Structural and luminescence enhancement properties of Eu3＋/Ag nanocrystallites doped SiO2-TiO2 matrices

We reported here the structural and optical characterisation of silver nanocrystallites/Eu3+ :SiO2-TiO2 matrices synthesised through sol-gel route. Structural characterisations were done by using energy dispersive spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), atomic force microscope (AFM) and transmission electron microscopy (TEM) measurements and optical characterisations were performed by absorption and emission spectroscopy. The TEM and XRD measurements confirmed the presence of nanocrystals. A broad absorption band was observed due to surface plasmon resonance of silver nanocrystals. The effect of silver nanocrystals on the emission spectrum of Eu3+ doped SiO2-TiO2 matrices was discussed. An attempt was made to explain this fluorescence enhancement by invoking phenomena such as energy transfer, asymmetry ratio, surface plasmon, surface roughness, crystallinity and grain boundary. Our analysis, based on the experimental results, suggested that all the phenomena except crystallinity and grain boundary had favourable effects on fluorescence enhancement. We also estimated the relevant parameters associated with the phenomena that affected the fluorescence emission from the Eu3+ ions in the matrix. It was seen that the theoretical estimate of fluorescence enhancement agreed well with the experimental estimate.     

One‐pot synthesis of {Mo6I8}4+‐doped polystyrene microspheres via a free radical dispersion copolymerisation reaction

Molybdenum octahedral clusters, when incorporated into an appropriate polymer matrix, are considered as promising agents for a range of biological applications. This work describes the one‐pot synthesis, morphology and cellular toxicity of nano‐sized polystyrene beads doped with luminescent cluster complexes [{Mo₆X₈}(NO₃)₆]^2? (X = Cl, Br or I). Specifically, the particles were obtained by free radical dispersion copolymerisation of styrene and methacrylic acid or 4‐vinylpyridine in the presence of the cluster complexes. The effects of the cluster loading in the reaction mixture on both the content of the final material and number‐average molar mass of the copolymers were evaluated. © 2017 Society of Chemical Industry     

Rational design and synthesis of upconversion luminescence-based optomagnetic multifunctional nanorattles for drug delivery

Optomagnetic multifunctional composite based on upconversion luminescence nanomaterial is regarded as a promising strategy for bioimaging,disease diagnosis and targeted delivery of drugs.To explore a mesoporous nanostructure with excellent water dispersibility and high drug-loading capacity,a novel nanorattle-structured Fe3O4@SiO2@NaYF4∶Yb,Er magnetic upconversion nanorattle (MUCNR) was suc-cessfully designed by using Fe3O4 as core and NaYF4∶Yb,Er nanocrystals as shell.The microstructures and crystal phase of the as-prepared MUCNRs were evaluated by transmission electron microscopy,X-ray powder diffraction and N2 adsorption/desorption isotherms.The Kirkendall effect was adapted to explain the formation mechanism of the MUCNRs.The loading content and encapsulation efficiency of doxorubicin hydrochloride (DOX) could reach as high as 18.2％ and 60.7％,respectively.Moreover,the DOX loading MUCNR (DOX-MUCNR) system showed excellent sustained drug release and strong pH-dependent performance,which was conducive to drug release at the slightly acidic microenvironment of tumor.Microcalorimetry was used to quantify the interactions between the carrier structure and drug release rate directly.The heat release rates in the heat-flow diagrams are basically consistent with the DOX release rate,thereby showing that microcalorimetry assay not only provides a unique thermody-namic explanation for the structure-activity relationship of Fe3O4@SiO2@NaYF4∶Yb,Er MUCNRs but also provides powerful guidance to avoid the blind selection or design of drug carriers.Therefore,our work firmly provided a comprehensive perspective for using Fe3O4@SiO2@NaYF4∶Yb,Er MUCNRs as a remark-able magnetic targeted drug carrier.     

Efficient Photomodulation of Visible Eu(III) and Invisible Yb(III) Luminescences using DTE Photochromic Ligands for Optical Encryption

This work describes a class of complex combining three dithienylethene units and a lanthanide ion used as an optical system displaying a double encryption method: i) a colorful code, drawn and erased under UV and visible irradiations respectively, due to coloration and discoloration of the photochromic entities, and ii) a concomitant gradual disappearance and progressive restoration of the associated lanthanide ion luminescence triggered with the same stimuli. The innovation of the system stems from the emission color tunability, i.e., with either a lanthanide ion emitting only in the visible range (Eu³⁺) or with another lanthanide ion emitting only in the near infrared (NIR) range (Yb³⁺), therefore observable, or not, to the naked eye. This system is the very first one to achieve efficient repeatable modulation of pure NIR luminescence on photochemical command. Furthermore, it is proven to be highly efficient when embedded in a PDMS polymer opening real opportunities for practical applications as anti‐counterfeiting.     

