Simultaneous Enhancement of the Luminescence Intensity and Stability of Deep-Red CsPbI3 Perovskite Quantum Dots Achieved by a Doping Strategy.

The phase instability of CsPbI3 perovskite quantum dots (PQDs) restricts their practical applications due to the easy conversion from the luminescent cubic phase to the non-luminescent orthorhombic phase. The elemental doping route has been regarded as one of the most effective strategies to achieve high-quality PQDs-based phosphors. Herein, a stoichiometric amount of nickel chloride (NiCl2) has been effectively doped into the CsPbI3 lattice. The incorporation of Ni2+ ions has little effect on the crystal phase, structure, and morphology of the CsPbI3 PQDs but greatly influences their luminescence properties. The Ni2+ doping not only improves the luminescence performance but also greatly enhances the stability against temperature, storage time, and polar solvent. The formation process and luminescence and stability improvement mechanisms have been discussed. Moreover, the influence of a series of other metal chlorides (KCl, NaCl, MgCl2, ZnCl2, SnCl2, and CaCl2) on the luminescence performance of CsPbI3 PQDs has been systematically investigated, revealing that the luminescence intensity increases by introducing CaCl2, SnCl2, or ZnCl2 but decreases after doping MgCl2, NaCl, or KCl into the CsPbI3 lattice. The as-proposed doping strategy may have a significant impact on tackling the intrinsic instability of all-inorganic CsPbX3 PQDs, shedding light on their future applications in light-emitting diode (LED) devices and solid-state lighting.

Controllable Synthesis, Formation Process, and Luminescence Performances of Diverse Yttrium Compounds with Hollow Structures.

Hollow spherical Y2O3 and YBO3 have been prepared by a facile template-directed strategy using phenol-formaldehyde (PF) resin spheres as templates. The PF@Y(OH)CO3 precursor can be fabricated by a simple precipitation route. The Y2O3 hollow spheres are obtained via a direct annealing process, and the hollow spherical YBO3 are fabricated via a hydrothermal route followed by an annealing process at the expense of the same PF@Y(OH)CO3 precursor. The whole synthesis procedure is performed in aqueous solution without any surfactant or catalyst. Moreover, YVO4 quasi-octahedral microcrystals with spherical holes are obtained. The formation mechanisms of the yttrium compounds with different morphologies have been discussed. By incorporating proper rare earth activator ions into the Y2O3, YBO3, and YVO4 hosts, the as-synthesized luminescent materials can exhibit eminent performances with both down-conversion and up-conversion luminescence. Furthermore, the as-fabricated light-emitting diode (LED) devices can emit dazzling characteristic emission light, which reveals that the phosphors have application potential in lighting and displays. This simple synthesis strategy may provide a new idea for the fabrication of inorganic compounds with perfect hollow structures and excellent properties.

Synthesis of Copper-Doped MnO2 Electrode Materials by One-Step Hydrothermal Method for High Performance.

By adjusting the amount of Cu(NO3)2·3H2O, Cu2+-doped birnessite ?-MnO2 spherical substances were synthesized by a simple hydrothermal synthesis process without any templates and surfactants. The structure, morphology, and specific surface area were characterized by XRD, SEM, TEM and BET. Further study shows that the 0.25 mmol Cu-doped MnO2 sample is expected to provide higher specific capacitance (636.3 F g-1 at 1 A g-1 current density) compared with pure δ-MnO2 (335.6 F g-1 at the current density of 1 A g-1) and long-term cyclic stability (105.01 % capacitance retention after 1500 cycles at current density of 5 A g-1). Electrochemical impedance spectroscopy proved the low resistance characteristics of the prepared samples. All the results show that the copper-doped MnO2 material is not only low cost, but also of excellent electrochemical performance, thus possesses great potential in future energy development.

Defect-related luminescent bur-like hydroxyapatite microspheres induced apoptosis of MC3T3-E1 cells by lysosomal and mitochondrial pathways.

