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1.
J Synchrotron Radiat ; 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38917023

RESUMO

Introducing a new Main Editor of JSR.

2.
Inorg Chem ; 62(1): 87-97, 2023 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-36529981

RESUMO

The liquid-liquid extraction (LLE) process for lanthanide-actinide separation from the nuclear fuel cycle has several drawbacks such as, the requirement of cooling for decay heat control, the handling of large volumes of toxic volatile organic compounds (VOCs), and secondary waste generation. Alternatively reprocessing without spent fuel cooling is done by pyroprocessing, which uses high-temperature corrosive molten salts and requires elevated temperature, and is an energy-intensive process. In recent years, some of the shortcomings of both LLE and pyroprocessing are overcome by the use of room temperature ionic liquids (RTILs) as the solvents. In the present work, an attempt was made to exploit the potential of the neoteric, less-corrosive, low-VOC RTILs toward direct dissolution-based separations at ambient conditions. The present paper involves the selective dissolution of Eu2O3 in an RTIL, i.e., C4mim·NTf2 containing 2-thenoyltrifluoroacetone (HTTA) within ca. 30 min at ambient conditions; while the dissolution of AmO2 and UO2 were found to be very poor, making this an attractive method for lanthanide-actinide separation, a key step in radioactive waste management, i.e., an actinide partitioning and transmutation strategy. The quantitative dissolution of Eu2O3 from simulated spent nuclear fuel with different Eu2O3 loading was also shown. Water plays a crucial role in deciding the kinetics of dissolution and amount of the dissolved oxide. The combination of X-ray absorption, fluorescence, and UV-vis spectroscopic studies suggested the formation of the dehydrated anionic complex Ln(TTA)4- to play pivotal role in the oxide dissolution process. The structure of the complex was analyzed by density functional theory and extended X-ray absorption fine structure. The mechanism of oxide dissolution was proposed and electrochemical studies were performed to understand the possible recovery option using electrodeposition of the dissolved Eu3+.

3.
PLoS Genet ; 15(2): e1007959, 2019 02.
Artigo em Inglês | MEDLINE | ID: mdl-30763303

RESUMO

The nuclear division takes place in the daughter cell in the basidiomycetous budding yeast Cryptococcus neoformans. Unclustered kinetochores gradually cluster and the nucleus moves to the daughter bud as cells enter mitosis. Here, we show that the evolutionarily conserved Aurora B kinase Ipl1 localizes to the nucleus upon the breakdown of the nuclear envelope during mitosis in C. neoformans. Ipl1 is shown to be required for timely breakdown of the nuclear envelope as well. Ipl1 is essential for viability and regulates structural integrity of microtubules. The compromised stability of cytoplasmic microtubules upon Ipl1 depletion results in a significant delay in kinetochore clustering and nuclear migration. By generating an in silico model of mitosis, we previously proposed that cytoplasmic microtubules and cortical dyneins promote atypical nuclear division in C. neoformans. Improving the previous in silico model by introducing additional parameters, here we predict that an effective cortical bias generated by cytosolic Bim1 and dynein regulates dynamics of kinetochore clustering and nuclear migration. Indeed, in vivo alterations of Bim1 or dynein cellular levels delay nuclear migration. Results from in silico model and localization dynamics by live cell imaging suggests that Ipl1 spatio-temporally influences Bim1 or/and dynein activity along with microtubule stability to ensure timely onset of nuclear division. Together, we propose that the timely breakdown of the nuclear envelope by Ipl1 allows its own nuclear entry that helps in spatio-temporal regulation of nuclear division during semi-open mitosis in C. neoformans.


Assuntos
Aurora Quinase B/metabolismo , Divisão do Núcleo Celular/fisiologia , Cryptococcus neoformans/metabolismo , Proteínas Fúngicas/metabolismo , Transporte Ativo do Núcleo Celular , Aurora Quinase B/genética , Divisão do Núcleo Celular/genética , Segregação de Cromossomos , Cromossomos Fúngicos/genética , Simulação por Computador , Cryptococcus neoformans/citologia , Cryptococcus neoformans/genética , Dineínas/metabolismo , Proteínas Fúngicas/genética , Genes Fúngicos , Cinetocoros/metabolismo , Microtúbulos/metabolismo , Mitose , Modelos Biológicos , Mutação , Análise Espaço-Temporal
4.
Curr Opin Rheumatol ; 33(6): 495-504, 2021 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-34494608

