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1.
The aggregation of Aβ42 peptides is considered as one of the main causes for the development of Alzheimer's disease. In this context, Zn2+ and Cu2+ play a significant role in regulating the aggregation mechanism, due to changes in the structural and the solvation free energy of Aβ42. In practice, experimental studies are not able to determine the latter properties, since the Aβ42–Zn2+ and Aβ42–Cu2+ peptide complexes are intrinsically disordered, exhibiting rapid conformational changes in the aqueous environment. Here, we investigate atomic structural variations and the solvation thermodynamics of Aβ42, Aβ42–Cu2+, and Aβ42–Zn2+ systems in explicit solvent (water) by using quantum chemical structures as templates for a metal binding site and combining extensive all-atom molecular dynamics (MD) simulations with a thorough solvation thermodynamic analysis. Our results show that the zinc and copper coordination results in a significant decrease of the solvation free energy in the C-terminal region (Met35-Val40), which in turn leads to a higher structural disorder. In contrast, the β-sheet formation at the same C-terminal region indicates a higher solvation free energy in the case of Aβ42. The solvation free energy of Aβ42 increases upon Zn2+ binding, due to the higher tendency of forming the β-sheet structure at the Leu17-Ala42 residues, in contrast to the case of binding with Cu2+. Finally, we find the hydrophobicity of Aβ42–Zn2+ in water is greater than in the case of Aβ42–Cu2+.  相似文献   

2.
A series of Eu2+‐, Sm3+‐ and Eu2+/Sm3+‐doped SrZn2(PO4)2 samples were synthesized using a solid‐state reaction. SrZn2(PO4)2:Eu2+ presented a broad emission band due to 4f65d–4f7 transition of the Eu2+ ion. The spectra of SrZn2(PO4)2:Sm sintered in air and H2/N2 were identical in every aspect, except for a very small difference in intensity. A Eu2+–Sm3+ energy transfer scheme was proposed to realize the sensitization of Sm3+ ion emission by Eu2+ ions, and UV‐convertible Sm3+‐activated red phosphor was obtained in SrZn2(PO4)2:Eu2+, Sm3+. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

3.
The compound Na3SO4Cl X (X = Ce3+, Eu3+ or Dy3+) prepared by the wet chemical method was studied for its photoluminescence (PL) and energy transfer characteristics. The PL from Na3SO4Cl:Ce3+ shows strong emission at 322 nm at an excitation of 272 nm. Therefore, an efficient Ce3+ → Dy3+, Eu2+ → Dy3+ and Eu2+ → Eu3+ energy transfer had taken place in this host. The Dy3+ emission caused by Ce3+ → Dy3+ energy transfer under ultraviolet (UV) wavelengths peaked at around 477 nm and 572 nm due to 4 F9/26H15/2 and 6H13/2 transitions with yellow–orange emission in the Na3SO4Cl lattice. An intense Dy3+ emission was observed at 482 and 576 nm caused by the Eu2+ → Dy3+ energy transfer process and due to 4 F9/26H15/2 and 4 F9/26H13/2 transitions respectively. The Eu3+ blue to red light emission caused by the Eu2+ → Eu3+ energy transfer peaked at 593 nm and 617 nm due to 5D05D3 transitions. The presence of trivalent Eu in Na3SO4Cl suggested the presence of Eu3+ in the host compound that occupied two different lattice sites and that peaked at 593 and 617 nm due to 5D07 F1 and 5D07 F2 transitions respectively. The trivalent europium ion is very useful for studying the nature of metal coordination in various systems due to its non‐degenerate emitting 5D0 state. The present paper discusses the photoluminescence characteristics of Eu2+ → Dy3+ and Eu2+ → Eu3+ energy transfer. This compound may be useful as a lamp phosphor. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

