NIR-excited NIR and visible luminescent properties of amphipathic YVO<Subscript>4</Subscript>: Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> nanoparticles

This article reports the luminescence properties of amphipathic YVO₄:Er³⁺/Yb³⁺ nanoparticles (average grain size ca. 20 nm) obtained by an oleate-aided hydrothermal process. Depending on the upconversion (UPC) and downconversion (DWC) processes, they show luminescence in the visible and near-infrared (NIR) regions, respectively, by 980-nm excitation. The sample doped with Er³⁺:2.5 mol% and Yb³⁺:10 mol% showed the highest luminescence intensity in both the visible and NIR regions as a result of efficient energy transfer from Yb³⁺ to Er³⁺ ions. The hydrothermal treatment greatly enhanced both the DWC and UPC luminescence efficiencies. This is due to the reduction in the concentration of surface defects and ligands, accompanied by grain growth. NIR Fluorescence microscopy revealed for the first time that DWC luminescence is sufficiently intense for application of these nanocrystals as a NIR bioprobe.     

Green and red upconversion emissions of Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>-codoped SrTiO<Subscript>3</Subscript> powder prepared by a polymeric precursor method

Ultrafine Er³⁺/Yb³⁺-codoped SrTiO₃ (SEYT) powders in cubic form have been prepared by a poly-meric precursor method. The single phase perovskite for the obtained material was observed at low temperature. An efficient infrared-to-visible conversion in SEYT perovskite will be reported. Visible emissions at 550 and 663 nm corresponding to the ²S_3/2 − ⁴I_15/2 and ⁴F_9/2 − ⁴I_15/2 transitions, respectively, were observed under continuous wave excitation at 980 nm. An enhancement of the visible upconversion luminescence in Er³⁺/Yb³⁺ codoped samples was confirmed due to efficient energy transfer from Yb³⁺ to Er³⁺ ions. The quadratic pump power dependence of these emissions indicated the contribution of two photons to the upconversion process. The text was submitted by the authors in English.     

Ultraviolet upconversion luminescence in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Yb<Superscript>3+</Superscript>,Tm<Superscript>3+</Superscript> nanocrystals and its application in photocatalysis

Infrared-to-ultraviolet upconversion luminescence agent Y₂O₃:Yb³⁺,Tm³⁺ was prepared by a combustion method using citrate as a fuel/reductant. The prepared sample was characterized by X-ray diffraction, SEM, and fluorescence spectrophotometer. Two unusual ¹I₆ → ³H₆ (~297 nm) and ¹D₂ → ³H₆ (~363 nm) emissions from Tm³⁺ ions were observed at room temperature under 980-nm laser excitation. The change of upconversion emission intensity depending on the Yb³⁺ concentrations was discussed. The results showed that modest Yb³⁺ doping could make the upconversion emission of Tm³⁺ intense, and high Yb³⁺ concentrations might lead to fluorescence quenching. Moreover, the influence of ultraviolet upconversion luminescence on the photodegradation of methyl orange aqueous solution under solar light irradiation in the presence of TiO₂ catalyst doped with Y₂O₃:Yb³⁺,Tm³⁺ was also investigated. It was concluded from the experiment of this study that TiO₂/Y₂O₃:Yb³⁺,Tm³⁺ composite had higher photocatalytic activity than pure TiO₂ under solar light. This study would make TiO₂ utilize sunlight more efficiently and accelerate the practical application of photocatalytic technology in water treatment region.     

Hollow click-based porous organic polymers for heterogenization of [Ru(bpy)<Subscript>3</Subscript>]<Superscript>2+</Superscript> through electrostatic interactions

A facile approach for the heterogenization of transition metal catalysts using non-covalent interactions in hollow click-based porous organic polymers (H-CPPs) is presented. A catalytically active cationic species, [Ru(bpy)₃]²⁺ (bpy = 2,2’-bipyridyl), was immobilized in H-CPPs via electrostatic interactions. The intrinsic properties of [Ru(bpy)₃]²⁺ were well retained. The resulting Rucontaining hollow polymers exhibited excellent catalytic activity, enhanced stability, and good recyclability when used for the oxidative hydroxylation of 4-methoxyphenylboronic acid to 4-methoxyphenol under visible-light irradiation. The attractive catalytic performance mainly resulted from efficient mass transfer and the maintenance of the chemical properties of the cationic Ru complex in the H-CPPs.