RESUMO

PURPOSE OF REVIEW: Primary cilia, the antenna-like organelles on most mammalian cells, host key components of multiple morphogen signal transduction pathways. Mutations in genes responsible for primary cilia assembly and function generally result in pathological conditions known as ciliopathies, which underlie several diseases, including various forms of fibrosis. Primary cilia modulate cellular responses to extracellular cues, including TGF-ß and morphogens, such as Hedgehog. Aberrant morphogen signaling is recognized as essential for the transition of mesenchymal progenitor cells to myofibroblasts, the key step in fibrosis. This article aims to provide a critical overview of recent developments and insights in primary cilia biology relevant to fibrosis. RECENT FINDINGS: Several studies have highlighted the association of altered primary cilia with various forms of fibrosis. In a rather complex manner, the presence of primary cilia seems to be required for initiation of myofibroblast transition, whereas its loss promotes myofibroblast transition at a later stage. Recent evidence also suggested that noncanonical functions of ciliary transport proteins may influence, such cellular transitions independently of primary cilia. The possibility of opposing signaling regulations being topologically separated between primary cilia and plasma membrane could also be critical for fibrosis. SUMMARY: Recent progress in the field suggests that primary cilia are critical mediators of the pathogenesis of fibrosis. Understanding the potential role of primary cilia in fibrosis and the underlying mechanisms may pave the way for entirely new approaches for fibrosis prevention and treatment of SSc.


Assuntos
Cílios , Transdução de Sinais , Animais , Cílios/patologia , Fibrose , Humanos , Miofibroblastos , Organelas
5.
J Cell Sci ; 132(17)2019 09 06.
Artigo em Inglês | MEDLINE | ID: mdl-31391238

RESUMO

The adhesive force for cisternal stacking of Golgi needs to be reversible - to be initiated and undone in a continuous cycle to keep up with the cisternal maturation. Microscopic evidence in support of such a reversible nature of stacking, in the form of 'TGN peeling,' has been reported in various species, suggesting a potential evolutionarily conserved mechanism. However, knowledge of such mechanism has remained sketchy. Here, we have explored this issue in the budding yeast Pichia pastoris which harbors stacked Golgi. We observed that deletion of GRIP domain golgin P. pastoris (Pp)IMH1 increases the peeling of late cisterna, causing unstacking of the Golgi stack. Our results suggest that the PpImh1 dimer mediates reversible stacking through a continuous association-dissociation cycle of its GRIP domain to the middle and late Golgi cisterna under the GTP hydrolysis-based regulation of Arl3-Arl1 GTPase cascade switch. The reversible cisternal stacking function of PpImh1 is independent of its vesicle-capturing function. Since GRIP domain proteins are conserved in plants, animals and fungi, it is plausible that this reversible mechanism of Golgi stacking is evolutionarily conserved.This article has an associated First Person interview with the first author of the paper.


Assuntos
Complexo de Golgi/metabolismo , Proteínas da Matriz do Complexo de Golgi/metabolismo , Pichia/metabolismo , Transporte Biológico , Pichia/citologia
6.
J Cell Sci ; 132(20)2019 10 23.
Artigo em Inglês | MEDLINE | ID: mdl-31455607

RESUMO

Chasing an intriguing biological question on the disparity of sodium iodide symporter (NIS, officially known as SLC5A5) expression and function in the clinical scenario of breast cancer, this study addresses key molecular defects involved. NIS in cancer patients has primarily been recorded to be a cytoplasmic protein, thus limiting the scope for targeted radio-iodine therapy. We developed NIS transgene-overexpressing MCF-7 breast cancer cells, and found a few clonal derivatives that show predominant expression of NIS in the plasma membrane. The majority of clones, however, showed cytosolic NIS expression over long passages. Cells expressing membranous NIS show unperturbed dynamic trafficking of NIS through secretory pathway organelles when compared to cells expressing cytoplasmic NIS or to parental cells. Further, treatment of cells expressing membranous NIS with specific glycosylation inhibitors highlighted the importance of inherent glycosylation processing and an 84 gene signature glycosylation RT-Profiler array revealed that clones expressing NIS in their membrane cluster separately compared to the other cells. We further confirm a role of three differentially expressed genes, i.e. MAN1B1, MAN1A1 and MAN2A1, in regulating NIS localization by RNA interference. Thus, this study shows the important role of mannosidase in N-glycosylation processing in order to correctly traffic NIS to the plasma membrane in breast cancer cells.This article has an associated First Person interview with the first author of the paper.