4.
Research of the entry of rare earth elements Eu3+ and La3+ into plant cell   总被引:8,自引:0,他引:8  
Whether rare earth elements can enter into plant cells remains controversial. This article discusses the ultracellular structural localization of lanthanum (La3+) and europium (Eu3+) in the intact plant cells fed by rare earth elements Eu3+ and La3+. Eu-TTA fluorescence analysis of the plasmalemma, cytoplast, and mitochondria showed that Eu3+ fluorescence intensities in such structures significantly increased. Eu3+ can directly enter or be carried by the artificial ion carrier A23187 into plant cells through the calcium ion (Ca2+) channel and then partially resume the synthesis of amaranthin in the Amaranthus caudatus growing in the dark. Locations of rare earth elements La3+ and Eu3+ in all kinds of components of cytoplasmatic organelles were determined with transmission electron microscope, scanning electron microscope, and energy-dispersive X-ray microanalysis. The results of energy-dispersive X-ray microanalysis indicated that Eu3+ and La3+ can be absorbed into plant cells and bind to the membranes of protoplasm, chloroplast, mitochondrion, cytoplast, and karyon. These results provide experimental evidence that rare earth elements can be absorbed into plant cells, which would be the basis for interpreting physiological and biochemical effects of rare earth elements on plant cells.  相似文献   

5.
Rare‐earth ions play an important role in eco‐friendly solid‐state lighting for the lighting industry. In the present study we were interested in Eu3+ ion‐doped inorganic phosphors for near ultraviolet (UV) excited light‐emitting diode (LED) applications. Eu3+ ion‐activated SrYAl3O7 phosphors were prepared using a solution combustion route at 550°C. Photoluminescence characterization of SrYAl3O7:Eu3+ phosphors showed a 612 nm emission peak in the red region of the spectrum due to the 5D07F2 transition of Eu3+ ions under excitation at 395 nm in the near‐UV region and at the 466 nm blue excitation wavelength. These red and blue emissions are supported for white light generation for LED lighting. Structure, bonding between each element of the sample and morphology of the sample were analysed using X‐ray diffraction (XRD) and scanning electron microscopy (SEM), which showed that the samples were crystallized in a well known structure. The phosphor was irradiated with a 60Co‐γ (gamma) source at a dose rate of 7.2 kGy/h. Thermoluminescence (TL) studies of these Eu3+‐doped SrYAl3O7 phosphors were performed using a Nucleonix TL 1009I TL reader. Trapping parameters of this phosphor such as activation energy (E), order of kinetics (b) and frequency factor (s) were calculated using Chen's peak shape method, the initial rise method and Ilich's method.  相似文献   

6.
White-light-tunable LaMgAl11O19:x%Tb3+, y%Eu3+ series phosphors were prepared using the gel-combustion method. The structure and luminescence properties were studied, and the energy transfer of Eu3+ and Tb3+ in the LaMgAl11O19 system was also discussed. The results showed that the LaMgAl11O19 matrix exhibited strong emission in the blue-light region under the excitation of ultraviolet light, which resulted in conditions suitable for the preparation of white-light-tunable phosphors. The emission spectra of LaMgAl11O19:2%Tb3+, y%Eu3+ (y = 2%–9%) series phosphors were obtained through optimization experiments. It could be seen from the CIE diagram that by adjusting the doping quantities of Eu3+ and Tb3+ in the LaMgAl11O19 host, multicolor luminescence and white light emission in a single host could be achieved. By calculating the energy transfer efficiency and critical distance between Eu3+ and Tb3+ series phosphors, the mechanism of energy transfer between Tb3+ and Eu3+ was found to be the interaction between electric quadruples.  相似文献   