When orthopedic joints coated by hydroxyapatite (HA) were implanted in the human body, they release wear debris into the surrounding tissues. The generation and accumulation of wear particles will induce aseptic loosening. However, the potential bioeffect and mechanism of HA-coated orthopedic implants on bone cells are poorly understood. In this study, defect-related luminescent bur-like hydroxyapatite (BHA) microspheres with the average diameter of 7-9 µm which are comparable to that of the wear-debris particles from aseptically loosened HA implants or HA debris have been synthesized by hydrothermal synthesis and the MC3T3-E1 cells were set as a cells model to study the potential bioeffect and mechanism of BHA microspheres. The studies demonstrated that BHA microspheres could be taken into MC3T3-E1 cells via endocytosis involved in micropinocytosis- and clathrin-mediated endocytosis process, and exert cytotoxicity effect. BHA microspheres could induce the cell apoptosis by intracellular production of reactive oxygen species (ROS), which led to not only an increase in the permeability of lysosome and release of cathepsins B, but also mitochondrial dysfunction and DNA damage. Our results provide novel evidence to elucidate their toxicity mechanisms and might be helpful for more reasonable applications of HA-based orthopaedic implants in the future.

Monodisperse, Self-Activated Luminescent, and Mesoporous Silica Nanospheres for Drug Delivery.

Monodisperse mesoporous silica nanospheres with novel self-activated luminescence have been fabricated by a modified templating sol­gel method followed by heat treatment, without introducing any rare earth or transition metal ions as activators. The SEM, TEM, and N2 adsorption/desorption isotherms results show that the as-obtained mesoporous silica nanospheres exhibit well-defined morphology, good dispersion, high specific surface area and pore volume. MTT assay indicates that the sample exhibits no obvious cytotoxicity against the A549, HeLa, and MCF-7 cells, which make it suitable to be utilized as a drug carrier. Under ultraviolet excitation, the sample exhibits an intense blue emission. Interestingly, the photoluminescence intensity of the IBU drug loaded system increases with the increase of cumulatively released IBU. Due to the relationship between the luminescence properties and drug release behavior, the as-obtained luminescent drug carrier may be potential as a probe for monitoring or detecting the drug release process.

A traceable and bone-targeted nanoassembly based on defect-related luminescent mesoporous silica for enhanced osteogenic differentiation.

Osteoporosis is a degenerative bone disorder that affects millions of people worldwide. Despite many novel drugs or therapy strategies that have been developed, the curative effect of current treatments is far from satisfying. Development of effective treatments toward osteoporosis is imminent. Bone mesenchymal stem cells (BMSCs) are one kind of pluripotent stem cells, which are not only easy to separate and purify but also can self-renew and differentiate into osteogenic cells. In this work, a traceable drug delivery system based on gadolinium-labeled defect-related luminescent mesoporous silica nanoparticles (MSNs) was developed for bone marrow homing and enhanced osteogenic differentiation. The results showed that dexamethasone (DEX) could be loaded into nanocarriers and gave a sustained release behaviour. A unique defect-related luminescent property could be utilized to monitor the drug release effectively. In addition, the nanocarriers showed good biocompatibility and were uptaken mainly via an energy-dependent endocytosis process which was mediated by the macropinocytosis pathway. Furthermore, the nanocarriers can be simultaneously used as predominant contrast agents for magnetic resonance imaging. More importantly, DEX-loaded nanocarriers can significantly enhance the alkaline phosphatase activity and promote formation of matrix nodules of the BMSCs.

Up-Conversion Y2O3:Yb(3+),Er(3+) Hollow Spherical Drug Carrier with Improved Degradability for Cancer Treatment.

The rare earth hollow spheres with up-conversion luminescence properties have shown potential applications in drug delivery and bioimaging fields. However, there have been few reports for the degradation properties of rare earth oxide drug carriers. Herein, uniform and well-dispersed Y2O3:Yb(3+),Er(3+) hollow spheres (YOHSs) have been fabricated by a general Pechini sol-gel process with melamine formaldehyde colloidal spheres as template. The novel YOHSs with up-conversion luminescence has good drug loading amount and drug-release efficiency; moreover, it exhibits pH-responsive release patterns. In particular, the YOHSs sample exhibits low cytotoxicity and excellent degradable properties in acid buffer. After the sample was loaded with anticancer drug doxorubicin (DOX), the antitumor result in vitro indicates that YOHS-DOX might be effective in cancer treatment. The animal imaging test also reveals that the YOHSs drug carrier can be used as an outstanding luminescent probe for bioimaging in vivo application prospects. The results suggest that the degradable drug carrier with up-conversion luminescence may enhance the delivery efficiency of drugs and improve the cancer therapy in clinical applications.