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Dopant-controlled synthesis of water-soluble hexagonal NaYF<Subscript>4</Subscript> nanorods with efficient upconversion fluorescence for multicolor bioimaging

A novel strategy is proposed to directly synthesize water-soluble hexagonal NaYF₄ nanorods by doping rare-earth ions with large ionic radius (such as La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, and Gd³⁺), and the dopantcontrolled growth mechanism is studied. Based on the doping effect, we fabricated water-soluble hexagonal NaYF₄:(Yb,Er)/La and NaYF₄:(Yb,Er)/Ce nanorods, which exhibited much brighter upconversion fluorescence than the corresponding cubic forms. The sizes of the nanorods can be adjusted over a broad range by changing the dopant concentration and reaction time. Furthermore, we successfully demonstrated a novel depth-sensitive multicolor bioimaging for in vivo use by employing the as-synthesized NaYF₄:(Yb,Er)/La nanorods as probes.      

Luminescence of GaS:Er<Superscript>3+</Superscript> and GaS:Er<Superscript>3+</Superscript>,Yb<Superscript>3+</Superscript> layered crystals

Data are presented on the 300-K photoluminescence in GaS crystals doped with Er³⁺ or codoped with Er³⁺ and Yb³⁺. IR excitation (λ_ex = 976 nm) gives rise to anti-Stokes luminescence in GaS:Er³⁺ (0.1 at %) and GaS:Er³⁺,Yb³⁺ (0.1 + 0.1 at %) and leads to an increased intensity of the emission due to the ⁴ I _11/2 → ⁴ I _15/2 transitions. The anti-Stokes luminescence is shown to result from consecutive absorption of two photons by one Er³⁺ ion, and the increased intensity of Er³⁺ luminescence in GaS: Er³⁺,Yb³⁺ is due to energy transfer from Yb³⁺ to Er³⁺.     

Influence of Mn<Superscript>2+</Superscript> on the up-conversion emission performance of Mn<Superscript>2+</Superscript>, Yb<Superscript>3+</Superscript>, Er<Superscript>3+</Superscript>: ZnWO<Subscript>4</Subscript> green phosphors

The Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors are synthesized successfully through the high temperature solid state reaction method. The micro-structure and morphology have been investigated by means of XRD and EDS. The doped concentrations of Mn²⁺, Yb³⁺, Er³⁺ are measured by ICP. The absorption spectra and emission spectra with different doped concentrations of Mn²⁺ are presented to reveal the influence of Mn²⁺ on the green up-conversion performance. Excited with 970 nm LED, the up-conversion emission peak at 547 nm is obtained and the CIE spectra as well as the green light photo are also presented. The results indicate that the Mn²⁺ ions play the role of the luminescence adjustment in the up-conversion process, which can improve the up-conversion green emission intensity effectively. The luminescence adjustment mechanism of Mn²⁺ ions in Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors has been discussed. The crystal parameters of Dq, B and C are calculated to evaluate the energy level split effect.     

Large enhancement of upconversion luminescence in Er<Superscript>3+</Superscript>/In<Superscript>3+</Superscript>:Ba<Subscript>0.85</Subscript>Ca<Subscript>0.15</Subscript>TiO<Subscript>3</Subscript> lead-free piezoelectric ceramics

A series of In³⁺-doped Ba_0.85Ca_0.15TiO₃:0.75%Er³⁺/xIn³⁺ (BCT:Er/xIn) lead-free piezoelectric ceramics with excellent upconversion luminescence were synthesized by the solid state reaction method. The effects of In³⁺ content on the crystal structure, ferroelectric, dielectric, piezoelectric, and upconversion luminescence properties were systematically studied. Under 980 nm excitation, a giant enhancement of the green emission (550 nm) by 10 times is achieved upon 2.5% mol In³⁺ doping, which is rarely observed in rare-earth ions-doped perovskite ferroelectric materials. The ultraviolet-visible-near infrared absorption measurements show that the In³⁺ doping may improve the dissolution of Er³⁺ ions and modify the isolate-/clustered-Er³⁺ ratio for x?≤?2.5%, resulting in the enhancement of the absorption cross-section, thereby contributing to the enhancement of green luminescence. Unfortunately, the In³⁺ doping suppresses the ferroelectric and piezoelectric properties of the BCT:Er/xIn ceramics. This problem can be resolved by adding a small amount (1 mol%) of Yb³⁺ to the BCT:Er/xIn ceramics to restore their good ferroelectric and piezoelectric properties. Such In³⁺ and rare-earth ions co-doped ceramics with greatly enhanced upconversion luminescence and good ferroelectricity and piezoelectricity may have potential applications in electro-optical devices.     

