Aqueous synthesis of Cu-doped ZnSe quantum dots

In this paper, we described a simple growth-doping approach for aqueous synthesis of Cu-doped ZnSe quantum dots (Cu:ZnSe d-dots) with mercaptopropionic acid as stabilizer. The influences of the ratios of precursors and the concentration of Cu dopant ions on Cu:ZnSe d-dots synthesis were studied in detail in this study. The Cu dopant ions had significant influence on the optical properties of ZnSe d-dots. The bandgap emission of ZnSe was effectively restrained through Cu doping. The prolonged reflux facilitates the doping of Cu, which led to the red-shift of the emission of Cu:ZnSe d-dots from 465 to 495 nm. The stable Cu:ZnSe d-dots with high quality can be obtained under optimal conditions. As compared with cadmium-based nanocrystals synthesized in aqueous solution, Cu:ZnSe d-dots have much lower toxicity, indicating that they can be applied as outstanding fluorescent labels for biological assays, imaging of cells and tissues, even in vivo investigations.     

Synthesis and photoluminescence of water-soluble Mn-doped ZnS quantum dots

The water-soluble Mn²⁺-doped ZnS quantum dots (Mn:ZnS d-dots) were synthesized by using thioglycolic acid (TGA) as stabilizer in aqueous solutions in air, and characterized by X-ray powder diffraction (XRD), UV-vis absorption spectra and photoluminescence (PL) emission spectroscopy. The sizes of Mn:ZnS d-dots were determined to be about 2 nm using XRD measurements and the UV-vis absorption spectra. It was found that the Mn²⁺⁴T₁ → ⁶A₁ emission intensity of Mn:ZnS d-dots significantly increased with the increase of Mn²⁺ concentration, and showed a maximum when Mn²⁺ doping content was 1.5%. If Mn²⁺ concentration continued to increase, namely more than 1.5%, the Mn²⁺⁴T₁ → ⁶A₁ emission intensity would decrease. In addition, the effects of TGA/(Zn + Mn) molar ratio on PL were investigated. It was found that the peak intensity ratio of Mn²⁺⁴T₁ → ⁶A₁ emission to defect-states emission showed a maximum when the TGA/(Zn + Mn) molar ratio was equal to 1.8.     

Magnetic and luminescent properties of manganese-doped ZnSe crystals

Magnetic and photoluminescent properties of manganese-doped ZnSe crystals with different impurity concentrations were investigated. The concentration of Mn²⁺ ions in ZnSe crystals has been varied from 0.01 to 0.3 at%. Magnetic and photoluminescent studies have confirmed the introduction of Mn in ZnSe crystals. It was established that Mn²⁺ ions are responsible for the emission bands with maximum at 616 nm and 633 nm, which correspond to ⁴T₂→⁶A₁ and ⁴T₁→⁶A₁ intracentre transitions of Mn²⁺ ions respectively. It was found that the concentration quenching of the photoluminescent bands is associated with Mn²⁺ ions, which are due to the formation of Mn–Mn clusters. Magnetic properties studies have shown that at high doping levels the manganese atoms form Mn–Mn clusters in ZnSe. From the temperature dependence of magnetic susceptibility of ZnSe:Mn crystals that follows the Curie–Weiss law, it was possible to estimate the Curie–Weiss temperature Θ(x) and the effective Mn–Mn antiferromagnetic exchange constant (J₁).     

Uricase-Based Highly Sensitive and Selective Spectrophotometric Determination of Uric Acid Using BSA-Stabilized Au Nanoclusters as Artificial Enzyme

ABSTRACT

The enzymatic spectrophotometric analysis of uric acid based on BSA-stabilized Au nanoclusters (Au NCs) as peroxidase mimetics was first developed. Compared with natural enzyme horseradish peroxidase (HRP), which was used widely to detect H₂O₂ generated by uric acid, the BSA-stabilized Au NCs as peroxidase mimetics are easy to prepare, low cost, and stable. Kinetic analysis indicates that the BSA-stabilized Au NCs have even higher catalytic activity than HRP. Under the optimum conditions, the detection limit for uric acid is 3.6 × 10^?7 mol L^?1. The feasibility of the developed method for uric acid analysis in human serum was confirmed.     

