Fabrication of Fe3O4 core-TiO2/mesoSiO2 and Fe3O4 core-mesoSiO2/TiO2 Double Shell Nanoparticles for Methylene Blue Adsorption: Kinetic, Isotherms and Thermodynamic Characterization.

Herein, Fe3O4 core-TiO2/mesoSiO2 and Fe3O4 core-mesoSiO2/TiO2 double shell nanoparticles were prepared by first (R1) and second (R2) routes and applied for the removal of methylene blue. The reported adsorption capacities for R1-0.2, R1-0.4 and R2 samples were 128, 118 and 133 mg.g-1, respectively, which were obtained after 80 min as equilibrium contact time, and pH of 6 using a methylene blue concentration of 200 ppm. The adsorption of methylene blue using the prepared Fe3O4 core-meso SiO2/TiO2 double shell was analyzed by kinetic and isotherms models. In addition, thermodynamic investigations were applied to assess the spontaneous nature of the process. The obtained results confirmed that the pseudo-second order model is well fitted with the adsorption data and the Freundlich-isotherm assumption suggested a multilayer adsorption mechanism. In addition, results of the thermodynamic investigation indicated that ΔG° was in the range of -2.3 to -6.8 kJ/mol for R1-0.2, -2.8 to -6.3 kJ/mol for R1-0.4 and -2.0 to -5.2 kJ/mol for R2. In addition, the ΔH° and ΔS° values were found in the range of 26.4 to 36.19 kJ.mol-1 and 94.9 to 126.3 Jmol-1 K-1, respectively. These results confirm that the surfaces of Fe3O4 core-mesoSiO2/TiO2 and Fe3O4 core-TiO2/mesoSiO2 double shell exhibit a spontaneous tendency to adsorb methylene blue from the aqueous solutions. The achieved performance of Fe3O4 core-meso SiO2/TiO2 and Fe3O4 core-TiO2/meso SiO2 double shell as adsorbent for methylene blue removal will encourage future research investigations on the removal of a broad range of contaminants from wastewater.

In Vitro Safety Assessment of In-House Synthesized Titanium Dioxide Nanoparticles: Impact of Washing and Temperature Conditions.

Titanium dioxide nanoparticles (TiO2 NPs) have been widely used in food, cosmetics, and biomedical research. However, human safety following exposure to TiO2 NPs remains to be fully understood. The aim of this study was to evaluate the in vitro safety and toxicity of TiO2 NPs synthesized via the Stöber method under different washing and temperature conditions. TiO2 NPs were characterized by their size, shape, surface charge, surface area, crystalline pattern, and band gap. Biological studies were conducted on phagocytic (RAW 264.7) and non-phagocytic (HEK-239) cells. Results showed that washing amorphous as-prepared TiO2 NPs (T1) with ethanol while applying heat at 550 °C (T2) resulted in a reduction in the surface area and charge compared to washing with water (T3) or a higher temperature (800 °C) (T4) and influenced the formation of crystalline structures with the anatase phase in T2 and T3 and rutile/anatase mixture in T4. Biological and toxicological responses varied among TiO2 NPs. T1 was associated with significant cellular internalization and toxicity in both cell types compared to other TiO2 NPs. Furthermore, the formation of the crystalline structure induced toxicity independent of other physicochemical properties. Compared with anatase, the rutile phase (T4) reduced cellular internalization and toxicity. However, comparable levels of reactive oxygen species were generated following exposure to the different types of TiO2, indicating that toxicity is partially driven via non-oxidative pathways. TiO2 NPs were able to trigger an inflammatory response, with varying trends among the two tested cell types. Together, the findings emphasize the importance of standardizing engineered nanomaterial synthesis conditions and evaluating the associated biological and toxicological consequences arising from changes in synthesis conditions.

Thermal Fabrication of Magnetic Fe3O4 (Nanoparticle)@Carbon Sheets from Waste Resources for the Adsorption of Dyes: Kinetic, Equilibrium, and UV-Visible Spectroscopy Investigations.