7.
In this paper, the Eu3+–Eu2+ (4%, molar ratio)‐doped xAl2O3–ySiO2 (x = 0–2.5, y = 1–5) and xAl2O3–zMgO (x = 0–1.5, z = 0–3) composites phosphors with different Al2O3 to SiO2 (A/S) and Al2O3 to MgO (A/M) ratios were prepared using a high‐temperature solid‐state reaction under air atmosphere. The effects of the A/S and A/M on luminescence properties, crystal structure, electron spin resonance, and Commission Internationale de l’Eclairage chromaticity coordinates of the samples were systematically analyzed. These results indicated that the different A/S and A/M ratios in the matrix effectively affected the crystal phase, degrees of self‐reduction of Eu3+, and led the relative emission intensity of Eu2+/Eu3+ to change and adjust.  相似文献   

8.
A high intensity 464 nm excitable ZnWO4:Eu3+ red‐emitting phosphor for warm white lighting applications was prepared using a solid‐state reaction method by varying the dopant Eu3+ concentration. Crystalline purity and phase identification was confirmed and revealed using powder X‐ray diffraction and Rietveld refinement analysis. The surface morphology of Zn1‐xEuxWO4 (x = 0, 0.01, 0.02, 0.03, 0.04 and 0.05) was examined using scanning electron microscopy (SEM) techniques. From SEM analysis, the ZnWO4:Eu3+ phosphor prepared at 1–3% molar Eu3+ concentrations exhibited a small pebble‐like morphology with a smooth surface. On increasing the molar concentration of Eu3+ to >3%, the pebble stone morphology disappeared and a large, smooth irregular polygon‐shaped granular‐like morphology was obtained. Of the higher mol% Eu3+, the 4% Eu3+‐doped ZnWO4 showed the best photoluminescence properties with high intensity and sharp excitation at 395 and 464 nm, followed by red emission centred at 615 nm with excellent CIE coordinates (x = 0.58 and y = 0.41) in the core red region. Elemental composition and chemical state analysis were carried out for the 4% Eu3+‐doped ZnWO4 phosphor using X‐ray photoelectron spectroscopy and energy dispersive X‐ray spectroscopy studies. Based on all the above analyses, the Eu3+‐doped ZnWO4 phosphor was found to be a very efficient red‐emitting phosphor under near‐UV light as well as under visible light excitation and could be used for white LED and field emissive displays applications.  相似文献   

9.
In this study, Li6Y1–xEux(BO3)3 phosphor was successfully synthesized using a modified solid‐state diffusion method. The Eu3+ ion concentration was varied at 0.05, 0.1, 0.2, 0.5 and 1 mol%. The phosphor was characterized for phase purity, morphology, luminescent properties and molecular transmission at room temperature. The XRD pattern suggests a result closely matching the standard JCPDS file (#80‐0843). The emission and excitation spectra were followed to discover the luminescence traits. The excitation spectra indicate that the current phosphor can be efficiently excited at 395 nm and at 466 nm (blue light) to give emission at 595 and 614 nm due to the 5D07Fj transition of Eu3+ ions. Concentration quenching was observed at 0.5 mol% Eu3+ in the Li6Y1–xEux(BO3)3 host lattice. Strong red emission with CIE chromaticity coordinates of phosphor is x = 0.63 and y = 0.36 achieved with dominant red emission at 614 nm the 5D07 F2 electric dipole transition of Eu3+ ions. The novel Li6Y1–xEux(BO3)3 phosphor may be a suitable red‐emitting component for solid‐state lighting using double‐excited wavelengths, i.e. near‐UV at 395 nm and blue light at 466 nm. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

