Designing stimuli-responsive upconversion nanoparticles based on a mimetic immunoassay for potential accurate diabetic nephropathy diagnosis.

Diabetic nephropathy (DN) is the most common microvascular complication associated with incurable diabetes. The gold standard diagnostic method for DN is based on the detection of proteinuria but it overlooks cases of non-proteinuria (NP-DN). To address this limitation, urinary sialic acid (SA) has been confirmed as an effective biomarker for various DNs. Herein, we constructed an ultrasensitive non-proteinuria assay platform to accurately diagnose DN within 20 min. This platform utilized the ninhydrin reaction between acidic ninhydrin and urinary sialic acid (SA) as an effective biomarker for various DNs. A compound with a maximum absorption peak at 470 nm was produced in this reaction and contributed to the fluorescence decrease of the blue-emission core-shell upconverting nanoparticles through the inner filter effect (IFE). By integrating the inner filter effect (IFE) with a mimetic immunoassay, the imperceptible color was converted into highly sensitive fluorescence signals. This protocol shows a stable and high sensitivity with a detection limit of 20 nmol L-1 and provides 100% positive prediction for urine samples, demonstrating its potential for clinical diagnosis and long-term monitoring of DN.

Multi-color luminescence and anticounterfeiting application of upconversion nanoparticle.

Multi-color luminescence materials are important in the illumination, solid-state three-dimensional display, information storage, biological labelling and anticounterfeiting fields. Herein, we designed a novel core-shell structure upconversion nanoparticle (UCNP) material (NaYF4) with lanthanide ion doping to achieve multi-color luminescence under a single NIR excitation laser. Different from the typical single-sensitizer materials, the core-shell structure utilizes Nd3+, Yb3+, Tm3+ and Er3+ ions to obtain tuning of the color and brightness. The doping of Nd3+ ions enhances the weak color (red) light source to maintain the light color balance. Benefiting from the color adjustment of the sensitizers and the change of the core-shell coating, bright-white emission and flexible color emission from red to green, cyan and blue can be achieved via the diverse doped rare earth ions in a single UCNP under continuous-wave laser excitation (980 nm). Simultaneously, the emission color of the UCNPs can change with the intensity of the excitation light source and the wavelength. The bright-white emission can be used for lighting displays, and the flexible full-color emission can be applied in the anticounterfeiting and information storage fields.

Designing stimuli-responsive upconversion nanoparticles based on an inner filter effect mimetic immunoassay for phenylketonuria accuracy diagnosis.

Phenylketonuria (PKU) is the most common inborn error of amino acid metabolism caused by an inherited deficiency in L-phenylalanine-4-hydroxylase (PAH) activity. It is usually controlled by diet and monitored regularly with markers, as PKU is not curable. However, conventional methods for target biomarker analysis are invasive and labor intensive. Here, we report a rapid and sensitive, mimetic immunoassay for detecting phenylpyruvate (PhPY) based on stimuli-responsive upconversion nanoparticles with an inner filter effect (IFE). The strong and specific binding of PhPY and Fe3+ forms a complex with maximum absorption at approximately 640 nm. Upon the addition of LiYF4:Er,Ho@LiYF4 UCNPs (maximum emission at 699 nm), the inner filter effect is triggered along with a concurrent decrease in fluorescence. The proposed method demonstrates ultra sensitivity with a detection limit of 79.63 µg L-1, which is superior to most reported methods, thereby enabling phenylpyruvate assays on human urine.

Antibacterial and antibiofilm activities of chitosan nanoparticles loaded with Ocimum basilicum L. essential oil.

