Study ofAandBsites order in lanthanide-doped lead titanate ferroelectric system

2016 ◽  
Vol 31 (1) ◽  
pp. 23-30
Author(s):  
A. Pentón-Madrigal ◽  
Y. Mendez-González ◽  
A. Peláiz-Barranco ◽  
F. Calderón-Piñar ◽  
L. A. S. de Oliveira ◽  
...  
Keyword(s):  
Lead Titanate ◽  
Perovskite Structure ◽  
Ionic Radius ◽  
Phonon Mode ◽  
Lanthanide Ions ◽  
X Ray Diffraction ◽  
Ionic Radii ◽  
Optical Phonon Mode ◽  
Rietveld Refinements ◽  
X Ray

Pb0.88Ln0.08TiO3ferroelectric system, whereLn= La, Sm, Eu, and Dy, has been characterized using Scanning Electron Microscopy, Raman spectroscopy, and X-ray diffraction experiments. Softening of the lowest transverse optical phonon modeE(1TO) was evaluated as a function of the rare earths’ ionic radius suggesting partial occupation of lanthanide ions at theAandBsites of the perovskite structure. Using Rietveld refinements, it has been established a higher incorporation of Ln3+ions into theAsites of the perovskite structure than that of theBsites for the studied ceramics. The occupation atBsites increases slightly with the decreases of the ionic radii of the lanthanides.

A DFT study of spherands containing five anisyl groups — Highly preorganized to bind the alkali metal

2006 ◽  
Vol 84 (8) ◽  
pp. 1045-1049 ◽  
Author(s):  
Shabaan AK Elroby ◽  
Kyu Hwan Lee ◽  
Seung Joo Cho ◽  
Alan Hinchliffe
Keyword(s):  
Density Functional Theory ◽  
Binding Energy ◽  
Density Functional ◽  
Ionic Radius ◽  
Binding Energies ◽  
Cavity Size ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Good Agreement

Although anisyl units are basically poor ligands for metal ions, the rigid placements of their oxygens during synthesis rather than during complexation are undoubtedly responsible for the enhanced binding and selectivity of the spherand. We used standard B3LYP/6-31G** (5d) density functional theory (DFT) to investigate the complexation between spherands containing five anisyl groups, with CH2–O–CH2 (2) and CH2–S–CH2 (3) units in an 18-membered macrocyclic ring, and the cationic guests (Li+, Na+, and K+). Our geometric structure results for spherands 1, 2, and 3 are in good agreement with the previously reported X-ray diffraction data. The absolute values of the binding energy of all the spherands are inversely proportional to the ionic radius of the guests. The results, taken as a whole, show that replacement of one anisyl group by CH2–O–CH2 (2) and CH2–S–CH2 (3) makes the cavity bigger and less preorganized. In addition, both the binding and specificity decrease for small ions. The spherands 2 and 3 appear beautifully preorganized to bind all guests, so it is not surprising that their binding energies are close to the parent spherand 1. Interestingly, there is a clear linear relation between the radius of the cavity and the binding energy (R2 = 0.999).Key words: spherands, preorganization, density functional theory, binding energy, cavity size.

scholarly journals Interactions of tervalent lanthanide ions with bacterial collagenase (clostridiopeptidase A)

1981 ◽  
Vol 195 (3) ◽  
pp. 677-684 ◽  
Author(s):  
Christopher H. Evans
Keyword(s):  
Ionic Radius ◽  
Substrate Inhibition ◽  
Volume Ratio ◽  
Binding Pocket ◽  
Lanthanide Ions ◽  
Ionic Radii ◽  
Apparent Dissociation Constant ◽  
Substrate Complex ◽  
Bacterial Collagenase ◽  
Hydrolysis Of

