Zewei Quan

A magnetic, luminescent and mesoporous core–shell structured composite material as drug carrier

In this paper, hydrothermal synthesized Fe3O4 microspheres have been encapsulated with nonporous silica and a further layer of ordered mesoporous silica through a simple sol-gel process. The surface of the outer silica shell was further functionalized by the deposition of YVO4:Eu3+ phosphors, realizing a sandwich structured material with mesoporous, magnetic and luminescent properties. The multifunctional system was used as drug carrier to investigate the storage and release properties using ibuprofen (IBU) as model drug by the surface modification. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), N2 adsorption/desorption, photoluminescence (PL) spectra, and superconducting quantum interference device (SQUID) were used to characterized the samples. The results reveal that the material shows typical ordered mesoporous characteristics, and have monodisperse spherical morphology with smooth surface and narrow size distribution. Additionally, the multifunctional system shows the characteristic emission of Eu3+ (5D0-7F(1-4)) even after the loading of drug molecules. Magnetism measurement reveals the superparamagnetic feature of the samples. Drug release test indicates that the multifunctional system shows drug sustained properties. Moreover, the emission intensities of Eu3+ in the drug carrier system increase with the released amount of drug, thus making the drug release be easily tracked and monitored by the change of the luminescence intensity.

High-Index Faceted Noble Metal Nanocrystals

The formation of novel and complex structures with specific morphologies from nanocrystals via a direct assembly of atoms or ions remains challenging. In recent years, researchers have focused their attention on nanocrystals of noble metals and their controlled synthesis, characterization, and potential applications. Although the synthesis of various noble metal nanocrystals with different morphologies has been reported, most studies are limited to low-index facet-terminated nanocrystals. High-index facets, denoted by a set of Miller indices {hkl} with at least one index greater than unity, possess a high density of low-coordinated atoms, steps, edges, and kinks within these structures and serve as more active catalytic sites. With the potential for enhanced catalytic performance, researchers have used the insights from shape-controlled nanocrystal synthesis to construct noble metal nanocrystals bounded with high-index facets. Since the report of Pt tetrahexahedral nanocrystals, researchers have achieved significant progress and have prepared nanocrystals with various high-index facets. Because of the general order of surface energy for noble metals, high-index facets typically vanish faster in a crystal growth stage and are difficult to preserve on the surface of the final nanocrystals. Therefore researchers have had limited opportunities to examine high-indexed noble metal nanocrystals with a controlled morphology and investigate their resultant behaviors in depth. In this Account, we thoroughly discuss the basic concepts and state-of-the-art morphology control of some noble metal nanocrystals enclosed with high-index facets. We briefly introduce high-index facets from both crystallographic and geometrical points of view, both of which serve as methods to classify these high-index facets. Then, we summarize various typical noble metal nanocrystals terminated by different types of high-index facets, including {hk0} (h > k > 0), {hhl} (h > l > 0), {hkk} (h > k > 0), and {hkl} (h > k > l > 0). In each type, we describe several distinct morphologies including convex, concave, and other irregular shapes in detail. Based on these remarks, we discuss key factors that may induce the variations of Miller indices in each class, such as organic capping ligands and metallic cationic species. In a look at applications, we review several typical high-indexed noble metal nanocrystals showing enhanced electrocatalytic or chemical catalytic activities.

Bioactive, luminescent and mesoporous europium-doped hydroxyapatite as a drug carrier

Bioactive, luminescent and mesoporous europium-doped hydroxyapatite (Eu:HAp) was successfully prepared through a simple one-step route using cationic surfactant as template. The obtained multifunctional hydroxyapatite was performed as a drug delivery carrier to investigate the drug storage/release properties using ibuprofen (IBU) as a model drug. The structural, morphological, textural and optical properties were well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), N(2) adsorption/desorption, and photoluminescence (PL) spectra, respectively. The results reveal that the multifunctional hydroxyapatites exhibit the typical ordered characteristics of the hexagonal mesostructure, and have rod-like morphology with the particle size of 20-40 nm in width and 100-200 nm in length. The drug storage/release test indicates that the luminescent HAp shows much similar drug loading amount and cumulative release rate to those of pure HAp. Interestingly, the IBU-loaded samples still show red luminescence of Eu(3+) ((5)D(0)-(7)F(1),(2)) under UV irradiation, and the emission intensities of Eu(3+) in the drug carrier system vary with the released amount of IBU, thus making the drug release be easily tracked and monitored by the change of the luminescence intensity.

Shape-control and electrocatalytic activity-enhancement of Pt-based bimetallic nanocrystals.