Nanoencapsulation has been verified to be an effective technique to improve the physical stability of essential oils. In this study, Ocimum basilicum L. essential oil (BEO) was encapsulated into chitosan nanoparticles by emulsion and ionic gelation. The success of BEO loading was revealed by Fourier transform infrared (FTIR) spectroscopy, ultraviolet visible spectrophotometry and X-ray diffraction (XRD) analyses. Scanning electron microscopy (SEM) images and dynamic light scattering (DLS) illustrated regular distribution and spherical morphology with a particle size range of 198.7 - 373.4 nm. The prepared samples had an encapsulation efficiency (EE) range of 50.39 - 5.13% and a loading capacity (LC) range of 7.22-19.78%. Encapsulation of BEO into chitosan nanocarriers demonstrated strong antibacterial and antibiofilm capacity against E. coli and S. aureus with inhibition diameter of 15.3 mm and 21.0 mm, respectively, and the obtained nanoparticles were found to damage cell membranes and cause the leakage of biological macromolecules.

A Rapid and Facile Separation-Detection Integrated Strategy for Exosome Profiling Based on Boronic Acid-Directed Coupling Immunoaffinity.

Exosomes are a promising noninvasive tumor biomarker for cancer diagnosis and classification. However, efficient capture and precise analysis of exosomes in complex biological samples remain challenging. Here, sensitive profiling of exosomes with an integrated separation-detection strategy of 37 min is performed based on boronic acid-directed coupling immunoaffinity. The modification of g-C3N4 nanosheets with boronic acid (BCNNS) contributes to antibody binding under physiological conditions, which is accompanied by fluorescence enhancement. When exosomes are captured by an antibody equipped with BCNNS, a decrease in fluorescence can be induced; moreover, using the dispersion property of BCNNS, the exosomes can be separated by a simple centrifugation step. The protocol shows a favorable sensitivity with a detection limit of 2484 particles/mL. By changing only the fused antibody, exosome phenotype information profiling can be achieved, and exosomes derived from four different cell lines (HeLa, HepG2, MCF-7, and MCF-10A) can be successfully distinguished. More significantly, the positive prediction accuracy results reach 100% for serum samples from different individuals and have the advantage of multiple parameters; thus, the method has great potential in noninvasive diagnosis and point-of-care testing.

PEI-capped KMgF3:Eu2+ nanoparticles for fluorescence detection of nitroaromatics in municipal wastewater.

The probing and quantitative detection of nitroaromatics is key for public safety and the monitoring of wastewater. Currently, most techniques used for the detection of nitroaromatics require ideal conditions rather than real conditions, making practical applications challenging. As nitroaromatics have strong absorption in the range of 350-370 nm, we can design a kind of KMgF3:Eu2+ nanophosphor with a strong f-f transition emission located at 362 nm, and an energy resonance transfer system based on the overlap of the emission peak of nanophosphors and the absorption peak of nitroaromatics can be constructed to realize the quantitative detection of nitroaromatics in municipal wastewater. Based on this, in this paper, a fluorescence resonance energy transfer (FRET) sensor is designed by choosing polyethylenimine (PEI)-capped KMgF3:Eu2+ nanoparticles as an energy donor for the ultrasensitive detection of nitroaromatics, which can also work as an energy acceptor. The KMgF3:Eu2+ nanoparticle sensor shows great sensitivity and selectivity and good linear characteristics in both DI water and wastewater. The detection limits in municipal wastewater were 0.456, 0.598, 0.667, 0557 and 0.678 ng/mL for TNT, TNP, p-nitrotoluene, dinitrobenzene (DNB), and nitrobenzene (NB), respectively. The detection accuracy was identified by high-performance liquid chromatography (HPLC). The results showed that the sensor had superior sensitivity and great accuracy and could be used in practical applications.

Detection of nitroaromatics in aqueous media based on luminescence resonance energy transfer using upconversion nanoparticles as energy donors.