Thermal treatment is applied for the direct conversion of palm stalk waste to Fe3O4 (np)@carbon sheets (Fe3O4 (np)@CSs). The effect of conversion temperature was investigated. The TEM examination of the prepared magnetic Fe3O4 (np)@CSs showed the formation of Fe3O4 (np) in a matrix of carbon sheets as a coated layer with surface functional groups including carbonyl and hydroxyl groups. Removal of dyes such as methyl orange, methylene blue, and neutral red was achieved using fabricated Fe3O4 (np)@CSs which were prepared at 250 °C, 400 °C, and 700 °C in a weak acidic medium. By studying the contact time effect for the adsorption of methylene blue, neutral red, and methyl orange, using the fabricated Fe3O4 (np)@CSs which were prepared at 250 °C and 400 °C, equilibrium occurred between 120 min and 180 min. In addition, the first-order and second-order kinetic models were applied to the adsorption data. The results revealed that the adsorption data fit better with the second-order kinetic model. Furthermore, the Freundlich model was found to be more suitable for describing the process of the separation of the dyes onto Fe3O4 (np)@CSs which were prepared at 250 °C and 400 °C, suggesting heterogenous surfaces and multi-layer adsorption.

Optimization of Pulsed Laser Ablation and Radio-Frequency Sputtering Tandem System for Synthesis of 2D/3D Al2O3-ZnO Nanostructures: A Hybrid Approach to Synthesis of Nanostructures for Gas Sensing Applications.

In this paper, a unique hybrid approach to design and synthesize 2D/3D Al2O3-ZnO nanostructures by simultaneous deposition is presented. Pulsed laser deposition (PLD) and RF magnetron sputtering (RFMS) methods are redeveloped into a single tandem system to create a mixed-species plasma to grow ZnO nanostructures for gas sensing applications. In this set-up, the parameters of PLD have been optimized and explored with RFMS parameters to design 2D/3D Al2O3-ZnO nanostructures, including nanoneedles/nanospikes, nanowalls, and nanorods, among others. The RF power of magnetron system with Al2O3 target is explored from 10 to 50 W, while the ZnO-loaded PLD's laser fluence and background gases are optimized to simultaneously grow ZnO and Al2O3-ZnO nanostructures. The nanostructures are either grown via 2-step template approach, or by direct growth on Si (111) and MgO<0001> substrates. In this approach, a thin ZnO template/film was initially grown on the substrate by PLD at ~300 °C under ~10 milliTorr (1.3 Pa) O2 background pressure, followed by growth of either ZnO or Al2O3-ZnO, using PLD and RFMS simultaneously under 0.1-0.5 Torr (13-67 Pa), and Ar or Ar/O2 background in the substrate temperate range of 550-700 °C. Growth mechanisms are then proposed to explain the formation of Al2O3-ZnO nanostructures. The optimized parameters from PLD-RFMS are then used to grow nanostructures on Au-patterned Al2O3-based gas sensor to test its response to CO gas from 200 to 400 °C, and a good response is observed at ~350 °C. The grown ZnO and Al2O3-ZnO nanostructures are quite exceptional and remarkable and have potential applications in optoelectronics, such in bio/gas sensors.

Facile Strategy for Fabricating an Organosilica-Modified Fe3O4 (OS/Fe3O4) Hetero-nanocore and OS/Fe3O4@SiO2 Core-Shell Structure for Wastewater Treatment with Promising Recyclable Efficiency.