Dual-mode protein detection based on Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>-Au hybrid nanoparticles

A facile method of synthesizing Fe₃O₄-Au hybrid nanoparticles is reported utilizing the multifunctional nature of polyethyleneimine (PEI). An abundance of 5 nm gold nanoparticles were attached to 50 nm Fe₃O₄ nanoparticles via the covalent binding between the -NH₂ groups of the PEI and Au nanoparticles, as well as the electrostatic interaction between the negatively charged citrate-coated Au nanoparticles and the positively charged PEI-coated Fe₃O₄ nanoparticles. The as-prepared Fe₃O₄-Au hybrid nanoparticles, which combine the merits of magnetic materials and gold, were successfully employed for the first time in the dual-mode detection of carcinoembryonic antigen (CEA) via electrochemical and surface-enhanced Raman scattering (SERS) methods. Both methods make clever use of Fe₃O₄-Au nanoparticles and can accurately verify the presence of antigens. In particular, the electrochemical immunosensor detection displays a wide linear range (0.01–10 ng/mL) of response with a low detection limit (10 pg/mL), while the SERS method responds to even lower antigen concentrations with a wider detection range. The Fe₃O₄-Au hybrid nanoparticles therefore exhibit great potential for biomedical applications.      

Synthesis,characterization, theoretical investigation,and properties of monoclinic-phase InWO<Subscript>4</Subscript> hollow nanospheres

As a newly discovered member of the tungstate family, InWO₄ hollow nanospheres with a monoclinic wolframite structure were synthesized successfully. The crystal phase of InWO₄ was investigated via a combination of CASTEP geometric optimization and experimental simulation. InWO₄ has a space group of P2/c with two InWO₄ formula units per unit cell. The optimized cell dimensions are a = 5.16 Å, b = 5.97 Å, and c = 5.23 Å, with α = 90°, β = 92.11°, γ = 90°, giving a unit cell volume of 161.10 ų, which is consistent with the experimental measurements. More importantly, InWO₄ was a promising host material for different Ln³⁺ (Ln = Eu and Yb/Er) ions. For InWO₄:Yb³⁺/Er³⁺ excited at 980 nm, transitions from the ⁴G_11/2 (384 nm), ²H_9/2 (411 nm), and ⁴F_7/2 (487 nm) levels to the ground state (⁴I_15/2) of Er³⁺ were observed. In addition to the aforementioned properties, the InWO₄ hollow nanospheres can be used to improve the performance of dye-sensitized solar cells, which is chiefly attributed to theirlight scattering.

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Upconversion Luminescence of Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanocrystals Doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> Ions

The upconversion luminescence (UCL) of nanocrystalline gadolinium oxide (Gd₂O₃) doped with Er³⁺ and Yb³⁺ ions has been studied in the temperature range of 90–400 K. The nanocrystals were synthesized by chemical vapor deposition and possessed a cubic crystalline structure with an average particle size within 48–57 nm. It is established that the USL intensity in the red (⁴F_9/2 → ⁴I_15/2 transition in Er3+ ion) and green (⁴S_3/2 → ⁴I_15/2 transition) spectral regions depends on the sample temperature and concentration of dopant ions, as well as on the additional structural defects (anion vacancies) created in the crystal lattice by the introduction of Zn²⁺ ions or irradiation with high-energy (10 MeV) electrons. The luminescence efficiency and spectrum of the upconversion phosphor are determined by energy transfer processes.     

X-ray diffraction,optical absorption and emission studies on Er<Superscript>3+</Superscript>- and Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>NbO<Subscript>4</Subscript> powder

