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• Functional molecules can be loaded onto NaREF 4 (RE = rare earth) upconversion nanoparticles (UCNPs) through the formation of coordination bonds between the surface-exposed RE3+ ions and the appropriate chemical groups of functional molecules. Thus, the density of surface RE3+ ions directly determines the loading efficiency of NaREF 4 UCNPs. However, NaREF 4 is a binary cation system, rendering the surface-distributed Na+ and RE3+ ions remains a mystery. In this work, we introduce an effective strategy to significantly enhance the density of surface RE3+ ions, thus maximizing the loading capacity of NaREF 4 UCNPs. • The strategy is based on a heterovalent cation exchange (HCE) reaction in the surface region in which Na+ ions are replaced by RE3+ ions. The density of surface ligands enhances from 3.6 to 8.8 molecules/nm2 after reaction, suggesting that the loading efficiency increases by approximately 150%. • Benefiting from the improved loading capacity, we demonstrate such surface-RE-rich nanoparticles have the ability to offer higher colloidal stability and more desirable photodynamic therapy (PDT) efficacy. Surface modification of different functional molecules onto NaREF 4 (RE = rare earth) upconversion nanoparticles (UCNPs) impart their multiple functionalities. Functional molecules can be loaded onto NaREF 4 UCNPs through the formation of coordination bonds between the surface-exposed RE3+ ions and the appropriate chemical groups of functional molecules. The density of surface RE3+ ions directly determines the loading efficiency of NaREF 4 UCNPs. However, NaREF 4 is a binary cation system, rendering the surface-distributed Na+ and RE3+ ions remains a mystery. Here, we develop an effective strategy to significantly enhance the density of surface RE3+ ions, thus maximizing the loading capacity of NaREF 4 UCNPs. This strategy is based on a heterovalent cation exchange (HCE) reaction in the surface region in which Na+ ions are replaced by RE3+ ions. The density of surface ligands enhances from 3.6 to 8.8 molecules/nm2 after reaction, suggesting that the loading efficiency increases by approximately 150%. Benefiting from the improved loading capacity, we demonstrate such surface-RE-rich nanoparticles have the ability to offer higher colloidal stability and more desirable photodynamic therapy (PDT) efficacy. This work not only advances our understanding of cation exchange reactions in RE-based nanoparticles, but also provides significant value for considerable applications such as sensing, bioimaging, and therapy. [Display omitted] [ABSTRACT FROM AUTHOR]

The structure of the host lattice has a substantial influence on the optical properties of lanthanide-doped luminescent materials. Hexagonal-phase (β-phase) NaREF4(RE = rare earth) is the most commonly used crystal structure for lanthanide-doped upconversion nanoparticles (UCNPs) owing to its high upconversion (UC) efficiency. In this work, we report, for the first time, that more efficient cooperative sensitization upconversion (CSU) can be achieved in cubic-phase (α-phase) NaREF4UCNPs instead of their β-phase counterparts. With the passivation of an inert shell, the UC emission intensity of α-NaYbF4:Tb40%@CaF2is 10.5 times higher than that of β-NaYbF4:Tb40%@NaYF4. We propose that the high-symmetry crystal structure of the αphase facilitates the formations of [Yb–Yb] dimers and [Yb–Yb–Tb] clusters, which are particularly beneficial for CSU. Moreover, we prove that such Tb3+-based UCNPs are almost impervious to water quenching because of the large energy gap (∼15,000 cm−1) that existed in Tb3+between its lowest emit-ting level (5D4) and next low-lying level (7F0). Finally, their potential application for single-nanoparticle imaging has also been demonstrated. As expected, the α-core-shell UCNPs measured at the single-nanoparticle level are estimated to be 9-fold brighter than their β-core-shell counterparts. Importantly, the α-NaYbF4:Tb40%@CaF2UCNPs offer exciting opportunities for realizing single-nanoparticle imaging at ultralow irradiance (30 W/cm2).

Förster resonance energy transfer (FRET)-based homogeneous immunoassay obviates tedious washing steps and thus is a promising approach for immunoassays. However, a conventional FRET-based homogeneous immunoassay operating in the visible region is not able to overcome the interference of complex biological samples, thus resulting in insufficient detection sensitivity and poor accuracy. Here, we develop a near-infrared (NIR)-to-NIR FRET platform (Ex = 808 nm, Em = 980 nm) that enables background-free high-throughput homogeneous quantification of various biomarkers in complex biological samples. This NIR-to-NIR FRET platform is portable and easy to operate and is mainly composed of a high-performance NIR-to-NIR FRET pair based on lanthanide-doped nanoparticles (LnNPs) and a custom-made microplate reader for readout of NIR luminescence signals. We demonstrate that this NIR-to-NIR FRET platform is versatile and robust, capable of realizing highly sensitive and accurate detection of various critical biomarkers, including small molecules (morphine and 1,25-dihydroxyvitamin D), proteins (human chorionic gonadotropin), and viral particles (adenovirus) in unprocessed complex biological samples (urine, whole blood, and feces) within 5–10 min. We expect this NIR-to-NIR FRET platform to provide low-cost healthcare for populations living in resource-limited areas and be widely used in many other fields, such as food safety and environmental monitoring.

As a model hemimetabolous insect species and an invasive urban pest that is globally distributed, the American cockroach, Periplaneta americana, is of great interest in both basic and applied research. Previous studies on P. americananeuropeptide identification have been based on biochemical isolation and molecular cloning. In the present study, an integrated approach of genomics- and peptidomics-based discovery was performed for neuropeptide identification in this insect species. First, 67 conserved neuropeptide or neurohormone precursor genes were predicted via an in silicoanalysis of the P. americanagenome and transcriptome. Using a large-scale peptidomic analysis of peptide extracts from four different tissues (the central nervous system, corpora cardiac and corpora allata complex, midgut, and male accessory gland), 35 conserved (predicted) neuropeptides and a potential (novel) neuropeptide were then identified. Subsequent experiments revealed the tissue distribution, sex difference, and developmental patterns of two conserved neuropeptides (allatostatin B and short neuropeptide F) and a novel neuropeptide (PaOGS36577). Our study shows a comprehensive neuropeptidome and detailed spatiotemporal distribution patterns, providing a solid basis for future functional studies of neuropeptides in the American cockroach (data are available via ProteomeXchange with identifier PXD021660).