The development of a sustainable process for heavy metal ion remediation has become a point of interest in various fields of research, including wastewater treatment, industrial development, and health and environmental safety. In the present study, a promising sustainable adsorbent was fabricated through continuous controlled adsorption/desorption processes for heavy metal uptake. The fabrication strategy is based on a simple modification of Fe3O4 magnetic nanoparticles with organosilica in a one-pot solvothermal process, carried out in order to insert the organosilica moieties into the Fe3O4 nanocore during their formation. The developed organosilica-modified Fe3O4 hetero-nanocores had hydrophilic citrate moieties, together with hydrophobic organosilica ones, on their surfaces, which facilitated the further surface coating procedures. To prevent the formed nanoparticles from leaching into the acidic medium, a dense silica layer was coated on the fabricated organosilica/Fe3O4 (OS/Fe3O4). In addition, the prepared OS/Fe3O4@SiO2 was utilized for the adsorption of cobalt(II), lead(II), and manganese(II) from the solutions. The data for the adsorption processes of cobalt(II), lead(II), and manganese(II) on OS/(Fe3O4)@SiO2 were found to follow the pseudo-second-order kinetic model, indicating the fast uptake of heavy metals. The Freundlich isotherm was found to be more suitable for describing the uptake of heavy metals by OS/Fe3O4@SiO2 nanoparticles. The negative values of the ΔG° showed a spontaneous adsorption process of a physical nature. The super-regeneration and recycling capacities of the OS/Fe3O4@SiO2 were achieved, comparing the results to those of previous adsorbents, with a recyclable efficiency of 91% up to the seventh cycle, which is promising for environmental sustainability.

Monodisperse Ultrahigh Nitrogen-Containing Mesoporous Carbon Nanospheres from Melamine-Formaldehyde Resin.

An aqueous emulsion polymerization self-assembly approach is demonstrated for the first time to synthesize ultrahigh nitrogen containing mesoporous polymer nanospheres, using melamine-formaldehyde resin oligomers as precursors. In the synthesis, change from alkaline to acidic conditions is critical for the formation of monodisperse mesostructured polymer nanospheres. Owing to unique structure of triazine stabilized in the covalent polymeric networks during the pyrolysis process, the derived mesoporous carbon nanospheres possess an ultrahigh nitrogen content (up to 15.6 wt%) even after pyrolysis at 800 °C, which is the highest nitrogen content among mesoporous carbon nanospheres. Furthermore, these monodisperse mesoporous carbon nanospheres possess a high surface area (≈883 m2 g-1 ) and large pore size (≈8.1 nm). As an anode for sodium-ion batteries, the ultrahigh nitrogen-containing mesoporous carbon nanospheres exhibit superior rate capability (117 mAh g-1 at a high current density of 3 A g-1 ) and high reversible capacity (373 mAh g-1 at 0.06 A g-1 ), indicating a promising material for energy storage.

High-Fidelity NIR-II Multiplexed Lifetime Bioimaging with Bright Double Interfaced Lanthanide Nanoparticles.

Fluorescence lifetime imaging provides more possibility of in vivo multiplexing in second near infrared (NIR-II) window. However, it still faces the obstacle that fluorescent probes with differentiable lifetime often exhibit quite different fluorescence intensity, especially the short lifetime usually accompanies with a weak fluorescence intensity, resulting in the difficulty for simultaneously decoding multiplexed lifetime information due to the interference of background noise. To facilitate high-fidelity lifetime multiplexed imaging, we developed a series of Er3+ doped double interface fluorescent nanoprobes (Er-DINPs): α-NaYF4 @NaErF4 : Ce@NaYbF4 @NaErF4 : Ce@NaYF4 with strong fluorescence intensity and easily distinguishable fluorescence lifetime. Both in vitro and in vivo experimental results confirmed the advantage of these probes with comparable fluorescence intensity for high-fidelity multiplexed lifetime bioimaging.

NIR-II cell endocytosis-activated fluorescent probes for in vivo high-contrast bioimaging diagnostics.

Fluorescence probes have great potential to empower bioimaging, precision clinical diagnostics and surgery. However, current probes are limited to in vivo high-contrast diagnostics, due to the substantial background interference from tissue scattering and nonspecific activation in blood and normal tissues. Here, we developed a kind of cell endocytosis-activated fluorescence (CEAF) probe, which consists of a hydrophilic polymer unit and an acid pH-sensitive small-molecule fluorescent moiety that operates in the "tissue-transparent" second near-infrared (NIR-II) window. The CEAF probe stably presents in the form of quenched nanoaggregates in water and blood, and can be selectively activated and retained in lysosomes through cell endocytosis, driven by a synergetic mechanism of disaggregation and protonation. In vivo imaging of tumor and inflammation with a passive-targeting and affinity-tagged CEAF probe, respectively, yields highly specific signals with target-to-background ratios over 15 and prolonged observation time up to 35 hours, enabling positive implications for surgical, diagnostic and fundamental biomedical studies.

