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1.
Inorg Chem ; 63(26): 12042-12053, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38946343

RESUMO

The first fully inorganic Pt(IV) carbonato-complex trans-[Pt(CO3)2(OH)2]2- with a {PtO6} coordination sphere was isolated as the (Me4N)2[Pt(CO3)2(OH)2] (1) salt. The compound 1 was characterized using single-crystal and powder X-ray diffraction, Raman spectroscopy, infrared spectroscopy (FTIR), electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance spectroscopy (NMR), and thermogravimetric analysis (TG). Density functional theory (DFT) calculations were also performed to analyze the spectral features of the complex. 1 crystallizes in the triclinic system (P-1) with a Z of 1. The trans-[Pt(CO3)2(OH)2]2- anion has axial hydroxo ligands and κ2-CO3 ligands, which form an equatorial plane. This anionic complex exhibits notable stability in aqueous solutions, while the axial hydroxo ligand can be readily modified, as exemplified by the acylation of the trans-[Pt(CO3)2(OH)2]2- into trans-[Pt(CO3)2(OAc)2]2- anion. Furthermore, it has been shown that rigid and glittering platinum coatings can be electrochemically deposited from an aqueous solution of 1 without the addition of surfactants.

2.
Inorg Chem ; 62(24): 9732-9748, 2023 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-37291758

RESUMO

A combination of multinuclear nuclear magnetic resonance spectroscopy and theoretical calculation based on density functional theory was used for a speciation study of Pt in solutions prepared either by the interaction of [Pt(OH)6]2- with gaseous CO2 in an alkaline solution of platinum(IV) hydroxide ([Pt(OH)4(H2O)2]) or by the dissolution of [Pt(OH)4(H2O)2] in an aqueous KHCO3 solution. The formed solutions contained coexisting Pt(IV) carbonato complexes with κ1- and κ2-coordination modes. The gradual condensation of mononuclear Pt species in such bicarbonate solutions resulted in the formation of PtO2 nanoparticles aggregating into a solid precipitate on prolonged aging. The deposition of PtO2 particles from bicarbonate solutions was adapted for the preparation of Pt-containing heterogeneous catalysts: bimetallic Pt-Ni catalysts were prepared using various supporting materials (CeO2, SiO2, and g-C3N4) and tested for the activity in hydrazine-hydrate decomposition. All prepared materials showed high selectivity with respect to H2 production from the hydrazine-hydrate with PtNi/CeO2 showing the highest rate of H2 evolution. In the long-range evaluation, the PtNi/CeO2 catalyst operating at 50 °C showed an exceptional turnover number value of 4600 producing hydrogen at a 97% selectivity level and with a mean turnover frequency value of about 470 h-1. In the case of the PtNi/g-C3N4 catalyst, for the first time, the photodriven decomposition of hydrazine-hydrate was shown to enhance the productivity of the catalyst by 40%.

3.
Inorg Chem ; 62(31): 12203-12212, 2023 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-37487202

RESUMO

The MSb2 compounds with M = Cr, Fe, Ru, and Os have been investigated under high pressures by synchrotron powder X-ray diffraction. All compounds, except CrSb2, were found to retain the marcasite structure up to the highest pressures (more than 50 GPa). In contrast, we found that CrSb2 has a structural phase transition around 10 GPa to a metastable, MoP2-type structure with Cr coordinated to seven Sb atoms. In addition, we compared ambient temperature compression with laser-heating experiments and found that laser-heating at pressures below and above this phase transition results in the known CuAl2-type structure. Density functional theory calculations show that this tetragonal structure is the most stable in the whole pressure interval. However, a crossing of the marcasite's and MoP2-like structure's enthalpies occurs between 5 and 7.5 GPa, which is in good agreement with the experimental data. The phase transition to the MoP2-type structure observed in this work opens up for discovering other compounds with this new transition pathway from the marcasite structure.