Ultrasound and ionic liquid: an efficient combination to tune the mechanism of alkenes epoxidation

In this proof of concept study, the advantageous properties of both H₂O₂/NaHCO₃/imidazole/Mn(TPP)OAc oxidation system and MOPyrroNTf₂ ionic liquid have been combined under ultrasonic irradiation to give an exceptionally favorable environment for Mn(TPP)OAc catalyzed olefin oxidations. The results reveal the crucial role played by the ultrasonic irradiations that influence drastically the oxidation process. In MOPyrroNTf₂ and under ultrasonic irradiation, the mechanism probably involves an oxo-manganyl intermediate at the expense of the classical bicarbonate-activated peroxide route.     

Experimental verification of a high performed multiple-band metamaterial absorber

In this paper, a thin-film metamaterial absorber with multiple-band is experimental verified and calculated analysis. Two absorption peaks higher than 99% and 98% are obtained at normal incidence. The resonance of the local surface plasma (LSP) mode and the internal surface plasmon (ISP) mode lead to the two high absorption peaks. The impedance matched condition is obtained behind two high absorption peaks. Measured results indicate that high absorption performed can be observed with different dielectric layer combinations (Al₂O₃–ZnSe, Al₂O₃–Al₂O_3, and ZnSe–ZnSe), which indicates that the designed metamaterial absorber is insensitive to the dielectric layer combination. High absorption performed is obtained under both TE and TM configurations at various incident angles.     

Spectroscopic studies on the interaction between ZnSe nanoparticles with bovine serum albumin

The interaction between ZnSe nanoparticles (NPs) and bovine serum albumin (BSA) was studied by UV–vis, fluorescence spectroscopic techniques. The results showed that the fluorescence of BSA was strongly quenched by ZnSe NPs and the quenching mechanism was discussed to be a static quenching procedure, which was proved by quenching constant (K_q). The recorded UV–vis data and the fluorescence data quenching by the ZnSe NPs showed that the interaction between them leads to the formation of ZnSe–BSA complex. Based on the synchronous fluorescence spectra, it was established that the conformational change of BSA was induced by the interaction of ZnSe with the tyrosine micro-region of the BSA molecules. Furthermore, the temperature effects on the structural and spectroscopic properties of individual ZnSe NPs and protein and their bioconjugates (ZnSe–BSA) were also researched. It was found that, compared to the monotonic decrease of the individual ZnSe NPs fluorescence intensity, the temperature dependence of the ZnSe–BSA emission had a much more complex behavior, which was highly sensitive to the conformational changes of the protein.     

Effect of thermal annealing on the structure of ZnSe/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposite films

The ZnSe/Al₂O₃ nanocomposite films synthesized by laser evaporation followed by heat treatment are studied. X-ray diffraction and electron-microscopic investigations of the as-deposited films demonstrate the presence of ZnSe crystallites in an Al₂O₃ amorphous matrix. Annealing changes the structures of ZnSe and Al₂O₃, increases the ZnSe crystallite size, and causes the appearance of the ZnSeO₄ phase. The presence of aluminum oxide layers decreases the phase transformation temperature of zinc selenide.     