Assuntos
Neoplasias da Mama/metabolismo , Manose/metabolismo , Proteínas de Neoplasias/metabolismo , Simportadores/metabolismo , Neoplasias da Mama/genética , Neoplasias da Mama/patologia , Feminino , Glicosilação , Humanos , Células MCF-7 , Manose/genética , Proteínas de Neoplasias/genética , Transporte Proteico , Simportadores/genética
7.
J Biol Inorg Chem ; 26(4): 411-425, 2021 06.
Artigo em Inglês | MEDLINE | ID: mdl-33928437

RESUMO

The role of the pentapeptide, NHSFM, derived from the surface exposed part of the metal ion binding loop of the subunit II of cytochrome c oxidase on the maturation of the binuclear purple CuA center of the enzyme has been investigated using several experimental and computational methods. The copper ion was found to form 1:1 complex of the pentapeptide with a binding constant ~ 104 M-1 to 105 M-1, where a 4 ligand coordination from the peptide in a type 2 copper center was revealed. The pH dependence of the metal-peptide was associated with a [Formula: see text] of ~ 10 suggesting deprotonation of the N-terminal amine. EXAFS studies as well as DFT calculations of the metal-peptide complexes revealed pH dependent changes in the metal-ligand bond distances. Spectroscopic properties of the metal peptides calculated from TDDFT studies agreed with the experimental results. Restrained molecular dynamics (RMD) simulations indicated coordination of a carbonyl oxygen from the asparagine (N) side chain and of water molecules apart from histidine (H), methionine (M) and terminal amine of asparagine (N) in a distorted square planar geometry of Cu-NHSFM. Analyses of the backbone distances as well as B-factors for the metal peptide suggested that the peptide backbone becomes more compact and rigid on binding of the metal ion. This indicated that binding of copper ion to this pentapeptide in the protein possibly cause movement of the protein backbone bringing other coordinating residues closer to the copper ion, and thus helping in sequential uptake of copper ions to the protein.


Assuntos
Cobre/química , Complexo IV da Cadeia de Transporte de Elétrons/metabolismo , Domínio Catalítico , Cobre/metabolismo , Complexo IV da Cadeia de Transporte de Elétrons/genética , Concentração de Íons de Hidrogênio , Modelos Moleculares , Simulação de Dinâmica Molecular , Conformação Proteica , Subunidades Proteicas
8.
Inorg Chem ; 60(14): 10158-10166, 2021 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-34196540

RESUMO

Uranium- and iron-containing waste simulated effluent has been treated sequentially with a novel resin, viz., polyacrylamide hydroxamic acid (PAAHA). The motivation is to investigate the competitive interactions with transition metals during the removal of radiologically and chemically toxic uranium. The sequential sorption results indicate that the resin is more Fe selective compared to U and it retains more iron. X-ray absorption fine structure measurements, which comprise of both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques, have been carried out on the PAAHA resin at the Fe K-edge and U L3-edge to probe the change in the local coordination environment on sequential sorption of uranium and iron. EXAFS measurements conclude that the U-O distances and coordination are modified when the treatment sequences of U and Fe are interchanged, whereas the Fe local structure remains intact. The results obtained from EXAFS measurements have been verified by detail analysis of XANES data.