4.
J Chem Phys ; 159(6)2023 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-37551808

RESUMO

We employed high-pressure Brillouin scattering to study the pressure dependencies of acoustic modes of glycerol up to 14 GPa at 300 K. We observed longitudinal acoustic velocities and transverse acoustic velocities for the first time from 5 to 14 GPa. The results allow the determination of a complete set of elastic properties and an accurate determination of the pressure-volume (P-V) equation of state (EOS). EOS parameters, K0 = 14.9 ± 1.8 GPa and K'0 = 5.6 ± 0.5, were determined from fits to the data from ambient pressure to 14 GPa. Direct volume measurements of the P-V EOS are consistent with those determined by Brillouin scattering. A deviation from a Cauchy-like relationship for elastic properties was observed, and the pressure dependencies of the photoelastic constants and relaxation times were documented from 5 to 14 GPa. These results have broad implications for glass-forming liquids, viscoelastic theory, and mode coupling theory.

5.
Proc Natl Acad Sci U S A ; 117(18): 9747-9754, 2020 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-32312811

RESUMO

Sub-Neptunes are common among the discovered exoplanets. However, lack of knowledge on the state of matter in [Formula: see text]O-rich setting at high pressures and temperatures ([Formula: see text]) places important limitations on our understanding of this planet type. We have conducted experiments for reactions between [Formula: see text] and [Formula: see text]O as archetypal materials for rock and ice, respectively, at high [Formula: see text] We found anomalously expanded volumes of dense silica (up to 4%) recovered from hydrothermal synthesis above ∼24 GPa where the [Formula: see text]-type (Ct) structure appears at lower pressures than in the anhydrous system. Infrared spectroscopy identified strong OH modes from the dense silica samples. Both previous experiments and our density functional theory calculations support up to 0.48 hydrogen atoms per formula unit of ([Formula: see text])[Formula: see text] At pressures above 60 GPa, [Formula: see text]O further changes the structural behavior of silica, stabilizing a niccolite-type structure, which is unquenchable. From unit-cell volume and phase equilibrium considerations, we infer that the niccolite-type phase may contain H with an amount at least comparable with or higher than that of the Ct phase. Our results suggest that the phases containing both hydrogen and lithophile elements could be the dominant materials in the interiors of water-rich planets. Even for fully layered cases, the large mutual solubility could make the boundary between rock and ice layers fuzzy. Therefore, the physical properties of the new phases that we report here would be important for understanding dynamics, geochemical cycle, and dynamo generation in water-rich planets.

6.
Mol Phylogenet Evol ; 169: 107411, 2022 04.
Artigo em Inglês | MEDLINE | ID: mdl-35032647

RESUMO

The tick-borne flavivirus (TBFV) group contains at least 12 members where five of them are important pathogens of humans inducing diseases with varying severity (from mild fever forms to acute encephalitis). The taxonomy structure of TBFV is not fully clarified at present. In particular, there is a number of paraphyletic issues of tick-borne encephalitis virus (TBEV) and louping-ill virus (LIV). In this study, we aimed to apply different bioinformatic approaches to analyze all available complete genome amino acid sequences to delineate TBFV members at the species level. Results showed that the European subtype of TBEV (TBEV-E) is a distinct species unit. LIV, in turn, should be separated into two species. Additional analysis of TBEV and LIV antigenic determinant diversity also demonstrate that TBEV-E and LIV are significantly different both from each other and from the other TBEV subtypes. The analysis of available literature provided data on other virus phenotypic particularities that supported our hypothesis. So, within the TBEV + LIV paraphyletic group, we offer to assign four species to get a more accurate understanding of the TBFV interspecies structure according to the modern monophyletic conception.