Mn掺杂ZnSe量子点变温发光性质研究

量子点(QD)照明器件中电流导致的焦耳热会使其工作温度高于室温,因此研究量子点的发光热稳定性十分重要。本文利用稳态光谱和时间分辨光谱研究了具有不同壳层厚度的Mn掺杂ZnSe(Mn: ZnSe)量子点的变温发光性质,温度范围是80～500 K。实验结果表明,厚壳层(6.5单层(MLs))Mn: ZnSe量子点的发光热稳定性要优于薄壳层(2.6 MLs)的量子点。从80 K升温到400 K的过程中,厚壳层Mn: ZnSe量子点的发光几乎没有发生热猝灭,发光量子效率在400 K高温下依然可以达到60%。通过对比Mn: ZnSe量子点的变温发光强度与荧光寿命,对Mn: ZnSe量子点发光热猝灭机制进行了讨论。最后,为了研究Mn: ZnSe量子点的发光热猝灭是否为本征猝灭,对具有不同壳层厚度的Mn: ZnSe量子点进行了加热-冷却循环(300-500-300 K)测试,发现厚壳层的Mn: ZnSe量子点的发光在循环中基本可逆。因此,Mn: ZnSe量子点可以适用于照明器件,即使器件中会出现不可避免的较强热效应。     

On the luminescence of manganese(II) phosphates

Luminescent properties of manganese(II) phosphates prepared by thermal dehydration of Mn(H₂PO₄)₂·2H₂O have been studied. The emission spectrum consists of two bands whose relative intensity and spectral position depend on the chemical and crystalline structure of phosphates. The different courses of temperature quenching of luminescence intensity and excitation spectra of each emission band of Mn(H₂PO₄)₂·2H₂O, Mn(H₂PO₄)₂, MnH₂P₂O₇ and c-Mn₂P₄O₁₂ are discussed.     

Mn2+和RE3+在ZnS和ZnSe中的Auger猝灭

在改变MS结势垒区宽度的同时,我们测量了在ZnSe:Mn2+晶体、ZnS:Er3+和ZnS:Sm3+薄膜中的Mn2+、RE3+特征谱的电致发光衰减.测量了高阻和低阻ZnS:Mn2+在变化温度(77K—500K)时,Mn2+发光强度的改变.认为在室温以下,Mn2+和RE3+在低阻ZnS和ZnSe中的辐射跃迁均受到Auger猝灭的影响.     

A simple and sensitive fluorescence quenching method for the determination of H(2)O(2) using Rhodamine B and FE(3)O(4) nanocatalyst

In pH 1.99 sodium acetate-HCl buffer solutions at 60 °C, Rhodamine B exhibited a strong fluorescence peak at 584 nm using an excitation wavelength of 548 nm. The fluorescence quenching occurred when Fe₃O₄ nanoparticles catalyzed H₂O₂ oxidation of Rhodamine B. Under the chosen conditions, the fluorescence intensity at 584 nm decreased when the concentration of H₂O₂ increased. The fluorescence quenching intensity is linear with the concentration of H₂O₂ in the range of 10–200 nmol/L. Thus, a new and simple and sensitive nanocatalytic fluorescence method was proposed for the determination of H₂O₂ in synthetic sample, with satisfactory results.     

Effect of the luminol signal enhancer on the chemiluminescence intensity and kinetics

The novel p-phenol derivatives, 4-(1-imidazolyl)-phenol, 4-hydroxybiphenyl, 4-hydroxy-4′-iodobiphenyl were employed as highly potent signal enhancers of luminol-hydrogen peroxide (H₂O₂)-horseradish peroxidase (HRP) chemiluminescence (CL) system. The CL reaction conditions were optimized, and the enhancement characteristics of these enhancers were compared with each other. The employment of these molecules greatly affected important assay parameters. Practically, the use of a novel enhancer, even a slightly change of the structure (or concentration) of 4-substituted phenol derivative, could affect assay properties quite dramatically. Furthermore, the use of different enhancers in the luminol–H₂O₂–HRP system can affect not only the intensity of the CL signal, which is well known, but also its kinetics. The experiment data indicated that the stronger intensity was combined with a more rapid decrease of the CL signal.     