Tervalent cations of the lanthanide (rare-earth) elements reversibly inhibit bacterial collagenase (clostridiopeptidase A; EC 3.4.24.3). Sm3+, whose ionic radius is closest to that of Ca2+, is the most effective inhibitor, completely suppressing clostridiopeptidase activity at a concentration of 100μm in the presence of 5mm-Ca2+. Er3+ and Lu3+, which both have ionic radii smaller than either Ca2+ or Sm3+, inhibit less efficiently, and La3+, which is slightly larger than Ca2+ or Sm3+, inhibits only weakly. These findings indicate a closely fitting, stereospecific, Ca2+-binding pocket in clostridiopeptidase, which excludes ions that are only slightly larger than Ca2+ [ionic radius 0.099nm (0.99 Ȧ)]. By contrast, trypsin, an enzyme whose activity does not depend on Ca2+, requires lanthanide concentrations 50–100-fold greater for inhibition. Furthermore, the relative efficiency of inhibition of trypsin by lanthanides increases as the lanthanide ions become smaller and the charge/volume ratio increases. At a concentration of 50μm, Sm3+ lowers the apparent Km for the hydrolysis of Pz-peptide by clostridiopeptidase from 5.4mm to 0.37mm and the apparent Vmax. from 0.29 Wünsch–Heidrich unit to 0.018 unit. Thus Sm3+ enhances the affinity of this enzyme for its substrate; inhibition of hydrolysis of Pz-peptide may result from the excessive stability of the enzyme–Sm3+–substrate complex. Inhibition by Sm3+ is competitive with regard to Ca2+. The apparent dissociation constant, Kd, of Ca2+ is 0.27mm, where the Ki for Sm3+ is 12μm. Clostridiopeptidase is more thermolabile in the absence of Ca2+. With Sm3+, thermoinactivation of the enzyme at 53°C or 60°C is initially accelerated, but then becomes retarded as heating continues. Lanthanide ions bind to gelatin and collagen. In so doing, they appear to protect these substrates from lysis by clostridiopeptidase through mechanisms additional to supplanting Ca2+ at its binding site on the enzyme. Collagen and gelatin sequester sufficient lanthanide ions to gain partial protection from clostridiopeptidase in the absence of an extraneous source of these inhibitors.

Hidden superlattice in Tl2(SC6H4S) and Tl2(SeC6H4Se) solved from powder X-ray diffraction

2011 ◽  
Vol 67 (5) ◽  
pp. 409-415 ◽  
Author(s):  
Kevin H. Stone ◽  
Dayna L. Turner ◽  
Mayank Pratap Singh ◽  
Thomas P. Vaid ◽  
Peter W. Stephens
Keyword(s):  
Additional Data ◽  
Sulfur Compound ◽  
Closed Shell ◽  
Initial Structure ◽  
X Ray Diffraction ◽  
Rietveld Refinements ◽  
X Ray ◽  
Additional Data Collection ◽  
Superlattice Structures ◽  
Counting Statistics

The crystal structures of the isostructural title compounds poly[(μ-benzene-1,4-dithiolato)dithallium], Tl2(SC6H4S), and poly[(μ-benzene-1,4-diselenolato)dithallium], Tl2(SeC6H4Se), were solved by simulated annealing from high-resolution synchrotron X-ray powder diffraction. Rietveld refinements of an initial structure with one formula unit per triclinic cell gave satisfactory agreement with the data, but led to a structure with impossibly close non-bonded contacts. A disordered model was proposed to alleviate this problem, but an alternative supercell structure leads to slightly improved agreement with the data. The isostructural superlattice structures were confirmed for both compounds through additional data collection, with substantially better counting statistics, which revealed the presence of very weak superlattice peaks not previously seen. Overall, each structure contains Tl—S or Tl—Se two-dimensional networks, connected by phenylene bridges. The sulfur (or selenium) coordination sphere around each thallium is a highly distorted square pyramid or a `see-saw' shape, depending upon how many Tl—S or Tl—Se interactions are considered to be bonds. In addition, the two compounds contain pairs of TlI ions that interact through a closed-shell `thallophilic' interaction: in the sulfur compound there are two inequivalent pairs of Tl atoms with Tl—Tl distances of 3.49 and 3.58 Å, while in the selenium compound those Tl—Tl interactions are at 3.54 and 3.63 Å.