Inorganic Nanomaterials as Carriers for Drug Delivery.

For safe and effective therapy, drugs must be delivered efficiently and with minimal systemic side effects. Nanostructured drug carriers enable the delivery of small-molecule drugs as well as nucleic acids and proteins. Inorganic nanomaterials are ideal for drug delivery platforms due to their unique physicochemical properties, such as facile preparation, good storage stability and biocompatibility. Many inorganic nanostructure-based drug delivery platforms have been prepared. Although there are still many obstacles to overcome, significant advances have been made in recent years. This review focuses on the status and development of inorganic nanostructures, including silica, quantum dots, gold, carbon-based and magnetic iron oxide-based nanostructures, as carriers for chemical and biological drugs. We specifically highlight the extensive use of these inorganic drug carriers for cancer therapy. Finally, we discuss the most important areas in the field that urgently require further study.

Defect-Related Luminescent Hydroxyapatite-Enhanced Osteogenic Differentiation of Bone Mesenchymal Stem Cells Via an ATP-Induced cAMP/PKA Pathway.

Novel defect-related hydroxyapatite (DHAP), which combines the advantages of HAP and defect-related luminescence, has the potential application in tissue engineering and biomedical area, because of its excellent capability of monitoring the osteogenic differentiation and material biodegradation. Although the extracellular mechanism of DHAP minerals and PO4(3-) functioning in osteogenic differentiation has been widely studied, the intracellular molecular mechanism through which PO4(3-) mediates osteogenesis of bone mesenchymal stem cells (BMSCs) is not clear. We examined a previously unknown molecular mechanism through which PO4(3-) promoted osteogenesis of BMSCs with an emphasis on adenosine-triphosphate (ATP)-induced cAMP/PKA pathway. Our studies showed that DHAP could be uptaken into lysosome, in which PO4(3-) was released from DHAP, because of the acid environment of lysosome. The released PO4(3-) interacted with ADP to form ATP, and then degraded into adenosine, an ATP metabolite, which interacted with A2b adenosine receptor to activate the cAMP/PKA pathway, resulting in the high expression of osteogenesis-related genes, such as Runx2, BMP-2, and OCN. These findings first revealed the function of ATP-metabolism in bone physiological homeostasis, which may be developed to cure bone metabolic diseases.

Effects of Cerium Oxide Nanoparticles on the Proliferation, Osteogenic Differentiation and Adipogenic Differentiation of Primary Mouse Bone Marrow Stromal Cells In Vitro.

The effects of cerium oxide nanoparticles (nanoceria) on the proliferation, osteogenic and adipogenic differentiation of primary mouse bone marrow stromal cells (BMSCs) were studied by employing 3-(4,5-dimethylthiazol-2-yl)-2,5-dipheny tetrazolium bromide (MTT), alkaline phosphatase (ALP) activity, collagen production, alizarin red-S (ARS) and oil red o stain assays. The results indicated that nanoceria increased the viability of BMSCs at all tested concentrations with evident dose dependence for 24 and 72 h. On day 14, nanoceria inhibited the osteogenic differentiation of BMSCs at all tested concentrations. On day 19 and 24, nanoceria inhibited the formation of mineralized matrix nodules of BMSCs at all tested concentrations. On day 17, nanoceria inhibited the adipogenic differentiation of BMSCs at all tested concentrations. This suggests that the effects of nanoceria on the proliferation, osteogenic differentiation and adipogenic differentiation of BMSCs are very complicated. Both the concentration and culture time have significant influence on the proliferation, osteogenic differentiation and adipogenic differentiation of BMSCs. These results will be helpful for rational applications of nanoceria in the future.

Hybrid Mesoporous Silica-Based Drug Carrier Nanostructures with Improved Degradability by Hydroxyapatite.

Potential bioaccumulation is one of the biggest limitations for silica nanodrug delivery systems in cancer therapy. In this study, a mesoporous silica nanoparticles/hydroxyapatite (MSNs/HAP) hybrid drug carrier, which enhanced the biodegradability of silica, was developed by a one-step method. The morphology and structure of the nanoparticles were characterized by TEM, DLS, FT-IR, XRD, N2 adsorption-desorption isotherms, and XPS, and the drug loading and release behaviors were tested. TEM and ICP-OES results indicate that the degradability of the nanoparticles has been significantly improved by Ca(2+) escape from the skeleton in an acid environment. The MSNs/HAP sample exhibits a higher drug loading content of about 5 times that of MSNs. The biological experiment results show that the MSNs/HAP not only exhibits good biocompatibility and antitumor effect but also greatly reduces the side effects of free DOX. The as-synthesized hybrid nanoparticles may act as a promising drug delivery system due to their good biocompatibility, high drug loading efficiency, pH sensitivity, and excellent biodegradability.