Er³⁺(/Yb³⁺)-doped Li₃NbO₄ powder were prepared by thermally sintering mixtures of Er₂O₃ (0.5, 1.0 mol%), Yb₂O₃ (0, 0.5, 1.0 mol%), Li₂CO₃ (48–49 mol%) and Nb₂O₅ (50 mol%) at 1125, 1150 and 1450 °C over the durations of 8–22 h. The crystalline phases contained in these samples were determined by using X-ray diffraction and discussed in comparison with a vapor-transport-equilibration-treated (VTE-treated) Er(2.0 mol%):LiNbO₃ single crystal and ErNbO₄ powder previously reported. The results show that the X-ray patterns of the rare-earth-doped samples reveal little difference each other, but large differences with those of the VTE crystal and ErNbO₄ powder. The doped rare-earth ions Er³⁺ (and Yb³⁺) present in the powder as the ErNbO₄ (and YbNbO₄) phase(s). The possibility that the highly Er-doped LiNbO₃ crystal contains Li₃NbO₄ precipitates is small. Optical absorption and emission studies show that the only Er-doped Li₃NbO₄ powder shows similar absorption and emission characteristics with the pure ErNbO₄. The codopant Yb³⁺ ion enhances the 980-nm-upconversion emissions of Er³⁺ ions, results in remarkable spectral alterations at 0.98 μm region, and causes the alterations of relative absorbance and relative emission intensity of individual peaks or bands at 1.5 μm region. On the other hand, the Yb-codoping hardly affects the Er³⁺ energy structure and the lifetime of Er³⁺ ion at 1.5 μm. The measured lifetimes at 1.5 μm of Er³⁺ ions in the singly Er³⁺- and doubly Er³⁺/Yb³⁺-doped mixtures have a nearly same value of ∼ 1.5 ms. For the pure ErNbO₄ powder, the lifetime is prolonged to ∼2 ms perhaps due to radiation trapping effect.     

Near-infrared downconversion in Ce<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> co-doped YAG

The phosphors YAG co-doped with Ce³⁺–Yb³⁺ ion pair were successfully synthesized by solid state reaction method varying the concentration of Yb³⁺ ions from 1 to 15 % mol. The phosphors were characterized by powder X-ray powder diffraction and surface morphology was studied by scanning electronic microscope. The photoluminescence (PL) properties were studied by spectrophotometers in near infra red (NIR) and ultra violet visible region. The synthesized phosphors can convert a photon of blue region (469 nm) into photons of NIR region (979 and 992 nm). The co-operative energy transfer was studied by time decay curve and PL spectra. The theoretical value of quantum efficiency was calculated from steady time decay measurement and the maximum efficiency approached up to 145.19 %. Hence this phosphor could be used as a downconversion luminescent convertor in front of crystalline silicon solar cell (c-Si) panels to reduce thermalization loss due to spectral mismatch of the solar cells.     

Luminescence of BaSiO<Subscript>3</Subscript> crystals doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript>

The Stokes and anti-Stokes luminescence of undoped and rare-earth-doped (Er³⁺ and Yb³⁺) BaSiO₃ has been studied in the temperature range 78–450 K under excitation at 10–1000 mV. The results indicate that the emission mechanism in BaSiO₃ crystals is hole recombination and that the anti-Stokes luminescence is due to consecutive sensitization; that is, the Yb³⁺ ions in the BaSiO₃ compound act as luminescence sensitizers, and the Er³⁺ ions, as activators.     

Easy access to selective binding and recyclable separation of histidine-tagged proteins using Ni<Superscript>2+</Superscript>-decorated superparamagnetic nanoparticles

The development of simple techniques for the separation and purification of recombinant proteins plays an important role in many of the advancements made in biotechnology and nanotechnology. Herein, we report an easy method for the efficient purification of polyhistidine affinity-tagged (His-tagged) proteins by using Ni²⁺-decorated superparamagnetic particles. Monodisperse Ni_0.3Fe_0.7Fe₂O₄ nanoparticles were prepared via a facile and economical one-pot hydrothermal process. Owing to the characteristic molecular recognition ability between nickel(II) ions and the polyhistidine affinity tag, the nanoparticles could be successfully employed to selectively bind and separate His-tagged cyan fluorescent protein (CFP) from an E. coli cell lysate in a recyclable process. Moreover, by changing the divalent metal precursors, various other metal-decorated magnetic nanoparticles can be obtained. This approach offers the possibility of constructing metal-decorated nanoparticles through a simple method and will be highly beneficial in further applications of nanoparticle-based technologies.      