Due to the increasing worldwide energy demand and environ-mental concerns, the need for alternative energy sources is growing stronger, and platinum catalysts in fuel cells may help make the technologies a reality. However, the pursuit of highly active Pt-based electrocatalysts continues to be a challenge. Scientists developing electrocatalysts continue to focus on characterizing and directing the construction of nanocrystals and advancing their electrochemical applications. Although chemists have worked on Pt-based bimetallic (Pt-M) preparations in the past, more recent research shows that both shape-controlled Pt-M nanocrystals and the assembly of these nanocrystals into supercrystals are promising new directions. A solution-based synthesis approach is an effective technique for preparing crystallographic facet-directed nanocatalysts. This is aided by careful selection of the metal precursor, capping ligand, reducing agent, and solvent. Incorporating a secondary metal M into the Pt lattice and manipulating the crystal facets on the surface cooperatively alter the electrocatalytic behavior of these Pt-M bimetallic nanocrystals. Specifically, chemists have extensively studied the {111}- and {100}-terminated crystal facets because they show unique atomic arrangement on surfaces, exhibit different catalytic performance, and possess specific resistance to toxic adsorbed carbon monoxide (COads). For catalysts to have maximum efficiency, they need to have resistance to COads and other poisonous carbon-containing intermediates when the catalysts operate under harsh conditions. A necessary design to any synthesis is to clearly understand and utilize the role of each component in order to successfully induce shape-controlled growth. Since chemists began to understand Pt nanocrystal shape-dependent electrocatalytic activity, the main obstacles blocking proton exchange membrane fuel cells are anode poisoning, sluggish kinetics at the cathode, and low activity. In this Account, we discuss the basic concepts in preparation of Pt-M bimetallic nanocrystals, focusing on several immaculate examples of manipulation at the nanoscale. We briefly introduce the prospects for applying Pt-M nanocrystals as electrocatalysts based on the electronic and geometric standpoints. In addition, we discuss several key parameters in the solution-based synthesis approach commonly used to facilitate Pt-M nanocrystals, such as reaction temperature and time, the combination of organic amines and acids, gaseous adsorbates, anionic species, and solvent. Each example features various nanoscale morphologies, such as spheres, cubes, octahedrons, and tetrahedrons. Additionally, we outline and review the superior electrocatalytic performances of the recently developed high-index Pt-M nanostructures. Next, we give examples of the electrocatalytic capabilities from these shape-defined Pt-M architectures by highlighting significant accomplishments in specific systems. Then, using several typical cases, we summarize electrochemical evaluations on the Pt-based shape-/composition-dependent nanocatalysts toward reactions on both the anode and the cathode. Lastly, we provide an outlook of current challenges and promising directions for shape-controlled Pt-M bimetallic electrocatalysts.

Tm3+ and/or Dy3+ doped LaOCl nanocrystalline phosphors for field emission displays

Blue, yellow and white light emissive LaOCl:Tm3+, LaOCl:Dy3+ and LaOCl:Tm3+,Dy3+ nanocrystalline phosphors were synthesized through the Pechini-type sol-gel process. X-Ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) and cathodoluminescence (CL) spectra were used to characterize the samples. Under UV radiation (229 nm) and low-voltage electron beam (0.5–5 kV) excitation, the Tm3+-doped LaOCl phosphor shows a very strong blue emission corresponding to the characteristic transitions of Tm3+ (1D2, 1G4 → 3F4, 3H6) with the strongest emission at 458 nm. The cathodoluminescent color of LaOCl:Tm3+ is blue to the naked eye with CIE coordinates of x = 0.1492, y = 0.0684. This phosphor has better CIE coordinates and higher emission intensity than the commercial product Y2SiO5:Ce3+. Notably, for the first time, white cathodoluminescence was realized by co-doping Tm3+ and Dy3+ with appropriate ratios in the LaOCl single host lattice, which can be potentially used as backlights. Luminescence mechanisms were proposed to explain the observed phenomena.

Self-assembled 3D Architectures of LuBO3 : Eu3+: Phase-selective synthesis, growth mechanism, and tunable luminescent properties

Rhombohedral-calcite and hexagonal-vaterite types of LuBO(3):Eu(3+) microparticles with various complex self-assembled 3D architectures have been prepared selectively by an efficient surfactant- and template-free hydrothermal process for the first time. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometry, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction, photoluminescence, and cathodoluminescence spectra as well as kinetic decays were used to characterize the samples. The pH, temperature, concentration, solvent, and reaction time have a crucial influence on the phase formation, shape evolution, and microstructure. The reaction mechanism is considered as a dissolution/precipitation process; it is proposed that the self-assembly evolution occurs by homocentric layer-by-layer growth. Under UV excitation and low-voltage electron beam excitation, calcite-type LuBO(3):Eu(3+) particles show a strong orange emission corresponding to the (5)D(0)-->(7)F(1) transition of Eu(3+) whereas vaterite-type LuBO(3):Eu(3+) particles exhibit a strong red emission with much higher R/O values (that is, chromatically redder fluorescence than that of crystals grown from a direct solid-state reaction). The tunable luminescent properties have potential applications in fluorescent lamps and field emission displays.