Assuntos
Vírus da Encefalite Transmitidos por Carrapatos , Encefalite Transmitida por Carrapatos , Carrapatos , Animais , Vírus da Encefalite Transmitidos por Carrapatos/genética , Epitopos , Humanos , Filogenia
7.
Inorg Chem ; 61(15): 5926-5942, 2022 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-35380806

RESUMO

The transformations of Pt complex species in concentrated NaOH solutions (1-12 M) of Na2[PtCl6] were studied with a combination of methods, including 195Pt nuclear magnetic resonance, ultraviolet-visible, and Raman spectroscopy. The two-step process was observed under the following conditions: (1) formation of the [Pt(OH)5Cl]2- anion that proceeds relatively fast even at room temperature and (2) further slow substitution of the last chlorido ligand with the formation of the [Pt(OH)6]2- anion. Overall, it was determined that the [PtCl6]2- to [Pt(OH)6]2- transformation (especially the first stage) is greatly accelerated under blue light (455 nm) irradiation. The structures of [Pt(OH)Cl5]2- and [Pt(OH)5Cl]2- were determined using the single-crystal X-ray diffraction data of the corresponding salts isolated for the first time. Analysis of the [Pt(OH)Cl5]2- reactivity showed that under analogous conditions, its hydrolysis proceeds 2 orders of magnitude slower than that of [PtCl6]2-, indicating that the formation of [Pt(OH)5Cl]2- from [PtCl6]2- (stage 1) does not follow a simple sequential substitution pattern. A model for [Pt(OH)5Cl]2- anion formation that includes the competing reaction of direct Cl ligand substitution and the self-catalyzed second-order reaction caused by a redox process is proposed. The influence of Pt speciation in alkaline solutions on the reductive behavior is shown, illustrating its impact on the preparation of Pt nanoparticles.

8.
Inorg Chem ; 61(25): 9667-9684, 2022 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-35700060

RESUMO

The systematic study of the platinum speciation in sulfuric acid solutions of platinum (IV) hydroxide {[Pt(OH)4(H2O)2], HHPA} was performed with the use of a combination of methods. Depending on the prevailing Pt form, the three regions of H2SO4 concentration were marked: (1) up to 3 M H2SO4 forms unstable solutions gradually generating the PtO2·xH2O particles; (2) 4-12 M H2SO4, where the series of mononuclear aqua-sulfato complexes ([Pt(SO4)n(H2O)6-n]4-2n, where n = 0···4) dominate; and (3) 12 M and above, where, along with [Pt(SO4)n(H2O)6-n]4-2n species, the polynuclear Pt(IV) species and complexes with a bidentate coordination mode of the sulfato ligand are formed. For the first time, the salts of the aqua-hydroxo Pt(IV) cation [Pt(OH)2(H2O)4]SO4 (triclinic and monoclinic phases) were isolated and studied with a combination of methods, including the single-crystal X-ray diffraction. The formation of PtO2·xH2O particles in sulfuric acid solutions (1-3 M) of HHPA and their spectral characteristics and morphology were studied. The deposition of PtO2·xH2O was highlighted as a convenient method to prepare various Pt-containing heterogeneous catalysts. This possibility was illustrated by the preparation of Pt/g-C3N4 catalysts, which show an excellent performance in catalytic H2 generation under visible light irradiation with a quantum efficiency up to 5% and a rate of H2 evolution up to 6.2 mol·h-1 per gram of loaded platinum.

9.
Int J Mol Sci ; 23(21)2022 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-36361635

RESUMO

Castration-resistant prostate cancer (CRPC) is a common form of prostate cancer in which docetaxel-based chemotherapy is used as the first line. The present study is devoted to the analysis of transcriptome profiles of tumor cells in the development of resistance to docetaxel as well as to the assessment of the combined effect with the XAV939 tankyrase inhibitor on maintaining the sensitivity of tumor cells to chemotherapy. RNA-Seq was performed for experimental PC3 cell lines as well as for plasma exosome samples from patients with CRPC. We have identified key biological processes and identified a signature based on the expression of 17 mRNA isoforms associated with the development of docetaxel resistance in PC3 cells. Transcripts were found in exosome samples, the increased expression of which was associated with the onset of progression of CRPC during therapy. The suppression of pathways associated with the participation of cellular microtubules has also been shown when cells are treated with docetaxel in the presence of XAV939. These results highlight the importance of further research into XAV939 as a therapeutic agent in the treatment of CRPC; moreover, we have proposed a number of mRNA isoforms with high predictive potential, which can be considered as promising markers of response to docetaxel.