Upconversion nanoparticle (UCNP)-based luminescence resonance energy transfer (LRET) systems are a powerful tool widely used to detect organic molecules or metal ions because of their simplicity and high sensitivity. The sandwich structure NaYF4:Er3+,Yb3+@NaYF4@NH2 UCNPs, as a highly selective and sensitive aqueous probe for detecting nitroaromatics, has been designed and prepared by a cothermolysis method and modified with polyetherimide to acquire amine groups on the surface of the core/shell UCNPs. The detection principle of nitroaromatics is based on LRET, which forms the Meisnheimer complex between the electron-deficient cyclobenzene of nitroaromatics and the electron-rich amino group on the surface of the sandwich structure UCNPs. As a consequence, nitroaromatics can be brought into close proximity to the sandwich structure UCNPs. With the increase of nitroaromatics (2,4,6-trinitrophenol and 2,4,6-trinitrotoluene) concentrations, the sandwich structure NaYF4:Er3+,Yb3+@NaYF4@NH2 UCNPs display a dramatic luminescent quenching effect at 407 nm and 540 nm under 980 nm excitation. The luminescent quenching intensity of the sandwich structure UCNPs is linearly correlated to the concentration of the nitroaromatics. The detection limit of 2,4,6-trinitrophenol (TNP) and 2,4,6-trinitrotoluene (TNT) are 0.78 and 0.77 ng ml-1, respectively. Therefore, the sandwich structure of NaYF4:Er3+,Yb3+@NaYF4@NH2 UCNPs can act as a valuable probe to detect nitroaromatics in public safety and security conditions.

Reply to the 'Comment on "A universal approach for calculating the Judd-Ofelt parameters of RE3+ in powdered phosphors and its application for the ß-NaYF4:Er3+/Yb3+ phosphor derived from auto-combustion-assisted fluoridation"' by D. Zhang, Q. Xu and Y. Zhang, Phys. Chem. Chem. Phys., 2019, 21, DOI: 10.1039/C8CP07577H.

In this Reply, we truthfully respond to the comments on our recent paper entitled "A universal approach for calculating the Judd-Ofelt parameters of RE3+ in powdered phosphors and its application for the ß-NaYF4:Er3+/Yb3+ phosphor derived from auto-combustion-assisted fluoridation" published in Phys. Chem. Chem. Phys. [Y. Zhang, B. Chen, S. Xu, X. Li, J. Zhang, J. Sun, X. Zhang, H. Xia, R. Hua, A universal approach for calculating the Judd-Ofelt parameters of RE3+ in powdered phosphors and its application for the beta-NaYF4:Er3+/Yb3+ phosphor derived from auto-combustion-assisted fluoridation, Phys. Chem. Chem. Phys., 20, 2018, 15876-15883]. In the Comment, the authors oppugned partial calculation results we reported in our original paper, thus we redid the calculations and compared the presently obtained results with the original ones and the author provided ones. The recalculations and comparisons confirmed that our calculations are reproducible and the results are correct. In the Comment, the authors also made some comments on the Judd-Ofelt calculation approaches for powdered samples reported by other researchers. Following the authors' train of thought we added some supplements to the comments to understand the application strategy of Judd-Ofelt theory. Furthermore, we extended some points of view regarding the fluorescence lifetime measurements the authors presented in the Comment.

A universal approach for calculating the Judd-Ofelt parameters of RE3+ in powdered phosphors and its application for the ß-NaYF4:Er3+/Yb3+ phosphor derived from auto-combustion-assisted fluoridation.

It is difficult to calculate the Judd-Ofelt (J-O) parameters for trivalent rare earth (RE)-doped powders due to the unavailable absorption spectrum that is necessarily used in the conventional J-O calculation procedure. In this study, a universal method starting from the diffuse-reflection spectrum for calculating the J-O parameters of RE3+-doped powdered samples was proposed. In this proposed method, by taking the Kubelka-Munk function into account, the absorption cross-section spectrum was derived from the diffuse-reflection spectrum in the RE3+-doped powdered sample using the connection between the absorption cross section and the radiative transition rate of RE3+. Then, the J-O parameters might be calculated from the absorption cross-section spectrum via the traditional J-O calculation technique. The NaYF4:Er3+/Yb3+ and NaYF4:Er3+ phosphors were prepared via an auto-combustion-assisted fluoridation technique, and the J-O calculation was carried out for the obtained samples. The obtained J-O parameters were compared with those reported in the literature and also verified by comparing the calculated radiative transition lifetimes with the experimental values. Finally, it was deduced that the proposed J-O calculation route was practicable.