Luminescence Studies on Low Temperature Synthesized ZnGa2O4:Ln3+ (Ln = Tb and Eu) Nanoparticles

2008 ◽  
Vol 8 (11) ◽  
pp. 5776-5780 ◽  
Author(s):  
C. Manikyala Rao ◽  
V. Sudarsan ◽  
R. S. Ningthoujam ◽  
U. K. Gautam ◽  
R. K. Vatsa ◽  
...  
Keyword(s):  
Energy Transfer ◽  
Oleic Acid ◽  
Steady State ◽  
Low Temperature ◽  
Ethylene Glycol ◽  
Urea Hydrolysis ◽  
Lanthanide Ions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Broad Emission

ZnGa2O4 nanoparticles doped with lanthanide ions (Tb3+ and Eu3+) were prepared at a low temperature of 120 °C based on urea hydrolysis in ethylene glycol medium. X-ray diffraction studies have confirmed that strain associated with nanoparticles changes as Tb3+ gets incorporated in the ZnGa2O4 lattice. Based on steady state emission and excitation studies of ZnGa2O4:Tb nanoparticles, it has been inferred that ZnGa2O4 host is characterized by a broad emission around 427 nm and there exists energy transfer between the host and Tb3+ ions. Unlike this, for ZnGa2O4:Eu nanoparticles, very poor energy transfer between the host and Eu3+ ions is observed. These nanoparticles when coated with ligands like oleic acid results in their improved dispersion in organic solvents like chloroform and dichloromethane.

Hydrothermal Synthesis of Lead Titanate Epitaxial Film for Non-Volatile Memory Device Application

2013 ◽  
Vol 652-654 ◽  
pp. 1846-1850
Author(s):  
Thin Thin Thwe ◽  
Than Than Win ◽  
Yin Maung Maung ◽  
Ko Ko Kyaw Soe
Keyword(s):  
Electron Microscopy ◽  
Silicon Dioxide ◽  
Lead Titanate ◽  
Conduction Mechanism ◽  
Epitaxial Film ◽  
Memory Device ◽  
X Ray Diffraction ◽  
X Ray ◽  
Non Volatile Memory ◽  
Scanning Electron

Hydrothermal synthesized lead titanate (PbTiO3¬) powder was prepared in a Teflon-lined stainless steel bomb at different bath temperatures. X-ray diffraction was performed to examine the phase assignment and crystallographic properties of hydrothermal synthesized lead titanate powder. Silicon dioxide (SiO2) was thermally deposited and adapted as intermediate layer on p-Si (100) substrates for MFIS (Metal/Ferroelectric/ Insulator/Semi-conductor) design. The microstructures of PbTiO3 film for both MFS and MFIS designs were observed by scanning electron microscopy (SEM). Charge conduction mechanism was also interpreted by C-2-V relationship. Polarization and electric field characteristics were measured by Sawyer-Tower circuit and good hysteresis nature was formed for both structures of the films. The loop of MFIS was wider than that of MFS cell. Also, the higher value of polarization (Ps=3.21E-03µC/cm2) for MFIS could be explained on the basis of higher dipole moment in this SiO2 buffer layer.

Morphological Characterization of Shape-Controlled TiO2 Anatase through XRPD Analysis

2016 ◽  
Vol 230 (9) ◽  
Author(s):  
Mauro Coduri ◽  
Michela Maisano ◽  
Maria Vittoria Dozzi ◽  
Elena Selli
Keyword(s):  
Morphological Characterization ◽  
Morphological Investigation ◽  
X Ray Diffraction ◽  
Preferential Growth ◽  
Rietveld Refinements ◽  
X Ray ◽  
Tio2 Anatase ◽  
Shape Controlled ◽  
Scherrer Equation