Precisely Controlled Vertical Alignment in Mesostructured Carbon Thin Films for Efficient Electrochemical Sensing.

Two-dimensional carbon materials, incorporating a large mesoporosity, are attracting considerable research interest in various fields such as catalysis, electrochemistry, and energy-related technologies owing to their integrated functionalities. However, their potential applications, which require favorable mass transport within mesopore channels, are constrained by the undesirable and finite mesostructural configurations due to the immense synthetic difficulties. Herein, we demonstrate an oriented monomicelle assembly strategy, for the facile fabrication of highly ordered mesoporous carbon thin films with vertically aligned and permeable mesopore channels. Such a facile and reproducible approach relies on the swelling and fusion effect of hydrophobic benzene homologues for directional monomicelle assembly. The orientation assembly process shows precise controllability and great universality, affording mesoporous carbon films with a cracking-free structure over a centimeter in size, highly tunable thicknesses (13 to 85 nm, an interval of ∼12 nm), mesopore size (8.4 to 13.5 nm), and switchable growth substrates. Owing to their large permeable mesopore channels, electrochemical sensors based on vertical mesoporous carbon films exhibit an ultralow limit of detection (50 nmol L-1) and great sensitivity in dopamine detection.

Neutrophil-like Cell-Membrane-Coated Nanozyme Therapy for Ischemic Brain Damage and Long-Term Neurological Functional Recovery.

Oxidative stress and a series of excessive inflammatory responses are major obstacles for neurological functional recovery after ischemic stroke. Effective noninvasive anti-inflammatory therapies are urgently needed. However, unsatisfactory therapeutic efficacy of current drugs and inadequate drug delivery to the damaged brain are major problems. Nanozymes with robust anti-inflammatory and antioxidative stress properties possess therapeutic possibility for ischemic stroke. However, insufficiency of nanozyme accumulation in the ischemic brain by noninvasive administration hindered their application. Herein, we report a neutrophil-like cell-membrane-coated mesoporous Prussian blue nanozyme (MPBzyme@NCM) to realize noninvasive active-targeting therapy for ischemic stroke by improving the delivery of a nanozyme to the damaged brain based on the innate connection between inflamed brain microvascular endothelial cells and neutrophils after stroke. The long-term in vivo therapeutic efficacy of MPBzyme@NCM for ischemic stroke was illustrated in detail after being delivered into the damaged brain and uptake by microglia. Moreover, the detailed mechanism of ischemic stroke therapy via MPBzyme@NCM uptake by microglia was further studied, including microglia polarization toward M2, reduced recruitment of neutrophils, decreased apoptosis of neurons, and proliferation of neural stem cells, neuronal precursors, and neurons. This strategy may provide an applicative perspective for nanozyme therapy in brain diseases.

Gold nanoparticles plated porous silicon nanopowder for nonenzymatic voltammetric detection of hydrogen peroxide.

