FONPs derived from the quinazolinone-based 2-(furan-2-yl)-2,3-dihydroquinazolin-4(1H)-one derivative FHDQ. Self-assembly of FHDQ in an aqueous medium resulted in the formation of FONPs through H-type aggregation and showed excellent fluorescence properties. The presence of other coexisting species solutions did not affect the selective fluorescence quenching observed with the addition of 4-nitrophenol (4-NP). The photophysical properties, i.e., UV-Vis absorbance, fluorescence emission, and lifetime measurements together with zeta particle sizer, support excited-state complex formation followed by a dynamic fluorescence quenching phenomenon in the emission of FDHQNPs. In the concentration range of 0 to 36 µg.[Formula: see text], the detection limit of this turn-off sensor FDHQNPs against 4-NP was determined to be 0.01611 µM. Finally, the practicability of the FDHQNPs for the analysis of 4-NP in environmental samples was demonstrated.

Organic Optoelectronic Materials: A Rising Star of Bioimaging and Phototherapy.

Recently, many organic optoelectronic materials (OOMs), especially those used in organic light-emitting diodes (OLEDs), organic solar cells (OSCs), and organic field-effect transistors (OFETs), are explored for biomedical applications including imaging and photoexcited therapies. In this review, recently developed OOMs for fluorescence imaging, photoacoustic imaging, photothermal therapy, and photodynamic therapy, are summarized. Relationships between their molecular structures, nanoaggregation structures, photophysical mechanisms, and properties for various biomedical applications are discussed. Mainly four kinds of OOMs are covered: thermally activated delayed fluorescence materials in OLEDs, conjugated small molecules and polymers in OSCs, and charge-transfer complexes in OFETs. Based on the OOMs unique optical properties, including excitation light wavelength and exciton dynamics, they are respectively exploited for suitable biomedical applications. This review is intended to serve as a bridge between researchers in the area of organic optoelectronic devices and those in the area of biomedical applications. Moreover, it provides guidance for selecting or modifying OOMs for high-performance biomedical uses. Current challenges and future perspectives of OOMs are also discussed with the hope of inspiring further development of OOMs for efficient biomedical applications.

Hybrid Nanoplatforms Comprising Organic Nanocompartments Encapsulating Inorganic Nanoparticles for Enhanced Drug Delivery and Bioimaging Applications.

Organic and inorganic nanoparticles (NPs) have attracted significant attention due to their unique physico-chemical properties, which have paved the way for their application in numerous fields including diagnostics and therapy. Recently, hybrid nanomaterials consisting of organic nanocompartments (e.g., liposomes, micelles, poly (lactic-co-glycolic acid) NPs, dendrimers, or chitosan NPs) encapsulating inorganic NPs (quantum dots, or NPs made of gold, silver, silica, or magnetic materials) have been researched for usage in vivo as drug-delivery or theranostic agents. These classes of hybrid multi-particulate systems can enable or facilitate the use of inorganic NPs in biomedical applications. Notably, integration of inorganic NPs within organic nanocompartments results in improved NP stability, enhanced bioavailability, and reduced systemic toxicity. Moreover, these hybrid nanomaterials allow synergistic interactions between organic and inorganic NPs, leading to further improvements in therapeutic efficacy. Furthermore, these platforms can also serve as multifunctional agents capable of advanced bioimaging and targeted delivery of therapeutic agents, with great potential for clinical applications. By considering these advancements in the field of nanomedicine, this review aims to provide an overview of recent developments in the use of hybrid nanoparticulate systems that consist of organic nanocompartments encapsulating inorganic NPs for applications in drug delivery, bioimaging, and theranostics.

Organic Nanoparticles with Aggregation-Induced Emission and Two-Photon Excitation for Fluorescence Imaging of Living Cells/Tissues.

Aggregation-induced emission (AIE) nanoparticles (NPs) have been applied in bioimaging for cancer diagnosis due to high fluorescence efficiency. However, the poor cell permeability as well as autofluorescence of biological cells/tissues caused by ultraviolet (UV) irradiation is still the key problem of AIE luminophores for biological imaging. Here, we report green-emitting organic AIE luminophores for fluorescence imaging of living cells/tissues, which possess high fluorescence quantum yields and strong AIE under two-photon excitation with near-infrared light beyond 800 nm. These AIE luminophores can bind with bovine serum albumin (BSA) to form biocompatible BSA/AIE-NPs due to their terminal aldehyde groups providing specific anchor sites with the receptor groups in BSA. Furthermore, one/two-photon fluorescence bioimaging for Hela cancer cells has been successfully carried out with BSA/AIE-NPs as the fluorescent probe, and BSA/AIE-NPs show excellent stain properties with a fast permeability of only 5 min, high cellular uptakes, and strong fluorescence. The results demonstrate the great advantages of BSA/AIE-NPs in fast fluorescence biological imaging as well as further cancer diagnosis and therapy.