Assuntos
Antineoplásicos , Neoplasias de Próstata Resistentes à Castração , Masculino , Humanos , Docetaxel/farmacologia , Docetaxel/uso terapêutico , Neoplasias de Próstata Resistentes à Castração/tratamento farmacológico , Neoplasias de Próstata Resistentes à Castração/genética , Neoplasias de Próstata Resistentes à Castração/metabolismo , Transcriptoma , beta Catenina/metabolismo , Isoformas de RNA , Resistencia a Medicamentos Antineoplásicos/genética , Linhagem Celular Tumoral , Antineoplásicos/farmacologia , Antineoplásicos/uso terapêutico
10.
Exp Eye Res ; 203: 108394, 2021 02.
Artigo em Inglês | MEDLINE | ID: mdl-33310058

RESUMO

Micro-CT visualization allows reconstruction of eye structures with the resolution of light microscopy and estimation of tissue densities. Moreover, this method excludes damaging procedures and allows further histological staining due to the similar steps in the beginning. We have shown the feasibility of the lab-based micro-CT machine usage for visualization of clinically important compartments of human eye such as trabecular outflow pathway, retina, iris and ciliary body after pre-treatment with iodine in ethanol. We also identified the challenges of applying this contrasting technique to lens, cornea, and retina and proposed alternative staining methods for these tissues. Thereby this work provides a starting point for other studies for imaging of human eyes in normal and pathological conditions using lab-based micro-CT systems.


Assuntos
Enucleação Ocular , Olho/anatomia & histologia , Olho/diagnóstico por imagem , Microtomografia por Raio-X , Câmara Anterior/anatomia & histologia , Câmara Anterior/diagnóstico por imagem , Segmento Anterior do Olho/anatomia & histologia , Segmento Anterior do Olho/diagnóstico por imagem , Estudos de Viabilidade , Humanos , Imageamento Tridimensional , Cristalino/anatomia & histologia , Cristalino/diagnóstico por imagem , Retina/anatomia & histologia , Retina/diagnóstico por imagem
11.
Inorg Chem ; 58(9): 6075-6087, 2019 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-30951300

RESUMO

A series of tetraalkylammonium salts with anionic platinum nitrato complexes (Me4N)2[Pt2(µ-OH)2(NO3)8] (1), (Et4N)2[Pt2(µ-OH)2(NO3)8] (2), ( n-Pr4N)2[Pt2(µ-OH)2(NO3)8] (3b), ( n-Pr4N)2[Pt(NO3)6] (3a), and ( n-Bu4N)2[Pt(NO3)6] (4) were isolated from nitric acid solutions of [Pt(H2O)2(OH)4] in high yield. The structures of salts 2, 3a, 3b, and 4, prepared for the first time, were characterized by X-ray diffraction. The sorption of [Pt(NO3)6]2- and [Pt2(µ-OH)2(NO3)8]2- complexes onto the ceria surface from acetone solutions of salts 4 and 1 was examined. The dimeric anion was shown to quickly and irreversibly chemisorb onto the CeO2 carrier, selectively transforming into Pt(II) centers after thermal treatment, becoming active in the low-temperature CO oxidation reaction ( T50% = 110 °C at a space velocity of 240 000 h-1). By contrast, the homoleptic complex [Pt(NO3)6]2- did not interact with the ceria, which may be attributed to the substitutional inertness of the [Pt(NO3)6]2- anion. We believe that the strategy based on the sorption of polynuclear platinum nitrato complexes is an effective route to prepare ionic platinum species uniformly distributed on an oxide carrier for various catalytic applications.