10.
The preferential selectivity of dicyclohexano-18-crown-6 (DCH18C6) for bivalent Sr+2 ion over tetravalent Th+4 ion was investigated using generalized gradient approximated (GGA) BP86 and the hybrid B3LYP density functional, employing split valence plus polarization (SV(P)) and triple-zeta valence plus polarization (TZVP) basis sets in conjunction with the COSMO (conductor-like screening model) solvation approach. The calculated theoretical selectivity of DCH18C6 for Sr+2 ion over Th+4 ion was found to be in accord with the selectivity for Sr+2 ion over Th+4 ion observed when performing liquid–liquid extraction experiments in different organic solvents. While 1:1(M:L) stoichiometric complexation reactions can be used to predict the preferential selectivity of Sr2+ ion over Th4+ ion, the results obtained are not consistent with the experimental results observed upon increasing the dielectric constant of the solvent. The calculated theoretical gas-phase data for the free energy of complexation, ?G, fail to explain the selectivity for Sr+2 ion over Th+4 ion. However, when 1:2 (M:L) stoichiometric complexation reactions (reported in previous X-ray crystallography studies) are considered, correct and consistent results for the selectivity for Sr+2 ion over a wide range of dielectric constants are predicted. The distribution constant for Sr2+ and Th4+ ions was found to gradually increase with increasing dielectric constant of the organic solvent, and was found to be highest in nitrobenzene. The selectivity data calculated from ??G ext are in excellent agreement with the results obtained from solvent extraction experiments.
Figure
Experimentally observed separation factors and theoretically predicted values of ΔΔG ext for Sr2+ ion over Th4+ ion with DCH18C6 in a nitrate medium. Solvent extraction with DCH18C6/nitrobenzene shows high selectivity and a high separation factor for Sr2+ over Th4+. DFT was successfully adopted to model the extraction mechanism of Sr2+/Th4+. The free energy of extraction ΔΔG ext failed to predict the experimental selectivity of Sr2+ over Th4+ for 1:1 stoichiometric complexation, but was able to predict this selectivity for 1:2 stoichiometric complexation with Th4+ ion. The ΔΔG ext values for the preferential selection of Sr2+ over Th4+ increase with increasing dielectric constant of the solvent  相似文献   

11.
The MgO–Ga2O3–SiO2 glasses and glass‐ceramics samples doped with Eu2+/Mn2+/Er3+ and heated in reductive atmosphere were prepared by the sol–gel method. The structure, morphology and the luminescence properties were studied using X‐ray diffraction, high‐resolution transmission electron microscope, fluorescence spectra, and up‐conversion emission. The luminescence characteristics of doped ions could be influenced by temperature and matrix component. The characteristic emission of Mn2+, Eu2+ and Er3+ were seen and the energy transfer efficiency from Eu2+ to Mn2+ was enhanced as Mn2+ concentration was increased. In addition, the two‐photon process was determined for the Er3+‐doped samples.  相似文献   

12.
A flow-dialysis apparatus suitable for the study of high affinity metal ion binding sites in macromolecules has been utilized to study 155Eu3+ exchange processes, as a function of pH, in both ‘native’ and ‘heat-denatured’ DNA. ‘Free exchange’ of 155Eu3+ was found to occur at a significantly faster rate at pH = 7.0 than at pH = 6.0 for both forms of DNA; while non-radioactive Eu3+-induced ‘displacement’ of bound 155Eu3+ occurred at a significantly faster rate at pH = 6.0 than at pH = 7.0 for both species of DNA. These results are consistent with a greater ‘entropic’ driving force for metal ion:DNA complexation at the lower pH value. The effect of ethidium bromide on 155Eu3+ exchange was also examined as a function of pH. The intercalating agent was found to accelerate 155Eu3+ displacement at pH = 6.0 and decelerate displacement at pH = 7.0. All three sets of experiments (i.e., free- exchange of bound 155Eu3+, Eu3+-induced displacement of bound 155Eu3+ and ethidium ion-induced displacement of bound 155Eu3+) indicate that the 155Eu3+ ion can serve as a useful probe of metal ion and drug binding sites in nucleic acid polymers, and constitutes a particularly sensitive probe at pH = 6.0.  相似文献   