Comprehensive study on structural,thermal, morphological and luminescence (RL,PL, TL) properties of CaLa2(WO4)4: Tb3+, Dy3+ phosphors synthesized via sol-gel method

Tb³⁺/Dy³⁺ co-doped CaLa₂(WO₄)₄ (CLW: Tb³⁺/Dy³⁺) and its derivatives were synthesized by the sol-gel method. The morphology, thermal, structure and luminescent-optical properties the as-prepared light-emitting phosphors were characterized by utilizing scanning electron microscopy (SEM), differential thermal analysis (DTA)-thermogravimetric analysis (TG), X-ray diffraction (XRD) and radioluminescence (RL or X-ray luminescence) - photoluminescence (PL) –thermoluminescence (TL or TSL) - optical absorption spectrometry. The Tb³⁺ and Dy³⁺ ions were singly or doubly doped and the results were examined in detail. Moreover, for these phosphors, the energy transfer mechanisms which depend on RL and PL spectra were determined. The samples excited by X-ray demonstrate characteristic luminescence peaks of Dy³⁺ (422, 480, 575, 663 and 747 nm) and Tb³⁺ (489, 544, 586, 620, 652 and 675 nm). These emissions are similar for RL and PL measurements. It could be said that the energy transfer efficiency of the host material is perfect for rare-earth ions. The synthesized phosphors exhibit various colors from yellow to blue under UV excitation. The optical band gaps of host CLW, CLW: Tb³⁺, CLW: Dy³⁺ and co-doped CLW: Tb³⁺/Dy³⁺ were calculated at values 3.83 eV, 3.44 eV, 3.64 eV and 3.52 eV, respectively. From the results obtained, the CaLa₂(WO₄)₄: Tb³⁺, Dy³⁺phosphors may be one of the potential candidates for light-emitting diode.     

Investigation of structural,optical, and magnetic properties of Nd-doped Sr2SnO4 Ruddlesden Popper oxide

The samples of Sr_2-xNd_xSnO₄ with x = 0, 0.01, 0.02, 0.04, 0.06, and 0.10 were synthesized by a high-temperature solid-state ceramic route. Rietveld refining of X-ray diffraction results showed that all the synthesized compositions are single phase under tetragonal crystal structure. The presence of functional group and local structure has been studied using FTIR and Raman spectroscopy, respectively. XPS study of samples showed the presence of oxygen vacancy and interstitial oxygen in the sample. Optical band gap of samples analyzed by UV-Vis spectra gradually increases with dopant concentration, and Photoluminescence (PL) spectroscopy study showed most intense emission around 1064 nm. Room-temperature magnetic hysteresis curve in sample SSN2 showed ferromagnetism, slowly decreasing with Nd and becoming antiferromagnetic for higher compositions. Utilizing the absorption state observed in PL as metastable state makes it promising candidate for laser and IR detector application and the ferromagnetic/antiferromagnetic nature of sample makes it suitable candidate for spintronics device applications.     

Recent Advances in Solution-Processed White Organic Light-Emitting Materials and Devices

Solution-processed white organic light-emitting diodes (WOLEDs) have drawn great attention both in the academic and industrial research communities due to the potential application in low-cost, large-area, solid-state lightings. Issues related to the device efficiencies are largely hampering progress in this field. Alongside the development of new materials and novel device architectures, distinct progress has been made for such white devices. In particular, the all-phosphorescent light-emitting strategy has been intensively developed in recent years, mainly focusing on a host guest, doping-system-based, single-active-layer structure and a solution-processed, multilayer device structure. Novel approaches, including white single polymers and excimer-/exciplex-based white devices, have also appeared as a promising choice and received great attention. As a prerequisite, the issue of the morphology of the emissive layer is also important and has an influence on the optoelectronic behavior of the device. Herein, major advances in solution-processed WOLEDs based on polymers, dendrimers, or solution-processed small molecules are summarized. Special attention is focused on the main progress in high-efficiency, solution-processed WOLEDs with the key strategies mentioned above and the morphology issue in these systems. The remaining challenges in pursuing the development of reliable and energy-saving lighting devices are also discussed.     

A Water‐Soluble Mechanochromic Luminescent Pyrene Derivative Exhibiting Recovery of the Initial Photoluminescence Color in a High‐Humidity Environment

Switching of the luminescence properties of molecular materials in response to mechanical stimulation is of fundamental interest and also has a range of potential applications. Herein, a water‐soluble mechanochromic luminescent pyrene derivative having two hydrophilic dendrons is reported. This pyrene derivative is the first example of a mechanochromic luminescent organic compound that responds to relative humidity. Mechanical stimulation (grinding) of this pyrene derivative in the solid state results in a change of the photoluminescence from yellow to green. Subsequent exposure to water vapor induces recovery of the initial yellow photoluminescence. The color change is reversible through at least ten cycles. It is also demonstrated that this compound can be applied as a mechano‐sensing material in frictional wear testing for grease, owing to its immiscibility in non‐polar solvents and its non‐crystalline behavior. Transmission electron microscope and atomic force microscope observations of samples prepared from dilute aqueous solutions of the pyrene derivative on suitable substrates, together with dynamic light scattering measurements for the compound in aqueous solution, indicate that this amphiphilic dumbbell‐shaped molecule forms micelles in water.     

Au/NaYF4 : Yb,Er Binary Superparticles: Synthesis and Optical Properties

Colloidal superparticles (SPs) are nanoparticle (NP) assemblies in the form of colloidal particles. Assembling nanoscopic objects into mesoscopic or macroscopic composite architectures allows for the bottom-up fabrication of functional nanomaterials. In this study, a method for single-step self-assembly synthesis of Au/NaYF₄ : Yb,Er SPs was developed using oil-in-water (O/W) microemulsions to simultaneously encapsulate gold nanoparticles (AuNPs) and NaYF₄ : Yb,Er upconversion nanoparticles (UCNPs) via evaporation at room temperature. The synthesized Au/NaYF₄ : Yb,Er SPs possess good dispersibility and stability. When the number of AuNPs added is increased, the SPs exhibit decreased upconversion luminescence, which can be ascribed to the Förster resonance energy transfer (FRET) from the NaYF₄ : Yb,Er UCNPs to the AuNPs. Time-resolved measurements of the green emission further confirm the existence of a new decay route corresponding to the FRET process. Our research provides a facile and versatile strategy for the synthesis of novel multifunctional nanocomposites with tunable upconversion luminescence properties, which can be of great significance in biological applications.