Juanjuan Peng

High-efficiency upconversion luminescent sensing and bioimaging of Hg(II) by chromophoric ruthenium complex-assembled nanophosphors.

A chromophoric ruthenium complex-assembled nanophosphor (N719-UCNPs) was achieved as a highly selective water-soluble probe for upconversion luminescence sensing and bioimaging of intracellular mercury ions. The prepared nanophosphors were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDXA), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). Further application of N719-UCNPs in sensing Hg(2+) was confirmed by optical titration experiment and upconversion luminescence live cell imaging. Using the ratiometric upconversion luminescence as a detection signal, the detection limit of Hg(2+) for this nanoprobe in water was down to 1.95 ppb, lower than the maximum level (2 ppb) of Hg(2+) in drinking water set by the United States EPA. Importantly, the nanoprobe N719-UCNPs has been shown to be capable of monitoring changes in the distribution of Hg(2+) in living cells by upconversion luminescence bioimaging.

Core–Shell Lanthanide Upconversion Nanophosphors as Four-Modal Probes for Tumor Angiogenesis Imaging

Multimodality imaging overcomes the shortage and incorporates the advantages of different imaging tools. Lanthanide-based nanoprobes are unique and have rich optical, magnetic, radioactive, and X-ray attenuation properties; however, simple doping of different lanthanide cations into one host can result in a material with multifunction but not the optimized properties. In this study, using NaLuF4:Yb,Tm as the core and 4 nm of (153)Sm(3+)-doped NaGdF4 (half-life of (153)Sm = 46.3 h) as the shell, we developed a lanthanide-based core-shell nanocomposite as an optimized multimodal imaging probe with enhanced imaging ability. The lifetime of upconversion luminescence (UCL) at 800 nm and relaxation rate (1/T1) were at 1044 μs and 18.15 s(-1)·mM(-1), respectively; however, no significant decrease in the attenuation coefficient was observed, which preserved the excellent X-ray imaging ability. The nanomaterial NaLuF4:Yb,Tm@NaGdF4((153)Sm) was confirmed to be effective and applicable for UCL imaging, X-ray computed tomography (CT), magnetic resonance imaging, and single-photon emission computed tomography (SPECT) in vivo. Furthermore, the NaLuF4:Yb,Tm@NaGdF4((153)Sm) nanoparticles were applied in tumor angiogenesis analysis by combining multimodality imaging of CT, SPECT, and confocal UCL imaging, which shows its value of multifunctional nanoparticles NaLuF4:Yb,Tm@NaGdF4((153)Sm) in tumor angiogenesis imaging.

Hollow silica nanoparticles loaded with hydrophobic phthalocyanine for near-infrared photodynamic and photothermal combination therapy.

Owing to the convenience and minimal invasiveness, phototherapy, including photodynamic therapy (PDT) and photothermal therapy (PTT), is emerging as a powerful technique for cancer treatment. To date, however, few examples of combination PDT and PTT have been reported. Phthalocyanine (Pc) is a class of traditional photosensitizer for PDT, but its bioapplication is limited by high hydrophobicity. In this present study, hollow silica nanospheres (HSNs) were employed to endow the hydrophobic phthalocyanine with water-dispersity, and the as-prepared hollow silica nanoparticles loaded with hydrophobic phthalocyanine (Pc@HSNs) exhibits highly efficient dual PDT and PTT effects. In vitro and in vivo experimental results clearly indicated that the dual phototherapeutic effect of Pc@HSNs can kill cancer cells or eradicate tumor tissues. This multifunctional nanomedicine may be useful for PTT/PDT treatment of cancer.

Polyphosphoric acid capping radioactive/upconverting NaLuF4:Yb,Tm,153Sm nanoparticles for blood pool imaging in vivo

Nanoparticles that circulate in the bloodstream for a prolonged period of time have important biomedicine applications. However, no example of lanthanide-based nanoparticles having a long-term circulation bloodstream has been reported to date. Herein, we report on difunctional radioactive and upconversion nanoparticles (UCNP) coated with polyphosphoric acid ligand, that is ethylenediamine tetramethylenephosphonic acid (EDTMP), for an application in single-photon emission computed tomography (SPECT) blood pool imaging. The structure, size and zeta-potential of the EDTMP-coated nanoparticles (EDTMP-UCNP) are verified using transmission electron microscopy and dynamic light scattering. Injection of radioisotope samarium-153-labeled EDTMP-UCNP (EDTMP-UCNP:(153)Sm) into mice reveal superior circulation time compared to control nanoparticles coated with citric acid (cit-UCNP:(153)Sm) and (153)Sm complex of EDTMP (EDTMP-(153)Sm). The mechanism for the extended circulation time may be attributed to the adhesion of EDTMP-UCNP on the membrane of red blood cells (RBCs). In vivo toxicity results show no toxicity of EDTMP-UCNP at the dose of 100 mg/kg, validating its safety as an agent for blood pool imaging. Our results provide a new strategy of nanoprobe for a long-term circulation bloodstream by introducing polyphosphoric acid as surface ligand.

Yolk-shell upconversion nanocomposites for LRET sensing of cysteine/homocysteine.