The influence of CdSe and ZnSe nanoparticles on the optical properties of Sm<Superscript>3+</Superscript> ions in lead borate glasses

The effect of glass composition and the presence of CdSe/ZnSe nanoparticles (NPs) on the optical absorption and fluorescence of Sm-doped lead borate glasses are studied. Three sets of glass samples xPbO:(99.5-x) B₂O₃:0.5Sm₂O₃, x = 29.5–69.5 mol%, xPbO:(96.5-x) B₂O₃:0.5Sm₂O₃: 3CdSe/ZnSe, x = 36.5, and 56.5 mol% are prepared. NPs are grown by annealing these glasses just below the glass transition temperature. Average size of both types of NPs increases with annealing time; however, CdSe NPs grew to a larger size range (2 to 20 nm) compared to ZnSe NPs (1 to 16 nm). We analyzed the hypersensitive transition, intensity parameters, radiative transition probability, stimulated emission cross section (σ_p), and the area ratio of the electric dipole/magnetic dipole transitions of Sm³⁺. The intensity parameters show a minimum at 11 h annealing for 36.5 mol% and a maximum for the same annealing duration in 56.5 mol% PbO containing CdSe NPs. The σ_p for 56.5 mol% of PbO with CdSe NPs is found to be a maximum when the average NP size is around 14 nm. ZnSe NPs containing glasses also show significant changes in σ_p when the average particle size is ~16 nm, for 36.5 mol% PbO. Our results suggest that the optical properties of Sm³⁺ in lead borate glasses are sensitive to its electronic environment which can be modified by varying the base glass composition and/or incorporating large NPs of CdSe/ZnSe. The large σ_p values that we observe for some of the glass compositions make them attractive materials for photonic devices and photovoltaic applications.

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Graphical abstract

     

Electronic structure analysis of Mn- and Fe-codoped In2O3 by photoemission yield measurements

The valence band electronic structures of Mn- and/or Fe-doped In₂O₃, i.e., In₂O₃:Mn, In₂O₃:Fe, and In₂O₃:(Mn, Fe), are investigated by photoemission yield measurements. Significant changes are observed in the threshold energy of photoemission, depending on the doped magnetic ions, which indicates that an additional occupied band appears above the top of the valence band of In₂O₃ owing to doping with Mn and/or Fe ions. It is confirmed that the order of the threshold energies of photoemission, E_PET, is E_PET(In₂O₃:Mn)<E_PET(In₂O₃:(Mn, Fe))<E_PET(In₂O₃:Fe)<E_PET(In₂O₃). To gain a better understanding of these results, first-principles molecular orbital calculations are also carried out, which successfully explain the observed changes in the photoemission threshold energies.     

The photoluminescence properties of TiO2-sheathed ZnSe nanowires

ZnSe nanowires have been synthesized by thermal evaporation of ZnSe powders on gold-coated Al₂O₃(0 0 0 1) substrates and then sheathed with TiO₂ by sputtering. Our results show that sheathing Zn nanowires with thin TiO₂ layers can significantly enhance the photoluminescence (PL) emission intensity. XPS analysis results suggest that the PL enhancement is attributed to increases in the concentrations of deep levels such as oxygen and titanium interstitials as well as the density of interface states. The PL emission of ZnSe nanowires is also enhanced by thermal annealing. Annealing in an argon atmosphere is more efficient in enhancing the PL emission than annealing in an oxygen atmosphere.     

Controlling spin off state by gas molecules adsorption on metal-phthalocyanine molecular junctions and its possibility of gas sensor

Employing Green's function (GF) technique in combination with spin-polarized density functional theory (DFT), we study the electronic structure and magnetic properties of metal phthalocyanine (MPc) (M?=?Mn, Fe, Co, Ni, Cu, Zn) with or without four different gas molecules (NO, CO, O₂ and NO₂) adsorbing on the M atom of MPc molecule. The corresponding stable adsorption structural configurations and transport properties of MPc molecular junctions are also investigated. Our results indicate that the magnetic moment of MPc for M?=?Mn, Fe and Co can be modified by the specific gas molecule adsorption, which is mainly ascribed to competitive relation of HOMO-LUMO Gap and Hund's rules. However, for M?=?Ni, Cu and Zn, it is difficult to detect gas molecule because the interaction of M atom and these gases is most of weak van der Waals interaction. Remarkably, the spin of MPc molecule can be switched to a magnetic off-state by specific gas absorption, giving rise to a potential application on controllable spintronic devices. In addition, CO, NO, O₂ and NO₂ gas molecules can be detected selectively by measuring spin filter efficiency of these MPc molecular junctions. On the basis of our results, MPc (M?=?Mn, Fe, Co) molecular junctions can be considered as a promising nanosensor device to detect individual gas molecules.     