A voltammetric approach was developed for the selective and sensitive determination of hydrogen peroxide using Au plated porous silicon (PSi) nanopowder modified glassy carbon electrode (GCE). The AuNPs-PSi hybrid structure was synthesized via stain etching procedure followed by an immersion plating method to deposit AuNPs onto PSi via a simple galvanic displacement reaction with no external reducing agent to convert Au3+ to Au0. The as-fabricated AuNPs-PSi catalyst was successfully characterized by XRD, Raman, FTIR, XPS, SEM, TEM and EDS techniques. Well crystalline nature of the as-fabricated hybrid structure with AuNPs size ranging from 5 to 40 nm was observed. The specific surface area and total pore volume for both PSi and AuNPs plated PSi were evaluated using N2 adsorption isotherm technique. Cyclic voltammetry and electrochemical impedance spectroscopy techniques were applied to investigate the catalytic efficiency of AuNPs-PSi modified electrode compared to pure PSi/GCE and unmodified GCE. The sensing performance of the active material modified GCE was thoroughly examined with linear sweep voltammetry (LSV) and square wave voltammetry (SWV) techniques. The AuNPs-PSi/GCE exhibited a remarkable linear dynamic range between 2.0 and 13.81 mM (for LSV) and 0.5-6.91 mM for (SWV) with high sensitivity and low detection limit of 10.65 µAmM-1cm-2 and 14.84 µM for LSV, whereas 10.41 µAmM-1cm-2 and 15.16 µM using SWV techniques, respectively. The fabricated sensor electrode showed excellent anti-interfering ability in the presence of several common biomolecules as well as demonstrated good operational stability and reproducibility with low relative standard deviation. Moreover, the modified electrode showed acceptable recovery of H2O2 in a real sample analysis. Thus, the developed AuNPs-PSi hybrid nanomaterial represents an excellent electrocatalyst for the efficient detection and quantification of H2O2 by the electrochemical approach.

Rapid Room-Temperature Synthesis of Mesoporous TiO2 Sub-Microspheres and Their Enhanced Light Harvesting in Dye-Sensitized Solar Cells.

Submicron sized mesoporous spheres of TiO2 have been a potential alternative to overcome the light scattering limitations of TiO2 nanoparticles in dye-sensitized solar cells (DSSCs). Currently available methods for the growth of mesoporous TiO2 sub-microspheres involve long and relatively high temperature multi-stage protocols. In this work, TiO2 mesoporous sub-microspheres composed of ~5 nm anatase nanocrystallites were successfully synthesized using a rapid one-pot room-temperature CTAB-based solvothermal synthesis. X-Ray Diffraction (XRD) showed that the grown structures have pure anatase phase. Transmission electron microscopy (TEM) revealed that by reducing the surfactant/precursor concentration ratio, the morphology could be tuned from monodispersed nanoparticles into sub-micron sized mesoporous beads with controllable sizes (50-200 nm) and with good monodispersity as well. The growth mechanism is explained in terms of the competition between homogeneous nucleation/growth events versus surface energy induced agglomeration in a non-micelle CTAB-based soft templating environment. Further, dye-sensitized solar cells (DSSCs) were fabricated using the synthesized samples and characterized for their current-voltage characteristics. Interestingly, the DSSC prepared with 200 nm TiO2 sub-microspheres, with reduced surface area, has shown close efficiency (5.65%) to that of DSSC based on monodispersed 20 nm nanoparticles (5.79%). The results show that light scattering caused by the agglomerated sub-micron spheres could compensate for the larger surface areas provided by monodispersed nanoparticles.

Shape-tunable CuO-Nd(OH)3 nanocomposites with excellent adsorption capacity in organic dye removal and regeneration of spent adsorbent to reduce secondary waste.

Herein, we report for the first time, the synthesis of CuO-Nd(OH)3 nanocomposites via a co-precipitation method coupled with the hydrothermal aging process. Varying the pH of the reaction medium, the shape of the nanocomposites could be controlled which determines their surface areas. These CuO-Nd(OH)3 nanocomposites exhibit very high adsorption capacity with successful removal of ∼ 97% of brilliant blue G (BBG) from water in 180 min under ambient condition. The adsorption process primarily follows Lagergren pseudo-first-order kinetics. The Langmuir isotherm model fits well with a very high monolayer adsorption capacity of 394.1 mg g-1 at 30 °C. The mechanistic study supports chemisorption-type adsorption between the dye molecule and the adsorbent. Regeneration of the spent adsorbent makes the whole process cyclic and eco-friendly.

In Vivo High-resolution Ratiometric Fluorescence Imaging of Inflammation Using NIR-II Nanoprobes with 1550 nm Emission.