13.
The individual emission and energy transfer between Ce3+ and Eu2+ or Dy3+ in BaCa(SO4)2 mixed alkaline earth sulfate phosphor prepared using a co‐precipitation method is described. The phosphor was characterized by X‐ray diffraction (XRD) and photoluminescence (PL) studies and doped by Ce;Eu and Dy rare earths. All phosphors showed excellent blue–orange emission on excitation with UV light. PL measurements reveal that the emission intensity of Eu2+ or Dy3+ dopants is greater than when they are co‐doped with Ce3+. An efficient Ce3+ → Eu2+ [2T2g(4f65d) → 8S7/2(4f7)] and Ce3+ → Dy3+ (4 F9/26H15/2 and 4 F9/26H13/2) energy transfer takes place in the BaCa(SO4)2 host. A strong blue emission peak was observed at 462 nm for Eu2+ ions and an orange emission peak at 574 nm for Dy3+ ions. Hence, this phosphor may be used as a lamp phosphor. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

14.
Potassium fluoro‐phosphate (KFP) glass singly doped with different concentrations of europium (Eu3+) or samarium (Sm3+) or co‐doped (Sm3+/Eu3+) was prepared, and their luminescence spectra were investigated. The phase composition of the product was verified by X‐ray diffraction analysis. Optical transition properties of Eu3+ in the studied potassium phosphate glass were evaluated in the framework of the Judd–Ofelt theory. The radiative transition rates (AR), fluorescence branching ratios (β), stimulated emission cross‐sections (σe) and lifetimes (τexp) for certain transitions or levels were evaluated. Red emission of Eu3+ was exhibited mainly by the 5D07F2 transition located at 612 nm. Concentration quenching and energy transfer were observed from fluorescence spectra and decay curves, respectively. It was found that the lifetimes of the 5D0 level increased with increase in concentration and then decreased. By co‐doping with Sm3+, energy transfer from Sm3+ to Eu3+ occurred and contributed to the enhancement in emission intensity. Intense orange‐red light emission was obtained upon sensitizing with Sm3+ in KFP glass. This approach shows significant promise for use in reddish‐orange lighting applications. The optimized properties of the Sm3+/Eu3+ co‐doped potassium phosphate glass might be promising for optical materials.  相似文献   

15.
K. N. Shinde  K. Park 《Luminescence》2013,28(5):793-796
A series of efficient Li3Al2(PO4)3:Eu2+ novel phosphors were synthesized by the facile combustion method. The effects of dopant on the luminescence behavior of Li3Al2(PO4)3 phosphor were also investigated. The phosphors were characterized by X‐ray diffraction, field emission scanning electron microscope and photoluminescence techniques. The result shows that all samples can be excited efficiently by near‐ultraviolet excitation under 310 nm. The emission was observed for Li3Al2(PO4)3:Eu2+ phosphor at 425 nm, which corresponded to the d → f transition. The concentration quenching of Eu2+ was observed in Li3Al2(PO4)3:Eu2+ when the Eu concentration was at 0.5 mol%. The prepared powders exhibited intense blue emission at the 425 nm owing to the Eu2+ ion by Hg‐free excitation at 310 nm (i.e., solid‐state lighting excitation). Consequently, the availability of such a phosphor will significantly help in the development of blue‐emitting solid‐state lighting applications. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

16.
A series of color‐tunable Ca3–2x‐y‐zSiO4Cl2 (CSC):xCe3+,xLi+,yMn2+,zEu2+ phosphors with low temperature phase structure was synthesized via the sol–gel method. An energy transfer process from Ce3+ to Mn2+ in CSC:0.01Ce3+,0.01Li+,yMn2+ (y = 0.03–0.09) and the mechanism was verified to be an electric dipole–dipole interaction. The Ce3+ and Mn2+ emission intensities were greatly enhanced by co‐doping Eu2+ ions into CSC:0.01Ce3+,0.01Li+,0.07Mn2+ phosphors due to competitive energy transfers from Eu2+/Ce3+ to Mn2+, and Ce3+ to Eu2+. Under 332 nm excitation, CSC:0.01Ce3+,0.01Li+,0.07Mn2+,zEu2+ (z = 0.0005–0.002) exhibited tunable emission colors from green to white with coexisting orange, green and violet‐blue emissions. These phosphors could have potential application in white light‐emitting diodes.  相似文献   