Temporal Release of Cell Cycle Regulator α-Lipoic Acid: An NIR-Light (Two-Photon) Activatable Quinoxaline-Based Nano-Prodrug Delivery System.

The regulation of the cell cycle has recently opened up a new research perspective for cancer treatment. So far, no effort has been made for temporal control of cell cycles using a photocleavable linker. Presented herein is the first report of regulation of disrupted cell cycles through the temporal release of a well-known cell cycle regulator α-lipoic acid (ALA), enabled by a newly designed NIR-active quinoxaline-based photoremovable protecting group (PRPG). The suitable quinoxaline-based photocage of ALA (tetraphenylethelene conjugated) has been formulated as fluorescent organic nanoparticles (FONs) and used effectively as a nano-DDS (drug delivery system) for better solubility and cellular internalization. Fascinatingly, the enhanced TP (two-photon) absorption cross section of the nano-DDS (503 GM) signifies its utility for biological applications. Using green light, we have successfully controlled the time span of cell cycles and cell growth of skin melanoma cell lines (B16F10) by the temporal release of ALA. Further, in silico studies and PDH activity assay supported the observed regulatory behavior of our nano-DDS with respect to photoirradiation. Overall, this approach expands the research path toward a futuristic photocontrolled toolbox for cell cycle regulation.

Leaf chlorophyll fluorescence and reflectance of oakleaf lettuce exposed to metal and metal(oid) oxide nanoparticles.

BACKGROUND: Most nanoparticles (NPs) have a significant impact on the structure and function of the plant photosynthetic apparatus. However, their spectrum of action varies significantly, from beneficial stimulation to toxicity, depending on the type of NPs, the concentration used and plant genotypic diversity. Photosynthetic performance can be assessed through chlorophyll a fluorescence (ChlF) measurements. These data allow to indirectly obtain detailed information about primary light reactions, thylakoid electron transport reactions, dark enzymatic stroma reactions, slow regulatory processes, processes at the pigment level. It makes possible, together with leaf reflectance performance, to evaluate photosynthesis sensitivity to stress stimuli. RESULTS: We investigated effects of different metal and metal(oid) oxide nanoparticles on photosynthesis of oakleaf lettuce seedlings by monitoring the chlorophyll a fluorescence light radiation and reflectance from the leaves. Observations of ChlF parameters and changes in leaf morphology were carried out for 9 days in two-day intervals. Spectrophotometric studies were performed at 9th day. Suspensions of NPs with the following concentrations were used: 6% TiO2, SiO2; 3% CeO2, SnO2, Fe2O3; 0.004% (40 ppm) Ag; 0.002% (20 ppm) Au. Nanoparticles were applied directly on the leaves which caused small symptoms of chlorosis, necrosis and leaf veins deformation, but the plants fully recovered to the initial morphological state at 9th day. Leaf reflectance analysis showed an increase in FRI for SiO2-NPs and CeO2-NPs treatments and ARI2 for Fe2O3, however, WBI and PRI coefficients for the latter nanoparticle were lower than in control. Chlorophyll a fluorescence parameters have changed due to NPs treatment. Fe2O3-NPs caused an increase in Fv/F0, PIABS, ET0/RC, DI0/RC, ABS/RC in different time points in comparison to control, also Ag, Au and SnO2 treatment caused an increase in Fv/F0, PIABS or ET0/RC, respectively. On the other hand, TiO2-NPs caused a decrease in Fv/Fm and Fv/F0 parameters, but an increase in DI0/RC value was observed. SnO2-NPs decreased PIABS, but increased ET0/RC than compared to control. Nanoparticles affected the shape of the O-J-I-P curve in slight manner, however, further analyses showed unfavourable changes within the PSII antenna, manifested by a slowdown in the transport of electrons between the Chl molecules of the light-harvesting complex II and the active center of PSII due to NPs application. CONCLUSION: Changes in ChlF parameters and leaf reflectance values clearly proved the significant influence of NPs on the functioning of the photosynthetic apparatus, especially right after NPs application. The nature of these changes was strictly depended on the type of nanoparticles and sometimes underwent very significant changes over time. The greatest changes in ChlF parameters were caused by Fe2O3 nanoparticles, followed by TiO2-NPs. After slight response of O-J-I-P curves to treatment of the plants with NPs the course of the light phase of photosynthesis stabilized and at 9th day were comparable to the control curve.

Excimer-Mediated Ultrafast Intermolecular Nonradiative Decay Enables Giant Photothermal Performance for Optimized Phototheranostic.