Supported black phosphorus nanosheets as hydrogen-evolving photocatalyst achieving 5.4% energy conversion efficiency at 353 K.

Solar-driven water splitting using powdered catalysts is considered as the most economical means for hydrogen generation. However, four-electron-driven oxidation half-reaction showing slow kinetics, accompanying with insufficient light absorption and rapid carrier combination in photocatalysts leads to low solar-to-hydrogen energy conversion efficiency. Here, we report amorphous cobalt phosphide (Co-P)-supported black phosphorus nanosheets employed as photocatalysts can simultaneously address these issues. The nanosheets exhibit robust hydrogen evolution from pure water (pH = 6.8) without bias and hole scavengers, achieving an apparent quantum efficiency of 42.55% at 430 nm and energy conversion efficiency of over 5.4% at 353 K. This photocatalytic activity is attributed to extremely efficient utilization of solar energy (~75% of solar energy) by black phosphorus nanosheets and high-carrier separation efficiency by amorphous Co-P. The hybrid material design realizes efficient solar-to-chemical energy conversion in suspension, demonstrating the potential of black phosphorus-based materials as catalysts for solar hydrogen production.

Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution.

Few-layer black phosphorus (BP) nanosheets were first reported as a 2D material for the application of field-effect transistors in 2014 and have stimulated intense activity among physicists, chemists, and material and biomedical scientists, driving research into novel synthetic techniques to produce BP nanosheets. At present, exfoliation is the main route toward few-layer BP nanosheets via employing bulk BP as raw material. However, this is a complicated and time-consuming process, which is difficult for the large-scale synthesis of BP nanosheets. Moreover, BP degrades rapidly when exfoliated to nanoscale dimensions, resulting in the rapid loss of semiconducting properties. Here, we report the direct wet-chemical synthesis of few-layer BP nanosheets in gram-scale quantities in a bottom-up approach based on common laboratory reagents at low temperature, showing excellent stability due to partial oxidation of surface. Solvent and temperature are two critical factors, controlling not only the formation of BP nanosheets but also the thickness. The as-prepared BP nanosheets can extract hydrogen from pure water (pH = 6.8), exhibiting more than 24-fold higher activity than the well-known C3N4 nanosheets. Our results reporting the ability to prepare few-layer BP nanosheets with a facile, scalable, low-cost approach take us a step closer to real-world applications of phosphorene including next-generation metal-free photocatalysts for photosynthesis.

Dually functioned core-shell NaYF4:Er3+/Yb3+@NaYF4:Tm3+/Yb3+ nanoparticles as nano-calorifiers and nano-thermometers for advanced photothermal therapy.

To realize photothermal therapy (PTT) of cancer/tumor both the photothermal conversion and temperature detection are required. Usually, the temperature detection in PTT needs complicated instruments, and the therapy process is out of temperature control in the present investigations. In this work, we attempt to develop a novel material for achieving both the photothermal conversion and temperature sensing and control at the same time. To this end, a core-shell structure with NaYF4:Er3+/Yb3+ core for temperature detection and NaYF4:Tm3+/Yb3+ shell for photothermal conversion was designed and prepared. The crystal structure and morphology of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Furthermore, the temperature sensing properties for the NaYF4:Er3+/Yb3+ and core-shell NaYF4:Er3+/Yb3+@NaYF4:Tm3+/Yb3+ nanoparticles were studied. It was found that the temperature sensing performance of the core-shell nanoparticles did not become worse due to coating of NaYF4:Tm3+/Yb3+ shell. The photothermal conversion behaviors were examined in cyclohexane solution based on the temperature response, the NaYF4:Er3+/Yb3+@NaYF4:Tm3+/Yb3+ core-shell nanoparticles exhibited more effective photothermal conversion than that of NaYF4:Er3+/Yb3+ nanoparticles, and a net temperature increment of about 7 °C was achieved by using the core-shell nanoparticles.