9.
Phys Chem Chem Phys ; 23(38): 21769-21783, 2021 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-34549738

RESUMO

A series of disordered Ca1.5La0.5FeRuO6, CaLaFeRuO6 and La2FeRuO6 double perovskites were prepared by the solid-state reaction method and investigated by neutron powder diffraction, X-ray absorption near-edge structure (XANES) analysis at the Ru-K edge, Mössbauer spectroscopy, DC magnetization and resistivity measurements. All compounds crystallize in the orthorhombic crystal structure with the space group Pbnm down to 3 K, showing a random distribution of Fe and Ru at the B site. Thermogravimetric analysis indicates oxygen deficiency in the Ca-rich and formal oxygen hyperstoichiometry in the La-rich members of the present series. While Mössbauer spectra verify the Fe3+ state for all compositions, the XANES study reveals a variable Run+ oxidation state which decreases with increasing La content. The end member actually is a Ru3+/Ru4+ compound with possibly some cation vacancies. From magnetic susceptibility and neutron diffraction measurements, the presence of a G-type antiferromagnetic ordering was observed with a drastic increase in transition temperature from 275 K (Ca1.5La0.5FeRuO6) to 570 K (La2FeRuO6). Mössbauer spectroscopy confirms the presence of long-range ordering but, due to local variations in the exchange interactions, the magnetic states are microscopically inhomogeneous. All the samples are variable range hopping semiconductors. A complex interplay between structural features, charge states, anion or cation defects, and atomic disorder determines the magnetic properties of the present disordered 3d/4d double perovskite series.

10.
J Fluoresc ; 30(3): 703-715, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32385659

RESUMO

mEos3.2 is a photoconvertible fluorescence protein with comparatively low brightness, which limits its application in live Super resolution microscopy. To address this issue, we have used semi-rational protein engineering to develop mEosBrite, a new class of improved brightness variants. The improvement in the brightness was confirmed by expression in E.coli as well as mammalian cell lines. Furthermore, biophysical characterization suggests that all the three mEosBrite variant proteins display higher quantum yield, truly monomeric form, less cytotoxicity and lower protein aggregation as compared to the wild type mEos3.2 protein. Most importantly, because of their high photoconversion efficiency mEosBrite variants could be an excellent tool for single-molecule and intensity fluctuation based super-resolution microscopy.


Assuntos
Proteínas Luminescentes/química , Engenharia de Proteínas , Escherichia coli/metabolismo , Células HeLa , Humanos , Proteínas Luminescentes/genética , Microscopia de Fluorescência , Modelos Moleculares , Imagem Óptica
11.
Inorg Chem ; 58(5): 3073-3089, 2019 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-30789252

RESUMO

Pristine and Eu3+-doped BaZrO3 were synthesized via a solid-state reaction method, and the synthesized samples were systematically characterized. X-ray diffraction confirmed the formation of single and pure phases of cubic-structured BaZrO3. Extended X-ray absorption fine structure (EXAFS) spectroscopy revealed the site occupancy of Eu3+ and coordination environment around the different atomic sites. Photoluminescence (PL) excitation and emission spectra revealed the dominant absorption at 275 nm and a broad emission centered at 400 nm due to oxygen vacancies below the conduction band (CB). The PL emission intensity at 597 nm increased with increasing Eu3+ doping concentration; simultaneously, emission from the defect level decreased. This confirmed the efficient energy transfer from oxygen vacancies to Eu3+. Density functional theory was employed to calculate the density of states (DOS) to explain the mechanisms of the PL phenomenon. DOS also showed the presence of impurity states due to Eu3+ doping within the band-gap region. The coincidence of the oxygen vacancy state with Eu f state at the bottom of the CB confirmed the PL energy-transfer mechanisms from the oxygen vacancy to europium. The excited-state lifetime values of the 5D0 state decreased with increasing doping concentration due to the increase of the nonradiative transition rate. The internal quantum efficiency, small excited-state lifetime, and photometric parameters indicated that 3 mol % Eu3+-doped BaZrO3 can be a suitable candidate for the red-light-emitting device applications.

12.
Eur Phys J E Soft Matter ; 42(12): 154, 2019 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-31834534

RESUMO

Regulation of organelle size and shape is a poorly understood but fascinating subject. Several theoretical studies were reported on Golgi size regulation, but a combination of experimental and theoretical approaches is rare. In combination with the quantitative microscopy and a coarse-grained simulation model, we have developed a technique to gain insights into the functions of potential regulators of Golgi size in budding yeast Saccharomyces cerevisiae. To validate our method, we tested wild-type and arf1[Formula: see text] strain harboring early and late Golgi cisternae labeled with green and red fluorescent fusions. Our concentration-dependent maturation model prediction concurs with most of the experimental results for both wild-type and arf1[Formula: see text] strains. Decisive match of simulation and experimental data provide insight into such specific factor's function in regulating the Golgi size. Details of the complex multifactorial network of Golgi size regulation can be deciphered in the future using a similar combination of quantitative microscopy and in silico model.