Quantitatively imaging the spatiotemporal distribution of biological events in living organisms is essential to understand fundamental biological processes. Self-calibrating ratiometric fluorescent probes enable accurate and reliable imaging and sensing, but conventional probes using wavelength of 400-900 nm suffer from extremely low resolution for in vivo application due to the disastrous photon scattering and tissue autofluorescence background. Here, we develop a NIR-IIb (1500-1700 nm) emissive nanoprobe for high-resolution ratiometric fluorescence imaging in vivo. The obtained nanoprobe shows fast ratiometric response to hypochlorous acid (HOCl) with a detection limit down to 500 nM, through an absorption competition-induced emission (ACIE) bioimaging system between lanthanide-based downconversion nanoparticles and Cy7.5 fluorophores. Additionally, we demonstrate the superior spatial resolution of 1550 nm to a penetration depth of 3.5 mm in a scattering tissue phantom, which is 7.1-fold and 2.1-fold higher than that of 1064 and 1344 nm, respectively. With this nanoprobe, clear anatomical structures of lymphatic inflammation in ratiometric channel are observed with a precise resolution of ∼477 µm. This study will motivate the further research on the development of NIR-II probes for high-resolution biosensing in vivo.

Peroxynitrite Activatable NIR-II Fluorescent Molecular Probe for Drug-Induced Hepatotoxicity Monitoring.

Drug-induced hepatotoxicity represents an important challenge for safety in drug development. The production of peroxynitrite (ONOO-) is proposed as an early sign in the progression of drug-induced hepatotoxicity. Currently, reported ONOO- probes mainly emit in the visible range or the first NIR window, which have limited in vivo biosensing application due to the autofluorescence and photon scattering. Herein, we developed a peroxynitrite activatable second near-infrared window (NIR-II) molecular probe for drug-induced hepatotoxicity monitoring, based on the fusion of an NIR-II fluorescence turn-on benzothiopyrylium cyanines skeleton and the phenyl borate. In the presence of ONOO-, the probe IRBTP-B can turn on its NIR-II fluorescence by yielding its fluorophore IRBTP-O and display good linear response to ONOO-. Tissue phantom study confirmed reliable activated signals could be acquired at a penetration depth up to 5 mm. Using this probe, we disclose the upregulation of ONOO- in a preclinical drug-induced liver injury model and the remediation with N-acetyl cysteine (NAC) in vivo. We expect that this strategy will serve as a general method for the development of an activatable NIR-II probe based on the hydroxyl functionalized reactive sites by analyte-specific triggering.

Aqueous dispersible green luminescent yttrium oxide:terbium microspheres with nanosilica shell coating.

Tb-doped Y2O3 microspheres (MSs) were prepared via a homogeneous thermal degradation process at a low temperature and then coated with a nanosilica shell (Y2O3:Tb@SiO2) using a sol-gel process. The core MSs were highly crystalline and spherical with a porous surface, single cubic phase, and particle size of 100-250 nm. Transmission electron microscopy (TEM) images clearly showed the spherical shape of the as-prepared core MSs, which were fully covered with a thick and mesoporous nanosilica shell. Fourier transform infrared (FTIR) spectra displayed the well-resolved infrared absorption peaks of silica (SiO, SiOSi, etc.), confirming the presence of the silica surface coating. The core MSs retained their spherical shape even after heat treatment and subsequent silica surface coating. It was observed that the core/shell MSs are easily dispersible in aqueous media and form a semi-transparent colloidal solution. Ultraviolet/visible and zeta potential studies were tested to prove the changes in the surface chemistry of the as-designed core/shell MSs and compare with their core counterpart. The growth of the amorphous silica shell not only increased the particle size but also enhanced remarkably the solubility and colloidal stability of the MSs in aqueous media. The strongest emission lines originating from the characteristic intra-shell 4f-4f electronic transitions of Tb ions were quenched after silica layer deposition, but the MSs still showed strong green (5D4 → 7F5 at 530-560 nm as most dominant) emission efficiency, which indicates great potential in fluorescent bio-probes. The emission intensity is discussed in relation to the quenching mechanism induced by surface silanol (Si-OH) groups, particle size, and surface charge.

