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.

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.

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.

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.

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.

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.

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.

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.

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.

Bioconjugations of polyethylenimine-capped LaF3:Ce, Tb nanoparticles with bovine serum albumin and photoluminescent properties.

Water-soluble Ce3+ and Tb3+ co-doped LaF3 nanoparticles with surfaces functionalized by a layer of polyethylenimine (PEI) were synthesized via a facile one-step hydrothermal method. Bovine serum albumin (BSA) protein was conjugated with LaF3:Ce, Tb nanoparticles via free amino groups on the surfaces of the nanocrystals. The final products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), ultraviolet (UV) spectrophotometry, and photoluminescence (PL) spectroscopy. XRD results showed that pure hexagonal phase LaF3:Ce, Tb nanoparticles could be obtained via a PEI assisted hydrothermal process at 180 degrees C for 24 h. The FE-SEM results showed that the morphology of pure LaF3:Ce, Tb nanoparticles was spherical with an average diameter of -20 nm. The UV spectra showed that BSA had been conjugated with LaF3:Ce, Tb nanoparticles. The photoluminescent (PL) properties of LaF3:Ce, Tb nanoparticles were also studied. The strong green emission of Tb3+ in LaF3:Ce, Tb nanoparticles suggests that these nanoparticles may have potential applications for labels in biological imaging and immunoassays.

Bioconjugation of poly(acrylic acid)-capped BaYF5:Yb3+/Er3+ up-conversion nanoparticles to bovine serum albumin: synthesis and photoluminescent properties.

Water-soluble BaYF5:Yb3+/Er3+ nanoparticles with the surface functionalized by a layer of poly(acrylic acid) (PAA) were synthesized via a facile one-step PAA-assisted hydrothermal method. Bovine serum albumin (BSA) protein was conjugated with BaYF5:Yb3+/Er3+ upconversion nanoparticles via free carboxylic acid groups on the surface of nanoparticles. The final products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared (IR) spectrophotometry, ultraviolet (UV) spectrophotometry and photoluminescence spectroscopy (PL). The XRD results showed that PAA-capped BaYF5:Yb3+/Er3+ upconversion nanoparticles could be obtained via a PAA assisted hydrothermal process with the pH value of 8 at 200 degrees C for 24 h. The TEM results showed that the morphology of BaYF5:Yb3+/Er3+ nanoparticles was spherical particles with an average diameter of about 4 nm. The IR and UV spectra showed that BSA has been conjugated with BaYF5:Yb3+/Er3+ up-conversion nanoparticles. The luminescence properties of BaYF5:Yb3+/Er3+ up-conversion nanoparticles were also studied. The luminescence properties of the products suggest that BaYF5:Yb3+/Er3+ upconversion nanoparticles have promising applications for labels in biological assays.

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.

Study on luminescent properties of Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors prepared by co-precipitation.

Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors with different concentrations have been prepared by co-precipitation. XRD (X-ray diffraction) and SEM (scanning electron microscopy) were used to investigate the structure and morphology. The emission spectra, excitation spectra and fluorescence decay curves were measured, and partial J-O parameters and quantum efficiencies of Eu3+ 5D0 energy level were calculated. Furthermore, concentration quenching curves of Eu3+ in different hosts were drawn. The photoluminescent properties of Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors have been studied. The results indicate that Eu3+ 5D0-7F2 red luminescence can be effectively excited by 395 nm and 465 nm in Gd2WO6 and Gd2W2O9 hosts, similar to the familiar Gd2(WO4)3:Eu. Especially Gd2W2O9:Eu has strong red emission and high quenching concentration, so it has potential applications for trichromatic white LED as red fluorescent materials.

Fabrication and luminescent enhancement of Eu3+-doped Y2O3@YOF core-shell nanocrystals.

In this paper, a two-step synthesis method for preparing Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals is introduced. Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals were prepared by combining an autocombustion process with a low temperature solid state reaction. X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), photoluminescence (PL) and fluorescence decay were employed to characterize the prepared samples. The results of XRD, TEM and EDS indicated that the products prepared by this method were not a mixture of Y2O3:Eu3+ and YOF:Eu3+ nanocrystals, but Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals. Compared with Y2O3:Eu3+ nanocrystals, a 20% increment in luminescence intensity was observed in the Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals, thus suggesting that coating with a YOF:Eu3+-shell can efficiently block the nonradiative relaxation channels that are induced by surface defect states.

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.

Co-precipitation synthesis and characterization of Bi3+, Eu3+ co-doped nanocrystal Gd2WO6 phosphors.

Eu3+ single-doped and Bi3+/Eu3+ co-doped nanocrystal Gd2WO6 phosphors were successfully synthesized via a co-precipitation reaction. The structure and morphology of the phosphors were characterized by using X-ray powder diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). The influence of Bi(3+)-doping concentration on the excitation and emission spectra was studied. It was found that the introduction of Bi3+ can greatly affect the charge transfer band and the luminescence intensity of Eu3+ but does not cause a change in the profile of emission spectra of Eu3+.