Sandwich-structured nanocomposites of N-doped graphene and nearly monodisperse Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles as high-performance Li-ion battery anodes

Iron oxides have attracted considerable interest as abundant materials for high-capacity Li-ion battery anodes. However, their fast capacity fading owing to poorly controlled reversibility of the conversion reactions greatly hinders their application. Here, a sandwich-structured nanocomposite of N-doped graphene and nearly monodisperse Fe₃O₄ nanoparticles were developed as high-performance Li-ion battery anode. N-doped graphene serves as a conducting framework for the self-assembled structure and controls Fe₃O₄ nucleation through the interaction of N dopants, surfactant molecules, and iron precursors. Fe₃O₄ nanoparticles were well dispersed with a uniform diameter of ~15 nm. The unique sandwich structure enables good electron conductivity and Li-ion accessibility and accommodates a large volume change. Hence, it delivers good cycling reversibility and rate performance with a capacity of ~1,227 mA·h·g^–1 and 96.8% capacity retention over 1,000 cycles at a current density of 3 A·g^–1. Our work provides an ideal structure design for conversion anodes or other electrode materials requiring a large volume change.

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Hollow spherical rare-earth-doped yttrium oxysulfate: A novel structure for upconversion

A facile biomolecule-assisted hydrothermal route followed by calcination has been employed for the preparation of monoclinic yttrium oxysulfate hollow spheres doped with other rare-earth ions （Yb3＋ and Eu3＋ or Er3＋）. The formation of hollow spheres may involve Ostwald ripening. The resulting hybrid materials were used for upconversion applications. The host crystal structure allows the easy co-doping of two different rare-earth metal ions without significantly changing the host lattice. The luminescent properties were affected by the ratio and concentration of dopant rare-earth metal ions due to energy transfer and the symmetry of the crystal field. The type of luminescent center and the crystallinity of samples were also shown to have a significant influence on the optical properties of the as-prepared products.     

Highly-sensitive multiplexed <Emphasis Type="Italic">in vivo</Emphasis> imaging using pegylated upconversion nanoparticles

Lanthanide-based upconversion nanoparticles (UCNPs) have been widely explored in various fields, including optical imaging, in recent years. Although earlier work has shown that UCNPs with different lanthanide (Ln³⁺) dopants exhibit various colors, multicolor-especially in vivo multiplexed biomedical imaging-using UCNPs has rarely been reported. In this work, we synthesize a series of UCNPs with different emission colors and functionalize them with an amphiphilic polymer to confer water solubility. Multicolor in vivo upconversion luminescence (UCL) imaging is demonstrated by imaging subcutaneously injected UCNPs and applied in multiplexed in vivo lymph node mapping. We also use UCNPs for multicolor cancer cell labeling and realize in vivo cell tracking by UCL imaging. Moreover, for the first time we compare the in vivo imaging sensitivity of quantum dot (QD)-based fluorescence imaging and UCNP-based UCL imaging side by side, and find the in vivo detection limit of UCNPs to be at least one order of magnitude lower than that of QDs in our current non-optimized imaging system. Our data suggest that, by virtue of their unique optical properties, UCNPs have great potential for use in highly-sensitive multiplexed biomedical imaging.      

Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> nanostructures: A new photocatalyst

Uniform colloidal Bi₂S₃ nanodots and nanorods with different sizes have been prepared in a controllable manner via a hot injection method. X-ray diffraction (XRD) results show that the resulting nanocrystals have an orthorhombic structure. Both the diameter and length of the nanorods increase with increasing concentration of the precursors. All of the prepared Bi₂S₃ nanostructures show high efficiency in the photodegradation of rhodamine B, especially in the case of small sized nanodots—which is possibly due to their high surface area. The dynamics of the photocatalysis is also discussed.      

Active-layer evolution and efficiency improvement of (CH<Subscript>3</Subscript>NH<Subscript>3</Subscript><Subscript>3</Subscript>Bi<Subscript>2</Subscript>I<Subscript>9</Subscript>-based solar cell on TiO<Subscript>2</Subscript>-deposited ITO substrate

We systematically investigated the development of film morphology and crystallinity of methyl-ammonium bismuth (III) iodide (MA₃Bi₂I₉) through onestep spin-coating on TiO₂-deposited indium tin oxide (ITO)/glass. The precursor solution concentration and substrate structure have been demonstrated to be critically important in the active-layer evolution of the MA₃Bi₂I₉-based solar cell. This work successfully improved the cell efficiency to 0.42% (average: 0.38%) with the mesoscopic architecture of ITO/compact-TiO₂/mesoscopic-TiO₂ (meso-TiO₂)/MA₃Bi₂I₉/2,2′,7,7′-tetrakis(N,N-di-4-methoxyphenylamino)-9,9′spiro-bifluorene (spiro-MeOTAD)/MoO₃/Ag under a precursor concentration of 0.45 M, which provided the probability of further improving the efficiency of the Bi³⁺-based lead-free organic–inorganic hybrid solar cells.

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