Assuntos
Fator 1 de Ribosilação do ADP/metabolismo , Simulação por Computador , Complexo de Golgi/metabolismo , Microscopia , Modelos Biológicos , Tamanho das Organelas , Saccharomyces cerevisiae/citologia
13.
Yeast ; 35(8): 499-506, 2018 08.
Artigo em Inglês | MEDLINE | ID: mdl-29707810

RESUMO

Budding yeast Pichia pastoris has highly advanced secretory pathways resembling mammalian systems, an advantage that makes it a suitable model system to study vesicular trafficking. Golgins are large Golgi-resident proteins, primarily reported to play role in cargo vesicle capture, but details of such mechanisms are yet to be deciphered. Golgins that localize to the Golgi via their GRIP domain, a C-terminal Golgi anchoring domain, are known as GRIP domain Golgins. In this present study, we have identified and functionally characterized a homologue of one such GRIP domain Golgin protein, Imh1, from the budding yeast P. pastoris. We have demonstrated that the GRIP domain present at the C-terminal of P. pastoris Imh1 (PpImh1) functions as its Golgi-targeting sequence. Using a combination of yeast two-hybrid analysis, dynamic light scattering and electron microscopy, we have shown that PpImh1 can self-associate and form a homodimer. Analysis of purified recombinant PpImh1 by CD spectroscopy indicates the presence of an 85% α-helical structure, a characteristic of high-content α-helical coiled-coil sequences normally present in other Golgin family proteins. Two-hybrid analysis indicated self-interaction between C-terminal fragments, yet N-terminal fragments do not mediate any such form of self-interaction, suggesting that PpImh1 may form a parallel dimer. Electron microscopy data indicates that PpImh1 forms extended rod-like homo-dimeric molecules with splayed N-terminal end which can act as a tether for capturing vesicles. Our study provides the first evidence in support of the dimeric Y-shaped structure for any Golgin in the budding yeast.


Assuntos
Proteínas Fúngicas/química , Proteínas Fúngicas/metabolismo , Pichia/genética , Pichia/metabolismo , Proteínas de Transporte Vesicular/química , Proteínas de Transporte Vesicular/metabolismo , Sequência de Aminoácidos , Dimerização , Proteínas Fúngicas/genética , Complexo de Golgi/genética , Complexo de Golgi/metabolismo , Microscopia Eletrônica , Ligação Proteica , Conformação Proteica , Proteínas Recombinantes de Fusão/química , Proteínas Recombinantes de Fusão/genética , Proteínas Recombinantes de Fusão/metabolismo , Alinhamento de Sequência , Técnicas do Sistema de Duplo-Híbrido , Proteínas de Transporte Vesicular/genética
14.
Inorg Chem ; 57(7): 3963-3982, 2018 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-29546987

RESUMO

Activator-free zinc aluminate (ZA) nanophosphor was synthesized through a sol-gel combustion route, which can be used both as a blue-emitting phosphor material and a white-emitting phosphor material, depending on the annealing temperature during synthesis. The material also has the potential to be used in optical thermometry. These fascinating color-tunable emission characteristics can be linked with the various defect centers present inside the matrix and their changes upon thermal annealing. Various defect centers, such as anionic vacancy, cationic vacancy, antisite defect, etc., create different electronic states inside the band gap, which are responsible for the multicolor emission. The color components are isolated from the complex emission spectra using time-resolved emission spectroscopy (TRES) study. Interestingly, the lifetime values of the various defect centers were found to change significantly from milliseconds to microseconds upon thermal annealing, which makes the phosphors more diverse (i.e., either long-persistent blue-emitting phosphors or short-persistent white-emitting phosphors). Fourier transform infrared (FTIR) and diffuse reflectance spectroscopy (DRS) confirmed the presence of antisite defect centers such as AlZn+ or ZnAl- in the matrix. X-ray absorption fine structure (EXAFS) study showed that the spinel structure was more disordered in nature for low-temperature-annealed compounds. Electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) studies were also carried out in order to characterize various anionic and cationic vacancies and their clusters present in the compounds. Antisite defect centers such as AlZn+ or ZnAl-, which act as an electron or hole trap, were found to be responsible for the diverse lifetime behavior. To gain insight about the electronic states inside the band gap, density functional theory (DFT)-based calculations were performed for both pure and various vacancy-introduced spinel structures. Finally, based on the theoretical and experimental results, for the first time, a detailed investigation of various defect-induced emission behavior in ZA is presented, which also explains the mechanism of color tunability and dynamic lifetimes.