17.
LiCaBO3:Dy3+/Eu3+ phosphors were synthesized by a solid‐state reaction. The synthesized materials were characterized using powder X‐ray diffraction pattern (XRD) for confirmation. All the structural parameters were calculated from the XRD data. Scanning electron microscopy (SEM) images showed rod‐like morphology. Photoluminescence (PL) emission spectra showed two emissions (484 and 577 nm) in Dy3+‐doped LiCaBO3:Dy3+phosphors with the concentration quenching effect and the critical distance was calculated to be about 22.76 Å. LiCaBO3:Eu3+ phosphor was effectively excited by a near‐UV light of 392 nm. The emission spectra exhibited the transition from 5D0 level to 7FJ (J = 0–2) with main emission at 614 nm, which comes from the electrodipole transition because of the asymmetric point group. The quenching concentration of Eu3+ is about 0.2 mol%, and the critical distance was calculated to be about 38.93 Å. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

18.
A series of Bi3+,Eu3+‐doped BaMoO4 phosphors was synthesized using a hydrothermal method. The crystal structure, morphology and optical properties of the phosphors were studied using X‐ray diffraction (XRD), scanning electron microscope (SEM) and photoluminescence (PL) measurements. Three different particle morphologies were detected in the SEM observation. The energy dispersive spectroscopy (EDS) results indicated that the solubility of Bi3+ in spherical or rugby‐like BaMoO4 particles was very low and the excess Bi3+ element was cumulated in the irregular particles. Characteristic emissions of Eu3+ ions (5D0 → 7FJ; J = 0, 1, 2, 3, 4) were observed under excitation in ultraviolet (UV) light, with the most intense transition being the 5D0 → 7F2 transition. Energy transfer from MoO42? and Bi3+ to Eu3+ can be readily achieved. Red emission intensity of Eu3+ was enhanced by a factor of two by co‐doping with a small amount of Bi3+. Optical properties as a function of Bi3+ content were studied and the optimum Bi3+ content in BaMoO4 nanocrystals was determined to be 0.4 mol%.  相似文献   

19.
The Eu2+/Eu3+ mixed valence phosphor Ca2SiO2F2:Eu2+/Eu3+ was prepared using a solid‐state reaction synthesis method in a CO atmosphere, and the optical properties were investigated. The spectroscopic properties revealed that Ca2+ ions were occupied by both Eu2+ and Eu3+ ions in Ca2SiO2F2, and both ions were able to generate their characteristic emissions. A broad 5d → 4f Eu2+ band at ~470 nm and narrow 4f → 4f Eu3+ peaks upon excitation with n‐UV light were observed. The ratio between Eu2+ and Eu3+ emissions changed regularly, and the relative intensity of the red component from Eu3+ became systematically stronger with increasing overall Eu content. As a result, the emission color of these phosphors can be tunable from blue to pink under n‐UV light excitation.  相似文献   

20.
The activity of yeast alcohol dehydrogenase is markedly enhanced by Eu3+ ions. At pH 7.0 two binding constants for Eu3+, 1.0 × 10–2 and 2.0 × 10–3 M, were obtained using a Scatchard plot. The presence of Zn2+ ions restricts the Eu3+-induced increase in the activity of yeast alcohol dehydrogenase. Studies on the tryptophan fluorescence of the enzyme in the absence and presence of Eu3+ or Zn2+ ions showed that Eu3+ affects tertiary or quaternary structures, which is consistent with its activation of the enzyme. The presence of Zn2+ reverses the conformational changes caused by Eu3+. Comparison of the effects of Eu3+ with Zn2+ for apo-yeast alcohol dehydrogenase indicates that their binding sites on the protein are different.  相似文献   

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