Shape controllable synthesis and upconversion properties of NaYbF4/NaYbF4 : Er3+ and YbF3/YbF3 : Er3+ microstructures

Ytterbium fluoride compounds with different crystal phases and morphologies, such as β-NaYbF4 hexagonal microdisks, microprisms, microtubes, and α-NaYbF4 submicrospheres as well as YbF3 octahedra, have been synthesized via a facile hydrothermal route. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and photoluminescence (PL) spectra were used to characterize the samples. The intrinsic structural feature of ytterbium fluoride compounds and four external factors, namely the pH values in the initial reaction solution, the fluoride source, the use of an organic additive (Cit3−) and simple ions (Na+, NH4+, BF4−, BO3−), are responsible for the ultimate shape evolutions of the products. The possible formation mechanisms for products with various architectures are presented. Additionally, the upconversion (UC) photoluminescence properties of β-NaYbF4:Er3+ hexagonal microdisks, microtubes, α-NaYbF4 spheres and YbF3 octahedra were investigated in detail. To the best of our knowledge, this is the first report concerning controllable synthesis of ytterbium fluoride compounds with diverse crystal phases and morphologies. More importantly, this simple method is expected to allow the large-scale production of other complex rare earth fluoride compounds with controllable morphologies and sizes, and exploration of the morphology and phase-dependent photoluminescence properties.

Uniform Colloidal Alkaline Earth Metal Fluoride Nanocrystals: Nonhydrolytic Synthesis and Luminescence Properties

In this paper, we present a facile and general synthetic route to high-quality alkaline earth metal fluoride (AEF2, AE = Ca, Sr, Ba) nanocrystals and CaF2:Tb(3+) nanocrystals based on the thermal decomposition of corresponding trifluoroacetate precursors in hot oleylamine. X-ray diffraction, transmission electron microscopy, thermogravimetric and differential thermal analysis, Fourier transform infrared spectra, photoluminescence spectra, and kinetic decays were employed to characterize the samples. The use of single-source precursors plays an important role in the formation of high-quality AEF 2 nanocrystals, and the formation process is demonstrated in detail. The obtained AEF2 nanocrystals are nearly monodisperse in size and highly crystalline, and they can be well dispersed in nonpolar solvents to form stable and clear colloidal solutions, which all display purple emissions under ultraviolet excitation due to the numerous surface defects of nanocrystals with large surface/volume ratios. Furthermore, we demonstrate the feasibility of introducing Tb(3+) ions into the CaF2 host via this method, which shows strong green emission corresponding to the characteristic (5)D4-(7)F(J) (J = 3, 4, 5, 6) emission of Tb(3+) ions, which can be potentially used as labels for biological molecules.

Multicolor Tuning of Manganese-Doped ZnS Colloidal Nanocrystals

In this paper, we report a facile route which is based on tuning doping concentration of Mn(2+) ions in ZnS nanocrystals, to achieve deliberate color modulation from blue to orange-yellow under single-wavelength excitation. X-ray diffraction (XRD), transmission electron microscopy (TEM), as well as photoluminescence (PL) spectra were employed to characterize the obtained samples. In this process, the relative emission intensities of both ZnS host (blue) and Mn(2+) dopant (orange-yellow) are sensitive to the Mn(2+) doping concentration, due to the energy transfer from ZnS host to Mn(2+) dopant. As a result of fine-tuning of these two emission components, white emission can be realized for Mn(2+)-doped ZnS nanocrystals. Furthermore, the as-synthesized doped nanocrystals possess extremely narrow size distribution and can be readily transferred into aqueous solution for the next potential applications.

Solvent-Mediated Self-Assembly of Nanocube Superlattices

Self-organization of colloidal Pt nanocubes into two types of distinct ordered superlattices, simple-cubic and body-centered-tetragonal structures, has been achieved using a home-built setup. Detailed translational and orientational characteristics of these superstructures were determined using a transmission electron microscopy tomographic technique with 3D reconstruction analysis. The formation of these distinct superlattices is the result of a delicate choice of solvent (i.e., aliphatic hexane or aromatic toluene hydrocarbons), which serves as a dispersion medium to fine-tune the relative strengths of ligand-ligand and ligand-solvent interactions during the self-assembly process. This work provides important insights into the effects of ligand-solvent interactions on superlattice formation from nonspherical nanoparticles.