15.
Inorg Chem ; 57(2): 821-832, 2018 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-29292994

RESUMO

Studies have been carried out to understand the specific role of the alkali charge compensator on the luminescence properties of an alkali ion (Li+, Na+, and K+) codoped SrWO4:Eu phosphor. The oxidation state of the europium ion was found to be +3 on the basis of X-ray absorption near edge structure (XANES) measurements. This is the first report of its kind where opposite effects of Li+ ion and Na+/K+ ions on photoluminescence intensity have been observed. Li+ ion codoping enhanced the photoluminescence intensity from SrWO4:Eu3+ phosphor while Na+/K+ ion codoping did not. On the other hand, the luminescence lifetime is maximum for the Na+ ion codoped sample and minimum for the Li+ ion codoped sample. The results could be explained successfully using time-resolved luminescence, positron annihilation lifetime spectroscopy (PALS), and extended X-ray absorption fine structure (EXAFS) spectroscopy measurements. Changes in the Eu-O bond length and Debye-Waller Factor (σ2) upon Li+/Na+/K+ codoping were monitored through EXAFS measurements. PALS also highlighted the fact that Li+ codoping is not contributing to reduction in the cation vacancies and might be occupying interstitial sites rather than lattice positions due to its very small size. On europium doping there is lowering in symmetry of SrO8 polyhedra from S4 to C6, which is reflected in an intense electric dipole transition in comparison to the magnetic dipole transition. This is also corroborated using trends in Judd-Ofelt parameters. The results have shown that the luminescence lifetime is better when the vacancy concentration is lower as induced by Na+ and K+ codoping, while the emission intensity is higher in the samples when distortion around Eu3+ is reduced as induced by Li+ codoping.

16.
Inorg Chem ; 57(20): 12987-12998, 2018 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-30256631

RESUMO

A novel tripodal diglycolamide ligand containing a triazamacrocycle center (2,2',2''-(((1,4,7-triazonane-1,4,7-triyl)tris(2-oxoethane-2,1-diyl)) tris(oxy)) tris( N, N-dioctylacetamide), abbreviated as T9C3ODGA) was synthesized and characterized by conventional techniques. The ligand resulted in efficient extraction of actinide/lanthanide ions yielding the trend: Eu3+ > Pu4+ > Am3+ > NpO22+ > UO22+ > Sr2+ > Cs+. Similar to most of the other diglycolamide (DGA) ligands, Eu3+ was preferentially extracted as compared to Am3+; the separation factor ( DEu/ DAm) value at 3 M HNO3 was ca. 4.2. In contrast, separation from UO22+ ion was less effective as compared to that of other tripodal DGA ligands studied earlier. Solvent extraction studies indicated extraction of species of the ML2 (where L is T9C3ODGA) stoichiometry. The formation of an inclusion complex with no inner-sphere water molecule was confirmed from luminescence spectral studies. DFT computations predicted the presence of an inner-sphere nitrate ion in the most preferred complex, which was also supplemented by EXAFS and luminescence studies. The selectivity of T9C3ODGA could be explained on the basis of its more favorable interactions with Eu3+ as compared to those with Am3+ both in the gas and the solution phases.

17.
Inorg Chem ; 57(12): 6973-6980, 2018 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-29877695

RESUMO

Negative thermal expansion material TaVO5 is recently reported to have pressure induced structural phase transition and irreversible amorphization at 0.2 and above 8 GPa, respectively. Here, we have investigated the high pressure phase of TaVO5 using in situ neutron diffraction studies. The first high pressure phase is identified to be monoclinic P21/ c phase, same as the low temperature phase of TaVO5. On heating, amorphous TaVO5 transformed to a new crystalline phase, which showed signatures of higher coordination of vanadium indicating pressure induced amorphization (PIA). PIA observed in TaVO5 might be due to the kinetic hindrance of pressure induced decomposition (PID) into a compound with higher coordination of vanadium. Mechanism of PIA observed in TaVO5 is investigated by carrying out ex situ Raman, XRD, XPS, and XAS measurements. We have also proposed a pressure-temperature phase diagram of TaVO5 qualitatively delineating the phase boundaries between the ambient orthorhombic, monoclinic, and amorphous phases.