NaYF4:Sm3+/Yb3+@NaYF4:Er3+/Yb3+ core-shell structured nanocalorifier with optical temperature probe.

A core-shell structure with a NaYF4:Sm3+/Yb3+ core for photothermal conversion nanocalorifier and a NaYF4:Er3+/Yb3+ shell as temperature probe for potential applications in photothermal therapy (PTT) were synthesized by a thermal decomposition technique of rare-earth oleate complexes. The optical temperature reading-out property for the NaYF4:Sm3+/Yb3+@NaYF4:Er3+/Yb3+ core-shell structure was systematically investigated and it was found that in comparison with pure NaYF4:Er3+/Yb3+ particles, the temperature sensing performance of the NaYF4:Er3+/Yb3+ shell did not become worse due to the presence of NaYF4:Sm3+/Yb3+ core. Furthermore, the photothermal conversion behavior for core-shell nanoparticles was successfully examined by dint of temperature sensing of the NaYF4:Er3+/Yb3+ shell, and it was found that an excitation-power-density-dependent temperature increase of up to several tens degrees can be achieved. All the experimental results suggested that the core-shell structure may be an excellent nanocalorifier candidate for advanced temperature-controllable PTT.

Concentration-Dominated Temperature-Dependence of Upconversion Luminescence in Gd6WO12 Nanophosphor Co-Doped with Er3+ and Yb3+.

Nanosized Gd6WO12 phosphors containing various Er3+ concentrations and fixed Yb3+ concentration were synthesized by a co-precipitation method. The crystal structure and microscopic morphology of the obtained nanophosphors were characterized by means of X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). Two-photon processes for both the green and red upconversion (UC) emissions were confirmed by analyzing the dependence of UC intensities on 980 nm laser working current. UC emission intensity changing with temperature displays different trends for the samples with different Er3+ concentrations. The experimental results indicated that thermal quenching behavior of UC luminescence could not be simply explained by crossover mechanism. The enhancement for green UC emission in the sample with higher Er3+ concentration was discussed. Finally, the ErS+ concentration dependence of UC luminescence was experimentally observed, and its mechanisms were analyzed.

Hydrothermal Synthesis and Luminescence Properties of Eu²âº- and Eu³âº-Doped SrAIF5 Nanorods.

Eu²âº- and Eu³âº-doped SrAIF5 nanorods were synthesized via a hydrothermal process. The crystal structure and morphology of the final products were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The prepared nanorods' diameters range from 40 to 50 nm, and lengths range from 400 nm to 2 µm along with the doped concentration of rare earth. The f-f transitions of Eu²âº can be observed in the SrAlF5:Eu²âº nanorods at room temperature, and the photo-luminescent (PL) properties of SrAlF5:Eu³âº nanorods are also described.

Anomalous Temperature-Dependent Upconversion Luminescence of α-NaYF4:Yb³âº/Er³âº Nanocrystals Synthesized by a Microwave-Assisted Hydrothermal Method.