Defect-related luminescent mesoporous silica nanoparticles employed for novel detectable nanocarrier.

Uniform and well-dispersed walnut kernel-like mesoporous silica nanoparticles (MSNs) with diameters about 100 nm have been synthesized by a templating sol-gel route. After an annealing process, the as-obtained sample (DLMSNs) inherits the well-defined morphology and good dispersion of MSNs, and exhibits bright white-blue luminescence, higher specific surface area and pore volume, and better biocompatibility. The drug loading and release profiles show that DLMSNs have high drug loading capacity, and exhibit an initial burst release followed by a slow sustained release process. Interestingly, the luminescence intensity of the DLMSNs-DOX system increases gradually with the increase of cumulative released DOX, which can be verified by the confocal laser scanning images. The drug carrier DLMSNs can potentially be applied as a luminescent probe for monitoring the drug release process. Moreover, the DLMSNs-DOX system exhibits potent anticancer effect against three kinds of cancer cells (HeLa, MCF-7, and A549 cells).

Biocompatibility of defect-related luminescent nanostructured and microstructured hydroxyapatite.

Three defect-related luminescent hydroxyapatite (HAP) particles, S1, S2, and S3, with different morphologies (the samples S1 and S2 are nanorods with diameters of 25 nm and lengths of 30 and 100 nm, respectively; sample S3 is bur-like microspheres with diameters of 5-6 µm) were synthesized, and their biocompatibility was investigated by MTT, reactive oxygen species (ROS), interleukin-6 (IL-6), comet, and hemolysis assays. The results indicated that all samples were stable in cell culture medium and did not induce the synthesis of proinflammatory cytokine IL-6 or result in hemolysis. It was found that samples S1 and S3 inhibited osteoblast (OB) viability at concentrations of 5, 10, 20, 40, and 80 µg/mL for 24, 48, and 72 h. Sample S2 had no effect on the viability of OB at all tested concentrations for 24 and 48 h, but the viability of OB was increased at concentrations of 20, 40, and 80 µg/mL for 72 h. Samples S1 and S3 could increase the level of cellular ROS; sample S2 had no effect on the level of cellular ROS at a concentration of 20 µg/mL for 48 h. Although samples S1 and S3 induced significant DNA damage, sample S2 could not cause significant DNA damage at a concentration of 20 µg/mL for 72 h. The results suggest that longer nanorod HAP can show excellent biocompatibility and therefore may find potential applications in biomedical fields.

Size-dependent cytotoxicity of europium doped NaYF 4 nanoparticles in endothelial cells.

Lanthanide-doped sodium yttrium fluoride (NaYF4) nanoparticles exhibit novel optical properties which make them be widely used in various fields. The extensive applications increase the chance of human exposure to these nanoparticles and thus raise deep concerns regarding their riskiness. In the present study, we have synthesized europium doped NaYF4 (NaYF4:Eu(3+)) nanoparticles with three diameters and used endothelial cells (ECs) as a cell model to explore the potential toxic effect. The cell viability, cytomembrane integrity, cellular uptake, intracellular localization, intracellular reactive oxygen species (ROS), mitochondrial membrane potential (MMP), apoptosis detection, caspase-3 activity and expression of inflammatory gene were studied. The results indicated that these nanoparticles could be uptaken into ECs and decrease the cell viability, induce the intracellular lactate dehydrogenase (LDH) release, increase the ROS level, and decrease the cell MMP in a size-dependent manner. Besides that, the cells were suffered to apoptosis with the caspase-3 activation, and the inflammation specific gene expressions (ICAM1 and VCAM1) were also increased. Our results suggest that the damage pathway may be related to the ROS generation and mitochondrial damage. The results provide novel evidence to elucidate their toxicity mechanisms and may be helpful for more rational applications of these compounds in the future.

Controlled hydrolysis synthesis and luminescence properties of uniform TiO2 spheres with different titanium alkoxides.