The fabrication of lanthanide upconversion nanocomposites as probes has become a new research hotspot due to its special advantages via utilizing upconversion luminescence (UCL) as a detection signal. Herein, a hybrid organic dye modified upconversion nanophosphor is successfully developed as a nanoprobe for cysteine/homocysteine. Yolk-shell structured upconversion nanoparticles (YSUCNP) with lanthanide upconversion nanophosphor as moveable core and silica as mesoporous shell are synthesized, and a colorimetric chemodosimeter for cysteine/homocysteine is accommodated in the hollow cavities. Thus, cysteine/homocysteine can be quantitatively detected on the basis of luminescent resonance energy transfer (LRET) in a UCL turn-off pattern. The dye-loaded YSUCNP possess good dispersibility in aqueous solution; thus detection of the targeted molecule can be achieved in pure water. Cellular experiments carried out with laser-scanning upconversion luminescence microscopy further demonstrate that the dye-loaded YSUCNP can serve as an intracellular nanoprobe to detect cysteine/homocysteine. Moreover, this dye-loading protocol can be developed as a common approach to construct other chemodosimeter-modified UCNP hybrid nanoprobes, as proved by a UCL turn-on style sensor for cyanide.

Upconversion Nanophosphors Naluf4:Yb,Tm for Lymphatic Imaging In Vivo by Real-Time Upconversion Luminescence Imaging under Ambient Light and High-Resolution X-ray CT

Lanthanide upconversion nanophosphor (UCNP) has attracted increasing attention for potential applications in bioimaging due to its excellence in deep and high contrast imaging. To date, most upconversion imaging applications were demonstrated in dark surroundings without ambient light for higher signal-to-noise ratio, which hindered the application of optical imaging guided surgery. Herein, the new established NaLuF4-based UCNP (NaLuF4:Yb,Tm, ~17 nm) with bright upconversion emission around 800 nm as imaging signal was used to realize imaging under ambient light to provide more convenient for clinician. Moreover, due to the existance of heavy element lutetium (Lu) in the host lattice, the NaLuF4:Yb,Tm nanoparticles can also be used as an X-ray CT imaging agent to enhance the imaging depth and in vivo imaging resolution.

Long-term in vivo biodistribution and toxicity of Gd(OH)3 nanorods.

The long-term retention of nanomaterials in the body is one of the biggest concerns about the safety of these materials for in vivo application. So, it is important to develop some nanomaterials which can be relatively more easily excreted. Rare earth hydroxide, that can be degraded under acidic condition in vivo, is one of the suitable candidates. Herein, Gd(OH)(3) nanorods, which are considered as magnetic resonance imaging (MRI) contrast agents, have been synthesized to evaluate their excretion process and potential toxicity. The long-term in vivo biodistribution of the materials was investigated using single photon emission computed tomography (SPECT) imaging with (153)Sm-doped Gd(OH)(3) nanorods as probes. Biodistribution results showed that the uptake and retention of the Gd(OH)(3) nanorods took place primarily in the liver, spleen and lung. Then, most of the nanorods were excreted from the bodies of mice very rapidly. Body weight data for the mice indicated that, when intravenously injected with 100 mg/kg of the nanorods, the mice survived for 150 days without any apparent adverse effects to their health. In addition, histological, hematological and biochemical analysis indicated that these nanorods have no overt toxicity.

Radioisotope post-labeling upconversion nanophosphors for in vivo quantitative tracking

Lanthanide based upconversion nanophosphors (UCNPs) attracted increasing attention for potential applications in bioimaging, while its in vivo behaviors are not clear until now due to no available quantification imaging tools. Herein, we developed a unique rare-earth cation-exchange-based postlabelling method to introduce (153)Sm into the lattice of UCNPs, providing this (153)Sm-postlabeling UCNP having bifunction of radioactive property and upconversion luminescence under excitation at 980 nm laser. This (153)Sm-postlabelling method shows rapid treatment time of <1 min, high labeling yield of >99%, and without usage of organic solvents. More importantly, this (153)Sm-postlabelling method is also suitable for most of rare earth nanoparticles to track their in vivo behaviors. The dynamic quantification studies of the in vivo fate of the rare-earth nanoparticles were further investigated by radioactive detection method such as single-photon emission computed tomography (SPECT) and gamma counter. The imaging results revealed that UCNPs were mainly captured by the mononuclear phagocyte system (liver and spleen). The amount of nanoparticles in liver arrived at its peak quicker and was about 15 fold of that in spleen. And the nanoparticles will be slowly excreted with the bile. Therefore, the concept of postlabeling (153)Sm onto lanthanide-based UCNPs may serve as a facile strategy of fabricating multifunctional nanoprobes for upconversion luminescence (UCL) and SPECT dual-modality imaging.

Upconversion nanoparticles dramatically promote plant growth without toxicity

Upconversion nanophosphors (UCNPs) have been widely used in bioscience and bioimaging, but the effect of UCNPs on plants and on animals after subsequent oral ingestion of the plants has not been studied previously. Herein, we investigate the effects of UCNPs on plant development using mung beans as a model. Incubation at a high UCNP concentration of 100 μg/mL led to growth inhibition, while a low concentration of 10 μg/mL promoted their development. Confocal imaging showed that UCNPs accumulated in the seeds and were transferred from seeds and roots to stems and leaves through the vascular system. Quantitative study by radioanalysis showed the distribution of UCNPs in the plant on the 5th day after incubation decreased in the order (root > seed > leaf > stem). After UCNP-treated bean sprouts were orally ingested by mice, UCNPs were completely excreted with feces, without absorption of residual amounts. Histology and hematology results showed no detectable toxic effects of UCNP-treated mung beans on exposed mice.Graphical abstract