Yb³âº/Er³âºco-doped cubic-(α-) phase NaYF4 nanocrystals were prepared through a microwave- assisted hydrothermal method. Temperature-dependent upconversion luminescence (UCL) and sensing properties were systematically studied. It is interesting that anomalous temperature- dependent UCL behavior is observed. With increasing temperature (303-573 K), the UCL intensity of Er³âº does not quench monotonously but reaches a minimum around 483 K and then increases. However, it was found that the UCL spectra change in a different way with decreasing temperature (573-303 K) from the one measured with increasing temperature. The fluorescence intensity ratio of ²H11/2 --> 4I15/2 to 4S3/2 --> 4I15/2 at any measured temperature point remains almost constant in all measurement processes, indicating the consistency of temperature in each spectrum measurement at all temperature points regardless of the heating or the cooling process in our experiments. The results demonstrate that NaYF4:Yb³âº/Er³âº UC nanocrystal has good sensing stability and may have potential application in the nanoscale thermal sensor.

Preparation, Energy Transfer Characteristics and Colorimetric Properties of Na2Dy4(WO4)7:Eu³âº Nanophosphors.

Eu³âº-doped Na2Dy4(WO4)7 nanophosphors were synthesized via a co-precipitation method. The crystal structure and morphology of the nanophosphors were characterized by X-ray diffraction analysis and field emission scanning electron microscopy, respectively. For all Eu³âº doping concentrations, spherical particles with an average diameter of about 40 nm and consisting of a pure Na2Dy4(WO4)7 phase were obtained. The excitation and emission properties of the nanophosphors were examined by fluorescence spectroscopy and the energy transfer between Eu³âº and Dy³âº was studied. Furthermore, the influence of the Eu³âº concentration on the color coordinates and luminescence intensity is discussed. The nanophosphors could easily be excited by ultraviolet (UV) and near-UV light corresponding to the f-f transitions of Dy³âº. The color coordinates of the nanophosphors light emission are in the white light region and the Commission Internationale de l'Éclairage (CIE) coordinates of the nanophosphors light emission varied between (0.331, 0.354) and (0.405, 0.368) depending on the Eu³âº doping concentration.

Synthesis and Photoluminescent Properties of Eu²âº-Doped BaSiF6 Nanoparticles.

By adjusting the molar ratio of oleic acid (OA), oleylamine (OM), and 1-octadecene (OD) ligands in reaction solution, Eu²âº-doped BaSiF6 nanoparticles were synthesized using a thermal decomposition synthesis route. Eu²âº ions have been successfully doped into BaSiF6 host lattice and strong 4f-4f line emission of the Eu²âº in BaSiF6 matrix is observed. Meanwhile, the photoluminescent (PL) properties of BaSiF6:Eu²âº nanoparticles doping Eu²âº ions at different concentrations were also studied.

Concentration Quenching and Energy Transfer in Tm3+ and Dy3+ Single- and Double-Doped Nano-Sized GdVO4 Phosphors.

In this paper, Tm3+ and Dy3+ single- and double-doped nano-sized GdVO4 phosphors were prepared via a co-precipitation reaction. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and photoluminescence (PL) were utilized to characterize the as-prepared samples. The XRD and FE-SEM results reveal that the samples are single phase and that the average size is about 30 nm, respectively. Under 280 nm ultraviolet excitation, Dy3+ and Tm3+ single-doped nano-sized GdVO4 phosphors show the characteristic emissions of Dy3+ (4F9/2 --> 6H15/2 and 4F9/2 -*6H13/2 transitions) and Tm3+ (1G4 --> 3H6 transition), respectively. All the luminescence results from efficient energy transfer from the GdVO4 host to the doped Dy3+ and Tm3+ ions. Moreover, the interaction types for Dy3+ and Tm3+ ions in nano-sized GdVO4 host are confirmed as exchange and electrical dipole-dipole interaction by theoretical calculation. In Tm3+ and Dy3+ co-doped nanosized GdVO4 phosphors, the luminescence intensities of Dy3+ ions increase with increasing Tm3+ ion doping concentration, which suggests that energy transfer from Tm3+ to Dy3+ ions occurs. The responding luminescence mechanisms have been proposed in this paper. Finally, in order to evaluate the luminescence of Tm3+ and Dy3+ co-doped nano-sized GdVO4 phosphors, the color coordinates were calculated.