Au/Ag Nanobox-Based Near-Infrared Surface-Enhanced Raman Scattering for Hydrogen Sulfide Sensing.

Hydrogen sulfide (H2S) is a gaseous signaling agent that has important regulatory roles in many biological systems but remains difficult to measure in living biological specimens. Herein, we report a novel near-infrared (NIR) activated surface-enhanced Raman scattering (SERS) nanosensor for in vitro and in vivo H2S assay utilizing Au/Ag alloy nanoboxes with local surface plasmon resonance (LSPR) at 741 nm. This detection is realized by SERS spectrum changes of the NIR probes, which are labeled on Au/Ag nanoboxes under NIR laser irradiation, resulting from the reaction of H2S with Ag in the substrate of Au/Ag nanoboxes. Owing to the well-matching between the incident laser light frequency and the LSPR of the substrates at the NIR region, this SERS nanosensor with a high selectivity and sensitivity can be utilized to monitor the distribution of H2S in living cells and zebrafish embryos. Noticeably, the NIR SERS signal is detectable in tissues at depths of up to 12 mm, demonstrating its huge potential in the in vivo studies of pathophysiological processes involving H2S.

Small-Molecule Lanthanide Complexes Probe for Second Near-Infrared Window Bioimaging.

Over the past few years, significant efforts have been made to create new fluorescent probes operating at longer wavelengths, particularly in the second near-infrared (NIR-II) window from 1000 to 1700 nm, offering enhanced tissue penetration compared to light in the visible and first near-infrared window (700-900 nm). However, most of the reported NIR-II fluorophores meet such dilemmas; they are excreted slowly and largely retained within the reticuloendothelial system. Here, we report a rapidly excreted NIR-II lanthanide complex Nd-DOTA (over 50% excreted through the kidneys within 3 h postinjection) with a molecular mass only 0.54 kDa. The NIR-II imaging quality of Nd-DOTA was far superior to that of clinically approved ICG with good photostability and deep tissue penetration (7 mm). Superior tumor-to-normal tissue ratio was successfully achieved to facilitate the abdominal ovarian metastases surgical delineation. Metastases with ≤1 mm can be completely excised under NIR-II bioimaging guidance. Significantly, since the Nd-DOTA structure is same to the clinically approved magnetic resonance imaging (MRI) contrast Gd-DOTA, it will speed up the clinical translation for this novel kind of NIR-II probes in the future.

Near-infrared rechargeable "optical battery" implant for irradiation-free photodynamic therapy.

As a minimal or noninvasive therapeutic method for tumors, photodynamic therapy (PDT) induced by the external laser irradiations has attracted great attentions. However, the UV-visible responsive property with low tissue penetration and photothermal effect from the prolonged irradiation impedes their further applications. Herein, a near-infrared (NIR) rechargeable "optical battery" for irradiation-free PDT is fabricated by embedding upconversion materials, persistent luminescence materials, photosensitizer into biocompatible polydimethylsiloxane. After 5 s quickly charged by 980-nm NIR laser, the PDT "optical battery" can generate green persistent luminescence and produce cytotoxic singlet oxygen for continuous irradiation-free PDT (∼30 min) without external irradiation. Due to deep tissue penetration and discontinuous short exposure of NIR light charging source, the "optical battery" can still be charged to continuously generate singlet oxygen in deep tissue (∼4 mm) with low photothermal effect. The PDT implant can be easily optimized in size and shape aiming at different nidus sites and achieved different functions by adding other functional components (e.g. CaO2 for oxygen envolving to overcome hypoxia tumor). The effective tumor proliferation inhibiting capability of this NIR rechargeable "optical battery" may give rise to next generation of intelligent stimuli-responsive nanomedicine and noninvasive photo bio-stimulation research for future clinical applications.