Photoluminescence properties of Eu and Mn-activated BaMgP2O7 as a potential red phosphor for white-emission

A phosphate compound, BaMgP₂O₇ was co-doped with Eu²⁺ and Mn²⁺ for making a red-emitting phosphor. The phosphor was prepared by a solid-state reaction at high temperature. The photoluminescence properties were investigated under ultraviolet (UV) ray excitation. From a powder X-ray diffraction (XRD) analysis, the formation of single-phased BaMgP₂O₇ with a monoclinic structure was confirmed. In the photoluminescence spectra, the BaMgP₂O₇:Eu,Mn phosphor emits two distinctive colors: a blue band centered at 409 nm originating from Eu²⁺ and a red band at 615 nm caused by Mn²⁺. Also, efficient energy transfer from Eu²⁺ to Mn²⁺ in the BaMgP₂O₇:Eu,Mn system was verified by observing that the excitation spectra of BaMgP₂O₇:Eu,Mn emitted at 409 and 615 nm by Eu²⁺ emission and Mn²⁺ emission, respectively, are almost the same as that of BaMgP₂O₇:Eu monitored at 409 nm. The optimum concentration of Eu²⁺ ions in BaMgP₂O₇:0.015Eu excited at 309 nm wavelength is 1.5 mol%. With an increase of Mn²⁺ content up to 17.5 mol%, a systematic decline in the intensity of the excitation spectrum by Eu²⁺ and a gradual growth in the intensity of emission band by Mn²⁺ were observed. Accordingly, the optimum concentration of Mn²⁺ in BaMgP₂O₇:0.015Eu,Mn is 17.5 mol%. The maximum spectral overlap between emission of Eu²⁺ and excitation of Mn²⁺ is achieved in a composition of BaMgP₂O₇:0.015Eu,0.175Mn, resulting in considerable red-emission at 615 nm.     

Microstructural and magnetic properties of Ax:Zn1-xO (A=Mn,Gd and Mn/Gd) nanocrystals

We report the microstructural and magnetic properties of transition (3d) and rare earth (4f) metal substituted into the A_x:Zn_1?xO (A=Mn, Gd and Mn/Gd) nanocrystal samples synthesized by solgel method. The structural properties and morphology of all samples have been analysed using X-ray diffraction (XRD) method and scanning electron microscopy. The impurity phase in the XRD patterns for all samples is not seen, except (Mn/Gd):ZnO sample where a very weak secondary phase of Gd₂O₃ is observed. Due to the large mismatch of the ionic radii between Mn²⁺ and Gd³⁺ ions, the strain inside the matrix increases, unlike the crystallite size decreases with the substitution of Mn and Gd into ZnO system. A couple of additional vibration modes due to the dopant have been observed in Raman spectrum. The magnetic properties have been studied by vibrating sample magnetometer. The magnetic hysteresis shows that Mn:ZnO and Gd:ZnO have soft ferromagnetic (FM) behaviour, whereas (Mn/Gd):ZnO has strong FM behaviour at room temperature (RT). The enhancement of ferromagnetism (FM) in (Mn/Gd):ZnO sample might be related to short-range FM coupling between Mn²⁺ and Gd³⁺ ions via defects potential and/or strain-induced FM coupling due to the expansion lattice by doping. The experimental results indicate that RTFM can be achieved by co-substitution of 3d and 4f metals in ZnO which can be used in spintronics applications.