Developing organic photothermal materials (OPMs) with high photothermal performance for phototheranostic mainly focus on the manipulation of intramolecular nonradiative (intraNR) decay, which often requires quite complicated and time-consuming molecular engineering. In addition to intraNR decay, intermolecular nonradiative (interNR) decay is equally important and more convenient in governing photothermal performance. However, controlling interNR decay remains challenging due to the limited understanding of their origin and dynamics. Here, systemic investigation of intraNR and interNR decay directs the first demonstration of simple manipulation of interNR decay to produce a giant photothermal performance for optimized phototheranostic. Among three designed polymers with varying fluorine substitution, structure-performance studies reveal a dimer-initiated interNR decay to improve photothermal performance. Dimer is formed by intermolecular CF···H hydrogen bond. This finding inspires a simple aggregation control strategy to form excited dimer, namely, excimer. It initiates an ≈100-fold enhancement in interNR decay rate over conventional intraNR decay to produce ultrahigh photothermal conversion efficiency of 81% for efficient photoacoustic imaging-guided photothermal therapy in vivo. This study provides insights into interNR decay in achieving a giant photothermal effect and paves a convenient way to develop high-performance OPMs.

Organic Nanodelivery Systems as a New Platform in the Management of Breast Cancer: A Comprehensive Review from Preclinical to Clinical Studies.

Breast cancer accounts for approximately 25% of cancer cases and 16.5% of cancer deaths in women, and the World Health Organization predicts that the number of new cases will increase by almost 70% over the next two decades, mainly due to an ageing population. Effective diagnostic and treatment strategies are, therefore, urgently required for improving cure rates among patients since current therapeutic modalities have many limitations and side effects. Nanomedicine is evolving as a promising approach for cancer management, including breast cancer, and various types of organic and inorganic nanomaterials have been investigated for their role in breast cancer diagnosis and treatment. Following an overview on breast cancer characteristics and pathogenesis and challenges of the current treatment strategies, the therapeutic potential of biocompatible organic-based nanoparticles such as liposomes and polymeric micelles that have been tested in breast cancer models are reviewed. The efficacies of different drug delivery and targeting strategies are documented, ranging from synthetic to cell-derived nanoformulations together with a summary of the interaction of nanoparticles with externally applied energy such as radiotherapy. The clinical translation of nanoformulations for breast cancer treatment is summarized including those undergoing clinical trials.

Activatable Sonoafterglow Nanoprobes for T-Cell Imaging.

Real-time imaging of immune systems benefits early diagnosis of disease and precision immunotherapy; however, most existing imaging probes either have "always-on" signals with poor correlation to immune responses, or rely on light excitation with limited imaging depth. In this work, an ultrasound-induced afterglow (sonoafterglow) nanoprobe is developed to specifically detect granzyme B for accurate imaging of T-cell immunoactivation in vivo. The sonoafterglow nanoprobe (Q-SNAP) consists of sonosensitizers, afterglow substrates, and quenchers. Upon ultrasound irradiation, sonosensitizers generate singlet oxygen, which converts substrates to high-energy dioxetane intermediates that slowly release energy after ultrasound cessation. Due to the proximity, energy from substrates can be transferred to quenchers, leading to afterglow quenching. Only in the presence of granzyme B, quenchers are liberated from Q-SNAP, resulting in bright afterglow emission with a limit of detection (LOD, 2.1 nm) much lower than most existing fluorescent probes. Due to the deep-tissue-penetrating ultrasound, sonoafterglow can be induced through a tissue of 4 cm thickness. Based on the correlation between sonoafterglow and granzyme B, Q-SNAP not only distinguishes autoimmune hepatitis from healthy liver as early as 4 h after probe injection, but also effectively monitors the cyclosporin-A-mediated reversal of T-cell hyperactivation. Q-SNAP thus offers the possibilities of dynamic monitoring of T-cell dysfunction and evaluation of prophylactic immunotherapy in deep-seated lesions.

Charge Concentration Limits the Hydrogen Evolution Rate in Organic Nanoparticle Photocatalysts.

Time-resolved microwave conductivity is used to compare aqueous-soluble organic nanoparticle photocatalysts and bulk thin films composed of the same mixture of semiconducting polymer and non-fullerene acceptor molecule and the relationship between composition, interfacial surface area, charge-carrier dynamics, and photocatalytic activity is examined. The rate of hydrogen evolution reaction by nanoparticles composed of various donor:acceptor blend ratio compositions is quantitatively measured, and it is found that the most active blend ratio displays a hydrogen quantum yield of 0.83% per photon. Moreover, it is found that nanoparticle photocatalytic activity corresponds directly to charge generation, and that nanoparticles have 3× more long-lived accumulated charges relative to bulk samples of the same material composition. These results suggest that, under the current reaction conditions, with ≈3× solar flux, catalytic activity by the nanoparticles is limited by the concentration of electrons and holes in operando and not a finite number of active surface sites or the catalytic rate at the interface. This provides a clear design goal for the next generation of efficient photocatalytic nanoparticles.