AbstractPreferential growth of anatase crystallites along different directions is known to deeply affect their photocatalytic properties, especially with respect to the exposure of the reactive {001} facets. Its extent can be easily quantified through simple geometric calculations, on the basis of crystal sizes extracted for specific directions by means of X-Ray Diffraction data analysis. Nevertheless, the actual results depend on the method employed for such a quantification. Here we report on a comparative morphological investigation, performed by employing the Scherrer equation and the line profile from Rietveld refinements, on shape-controlled anatase photocatalysts produced by employing HF as capping agent. Compared to the Rietveld-based method, the use of the Scherrer equation produces a systematic underestimation of crystallite dimensions, especially concerning the [100] direction, which in turn causes the percentage of exposed {001} crystal facets to be underestimated. Neglecting instrumental-related effects may further reduce the estimate.

A first Mn member in the struvite morphotropic series, CsMn(H2O)6(PO4): hydrothermal synthesis, crystal structure and interconnections within the family of related phosphates

2018 ◽  
Vol 74 (8) ◽  
pp. 936-943
Author(s):  
Galina V. Kiriukhina ◽  
Olga V. Yakubovich ◽  
Ekaterina M. Kochetkova ◽  
Olga V. Dimitrova ◽  
Anatoliy S. Volkov
Keyword(s):  
Crystal Structure ◽  
Ionic Radius ◽  
The Novel ◽  
X Ray Diffraction ◽  
Unit Cell Parameters ◽  
Hydrothermal Conditions ◽  
X Ray ◽  
Cell Parameters ◽  
Structural Relationships ◽  
The Family

Caesium manganese hexahydrate phosphate, CsMn(H2O)6(PO4), was synthesized under hydrothermal conditions. Its crystal structure was determined from single-crystal X-ray diffraction data. The novel phase crystallizes in the hexagonal space group P63 mc and represents the first manganese member in the struvite morphotropic series, AM(H2O)6(TO4). Its crystal structure is built from Mn(H2O)6 octahedra and PO4 tetrahedra linked into a framework via hydrogen bonding. The large Cs atoms are encapsulated in the framework cuboctahedral cavities. It is shown that the size of the A + ionic radius within the morphotropic series AM(H2O)6(XO4) results is certain types of crystal structures and affects the values of the unit-cell parameters. Structural relationships with Na(H2O)Mg(H2O)6(PO4) and the mineral hazenite, KNa(H2O)2Mg2(H2O)12(PO4)2, are discussed.

scholarly journals The origins of binding specificity of a lanthanide ion binding peptide

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Takaaki Hatanaka ◽  
Nobuaki Kikkawa ◽  
Akimasa Matsugami ◽  
Yoichi Hosokawa ◽  
Fumiaki Hayashi ◽  
...  
Keyword(s):  
Water Molecule ◽  
Ionic Radius ◽  
Binding Specificity ◽  
Lanthanide Ions ◽  
Ion Binding ◽  
Deep Insight ◽  
Ionic Radii ◽  
Linear Peptide ◽  
High Affinity ◽  
Insight Into

Abstract Lanthanide ions (Ln3+) show similar physicochemical properties in aqueous solutions, wherein they exist as + 3 cations and exhibit ionic radii differences of less than 0.26 Å. A flexible linear peptide lanthanide binding tag (LBT), which recognizes a series of 15 Ln3+, shows an interesting characteristic in binding specificity, i.e., binding affinity biphasically changes with an increase in the atomic number, and shows a greater than 60-fold affinity difference between the highest and lowest values. Herein, by combining experimental and computational investigations, we gain deep insight into the reaction mechanism underlying the specificity of LBT3, an LBT mutant, toward Ln3+. Our results clearly show that LBT3-Ln3+ binding can be divided into three, and the large affinity difference is based on the ability of Ln3+ in a complex to be directly coordinated with a water molecule. When the LBT3 recognizes a Ln3+ with a larger ionic radius (La3+ to  Sm3+), a water molecule can interact with Ln3+ directly. This extra water molecule infiltrates the complex and induces dissociation of the Asn5 sidechain (one of the coordinates) from Ln3+, resulting in a destabilizing complex and low affinity. Conversely, with recognition of smaller Ln3+ (Sm3+ to Yb3+), the LBT3 completely surrounds the ions and constructs a stable high affinity complex. Moreover, when the LBT3 recognizes the smallest Ln3+, namely Lu3+, although it completely surrounds Lu3+, an entropically unfavorable phenomenon specifically occurs, resulting in lower affinity than that of Yb3+. Our findings will be useful for the design of molecules that enable the distinction of sub-angstrom size differences.