A series of uniform and well-dispersed TiO2 spheres have been successfully synthesized through a controlled hydrolysis route by using different titanium alkoxides as reactants. The types of titanium alkoxides and stirring time have an effect on the uniformity and dispersion of the TiO2 spherical particles. The addition of a small amount of salt also plays a crucial role for the formation of the monodisperse TiO2 spheres. Under ultraviolet excitation, the as-obtained Eu(3+)-doped TiO2 spheres exhibit red emission corresponding to the electric-dipole allowed 5D0-7F2 transition of Eu3+ ions, which is induced by the lack of inversion symmetry at the Eu3+ ions site. The Eu(3+)-doped TiO2 phosphors might find potential applications in the fields such as optical displays, photoelectric devices, and light-emitting diodes (LEDs).

Cerium oxide nanoparticles protect endothelial cells from apoptosis induced by oxidative stress.

Oxidative stress is well documented to cause injury to endothelial cells (ECs), which in turn trigger cardiovascular diseases. Previous studies revealed that cerium oxide nanoparticles (nanoceria) had antioxidant property, but the protective effect of nanoceria on ROS injury to ECs and cardiovascular diseases has not been reported. In the current study, we investigated the protective effect and underlying mechanisms of nanoceria on oxidative injury to ECs. The cell viability, lactate dehydrogenase release, cellular uptake, intracellular localization and reactive oxygen species (ROS) levels, endocytosis mechanism, cell apoptosis, and mitochondrial membrane potential were performed. The results indicated that nanoceria had no cytotoxicity on ECs but had the ability to prevent injury by H2O2. Nanoceria could be uptaken into ECs through caveolae- and clathrin-mediated endocytosis and distributed throughout the cytoplasma. The internalized nanoceria effectively attenuated ROS overproduction induced by H2O2. Apoptosis was also alleviated greatly by nanoceria pretreatment. These results may be helpful for more rational application of nanoceria in biomedical fields in the future.

Well-defined strontium tungstate hierarchical microspheres: synthesis and photoluminescence properties.

Uniform and well-dispersed SrWO4 microspheres have been successfully synthesized through a hydrothermal method by using trisodium citrate and SDS as surfactants. XRD and SEM results demonstrate that the as-synthesized SrWO4 particles are high purity well crystallized and exhibit a relatively uniform spherical morphology. The as-obtained SrWO4:Ln3+ (Ln = Tb, Eu, Dy, and Sm) microspheres show intense light emissions with different colors coming from different Ln3+ ions under ultraviolet excitation, which might find potential applications in the fields such as light emitting phosphors, advanced flat panel displays, and light-emitting diodes (LEDs).

Defect-related luminescent materials: synthesis, emission properties and applications.

Luminescent materials have found a wide variety of applications, including information displays, lighting, X-ray intensification and scintillation, and so on. Therefore, much effort has been devoted to exploring novel luminescent materials so far. In the past decade, defect-related luminescent materials have inspired intensive research efforts in their own right. This kind of luminescent material can be basically classified into silica-based materials, phosphate systems, metal oxides, BCNO phosphors, and carbon-based materials. These materials combine several favourable attributes of traditional commercially available phosphors, which are stable, efficient, and less toxic, being free of the burdens of intrinsic toxicity or elemental scarcity and the need for stringent, intricate, tedious, costly, or inefficient preparation steps. Defect-related luminescent materials can be produced inexpensively and on a large scale by many approaches, such as sol-gel process, hydro(solvo)thermal reaction, hydrolysis methods, and electrochemical methods. This review article highlights the recent advances in the chemical synthesis and luminescent properties of the defect-related materials, together with their control and tuning, and emission mechanisms (solid state physics). We also speculate on their future and discuss potential developments for their applications in lighting and biomedical fields.

A facile approach toward transition metal oxide hierarchical structures and their lithium storage properties.

A simple, non-template, non-surfactant and environmentally friendly hydrothermal method is presented based on the controlled release of the reactants into the reaction solvents to induce slow nucleation and growth of three-dimensional hierarchical nanostructures of transition metal oxides. This method is a general approach, which can be used to prepare Co(3)O(4), CuO, and Ni(OH)(2)/NiO. These metal oxides with hierarchical nanostructures can be used as anode materials for lithium-ion batteries with good Li storage performance, e.g. high specific capacities and stable cyclability.