18.
Inorg Chem ; 56(1): 167-178, 2017 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-27966936

RESUMO

Considering the fact that pyrophosphate-based hosts are in high demand for making highly efficient luminescence materials, we doped two visible lanthanide ions, viz. Sm3+ and Eu3+, in Zn2P2O7. Interestingly, it was oberved that pure Zn2P2O7 displayed blue-green dual emission on irradiation with ultraviolet light. Emission and lifetime spectroscopy shows the presence of defects in pyrophosphate samples which are responsible for such emission. DFT calculations clearly pinpointed that the electronic transitions between defect states located at just below the conduction band minimum (arises due to VO1+ and VO2+ defects) and valence band maximum, as well as impurity states situated in the band gap, can lead to dual emission in the blue-green region, as is also indicated by emission and lifetime spectra. X-ray absorption near edge spectroscopy (XANES) shows the stabilization of europium as well as samarium ion in the +3 oxidation state in α-Zn2P2O7. The fact that α-Zn2P2O7 has two different coordination numbers for zinc ions, i.e. five- and six-coordinate, the study of dopant ion distribution in this particular matrix will be an important step in realizing a highly efficient europium- and samarium-based red-emitting phosphor. Time resolved photoluminescence (TRPL) shows that both of these ions are heterogeneously distributed between five- and six-coordinated Zn2+ sites and it is the six-coordinated Zn2+ site which is the most favorable for lanthanide ion doping. Extended X-ray absorption fine structure (EXAFS) measurements also suggested that a six-coordinated zinc ion is the preferred site occupied by trivalent lanthanide ions, which is in complete agreement with TRPL results. It was observed that there is almost complete transfer of photon energy from Zn2P2O7 to Eu3+, whereas this transfer is inefficient and almost incomplete in case of Sm3+, which is indeed important information for the realization of pyrophosphate-based tunable phosphors.

19.
Appl Opt ; 56(27): 7525-7532, 2017 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-29047727

RESUMO

The DC magnetron sputter grown Co/Ti multilayers, with ultra-low bi-layer thicknesses and with Co layers deposited under mixed ambience of argon and dry air, have been investigated for use in the water window soft x-ray regime of 23-44 Å. Initially, deposition parameters have been optimized for obtaining smooth and continuous low thickness Co and Ti single-layer films, and, then, multilayers with five bi-layers of various bi-layer thicknesses were deposited. The samples have been primarily characterized by the grazing incidence x-ray reflectivity (GIXR) measurements with a hard x-ray laboratory source. Subsequently, a set of multilayers with an increasing number of bi-layers has been deposited with a constant bi-layer thickness of 42 Å. GIXR results show that hard x-ray reflectivity at the first Bragg peak is maximum for the 20 bi-layer sample, beyond which the reflectivity decreases. Finally, the samples with the most promising hard x-ray GIXR have been used for soft x-ray reflectivity measurement with synchrotron radiation, and ∼2.5% peak reflectivity has been obtained in the multilayer sample at a 30.7 Å wavelength for a 21.5° grazing angle of incidence. The fitting results for both hard and soft x-ray reflectivities have been thoroughly investigated to find out the cause of the saturation of reflectivity with the increase in the number of bi-layers.

20.
Appl Opt ; 56(22): 6114-6125, 2017 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-29047804

RESUMO

Gadolinium oxide is an excellent optical material that offers high transmission in a wide wavelength range of 200-1600 nm and exhibits a high bulk refractive index of ∼1.80 at 550 nm. In the present study, a set of Gd2O3 thin films has been deposited on fused silica substrates by RF sputtering of a Gd2O3 target under various O2 to Ar flow ratios. The samples have been characterized by grazing incidence x-ray diffraction (GIXRD) to study the long range structural behavior, by GIXR to study density and surface roughness of the films, by atomic force microscopy measurements to study morphological properties, by Rutherford backscattering measurements for compositional studies, and by transmission spectrophotometry and spectroscopic ellipsometry techniques to study their optical properties. It has been observed that the films deposited with 10% oxygen partial pressure have low density, high surface roughness, and high void content, which results in a low value of refractive index of this film, and film quality improves as oxygen partial pressure is further increased. Extended x-ray absorption fine structure measurement with synchrotron radiation has also been employed to extract local structural information around Gd sites, which has in turn been used to explain some of the observed macroscopic properties of the films.

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