Heterobimetallische 3d-4f-Komplexe mit Bis(1,2-dithiooxalato)nickelat(II) als planarem Brückenbaustein / Heterobimetallic 3d-4f-Complexes with Bis(1,2-dithiooxalato)nickelate(II) as Planar Bridging Block

2005 ◽  
Vol 60 (11) ◽  
pp. 1149-1157 ◽  
Author(s):  
Matthias Siebold ◽  
Alexandra Kelling ◽  
Uwe Schilde ◽  
Peter Strauch
Keyword(s):  
Room Temperature ◽  
Magnetic Moments ◽  
Lanthanide Ions ◽  
Water Molecules ◽  
Unit Cell Parameters ◽  
Ionic Radii ◽  
X Ray ◽  
Cell Parameters ◽  
Heterobimetallic Complexes ◽  
The Individual

Planar bis(1,2-dithiooxalato)nickelates(II) react in aqueous solutions of lanthanide ions to form pentanuclear, heterobimetallic complexes of the general composition [{Ln(H2O)n}2- {Ni(dto)2}3]・xH2O (Ln = Y3+, La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+; n = 4 or 5; x = 9 - 12). With [{Nd(H2O)5}2{Ni(S2C2O2)2}3]・xH2O (x = 10 - 12) (1) and [{Er(H2O)4}2{Ni(S2C2O2)2}3]・xH2O (x = 9 - 10) (2) we were able to isolate two complexes of this series as single crystals, which were characterized by X-ray structure analysis. Depending on the individual ionic radii of the lanthanide ions, the compounds crystallize in two different crystal systems with the following unit cell parameters: 1, monoclinic in P21/c with a = 11.3987(13), b = 11.4878(8), c = 20.823(2) Å , β = 98.907(9)° and Z = 2; 2, triclinic in P1̅ with a = 10.5091(6), b = 11.0604(6), c = 11.2823(6) Å , α = 107.899(4)°, β = 91.436(4)°, γ = 112.918(4)° and Z = 1. The channels and cavities appearing in the packing of the molecules are occupied by uncoordinated water molecules. High magnetic moments up to 14.65 BM./f.u. have been observed at room temperature due to the combined moments of the individual lanthanide ions.

scholarly journals Structural and morphological characterization of rare earth modified lead titanate

Cerâmica ◽  
2007 ◽  
Vol 53 (328) ◽  
pp. 422-447
Author(s):  
F. C. D. Lemos ◽  
D. M. A. Melo ◽  
P. S. de Lima ◽  
C. A. Paskocimas ◽  
E. Longo ◽  
...  
Keyword(s):  
Rare Earth ◽  
Lead Titanate ◽  
Pechini Method ◽  
Morphological Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
Different Temperatures ◽  
Crystallite Sizes ◽  
Modifier Cation

Rare earth modified lead titanate powders Pb1-xRExTiO3 (REPT), x = 0.01, 0.05, 0.07 and RE = Yb, Y, were prepared by the Pechini method. The materials were calcined under flowing oxygen at different temperatures from 300 to 700 ºC. Nanostructured REPT were investigated using X-ray diffraction, scanning electron microscopy and surface area analysis (BET). The results suggest that the modifier cation incorporated into the system has notable influence in the microstructure and a notable decrease in the crystallite sizes.

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