12.
Inorg Chem ; 57(4): 2269-2277, 2018 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-29420026

RESUMO

The structural evolution of lanthanide A2TiO5 (A = Dy, Gd, Yb, Er) at high pressure is investigated using synchrotron X-ray diffraction. The effects of A-site cation size and of the initial structure are systematically examined by varying the composition of the isostructural lanthanide titanates and the structure of dysprosium titanate polymorphs (orthorhombic, hexagonal, and cubic), respectively. All samples undergo irreversible high-pressure phase transformations, but with different onset pressures depending on the initial structure. While each individual phase exhibits different phase transformation histories, all samples commonly experience a sluggish transformation to a defect cotunnite-like (Pnma) phase for a certain pressure range. Orthorhombic Dy2TiO5 and Gd2TiO5 form P21am at pressures below 9 GPa and Pnma above 13 GPa. Pyrochlore-type Dy2TiO5 and Er2TiO5 as well as defect-fluorite-type Yb2TiO5 form Pnma at ∼21 GPa, followed by Im3̅m. Hexagonal Dy2TiO5 forms Pnma directly, although a small amount of remnants of hexagonal Dy2TiO5 is observed even at the highest pressure (∼55 GPa) reached, indicating kinetic limitations in the hexagonal Dy2TiO5 phase transformations at high pressure. Decompression of these materials leads to different metastable phases. Most interestingly, a high-pressure cubic X-type phase (Im3̅m) is confirmed using high-resolution transmission electron microscopy on recovered pyrochlore-type Er2TiO5. The kinetic constraints on this metastable phase yield a mixture of both the X-type phase and amorphous domains upon pressure release. This is the first observation of an X-type phase for an A2BO5 composition at high pressure.

13.
Phys Chem Chem Phys ; 20(9): 6187-6197, 2018 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-29431823

RESUMO

The effects of swift heavy ion irradiation-induced disordering on the behavior of lanthanide zirconate compounds (Ln2Zr2O7 where Ln = Sm, Er, or Nd) at high pressures are investigated. After irradiation with 2.2 GeV 197Au ions, the initial ordered pyrochlore structure (Fd3[combining macron]m) transformed to a defect-fluorite structure (Fm3[combining macron]m) in Sm2Zr2O7 and Nd2Zr2O7. For irradiated Er2Zr2O7, which has a defect-fluorite structure, ion irradiation induces local disordering by introducing Frenkel defects despite retention of the initial structure. When subjected to high pressures (>29 GPa) in the absence of irradiation, all of these compounds transform to a cotunnite-like (Pnma) phase, followed by sluggish amorphization with further compression. However, if these compounds are irradiated prior to compression, the high pressure cotunnite-like phase is not formed. Rather, they transform directly from their post-irradiation defect-fluorite structure to an amorphous structure upon compression (>25 GPa). Defects and disordering induced by swift heavy ion irradiation alter the transformation pathways by raising the energetic barriers for the transformation to the high pressure cotunnite-like phase, rendering it inaccessible. As a result, the high pressure stability field of the amorphous phase is expanded to lower pressures when irradiation is coupled with compression. The responses of materials in the lanthanide zirconate system to irradiation and compression, both individually and in tandem, are strongly influenced by the specific lanthanide composition, which governs the defect energetics at extreme conditions.

14.
J Am Chem Soc ; 137(2): 742-9, 2015 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-25531438

RESUMO

Three families of ZnTe magic-sized nanoclusters (MSNCs) were obtained exclusively using polytellurides as a tellurium precursor in a one-pot reaction by simply varying the reaction temperature and time only. Different ZnTe MSNCs exhibit different self-assembling or aggregation behavior, owing to their different structure, cluster size, and dipole-dipole interactions. The smallest family of ZnTe MSNCs (F323) does not reveal a crystalline structure and as a result assembles into lamellar triangle plates. Continuous heating of as synthesized ZnTe F323 assemblies resulted in the formation of ZnTe F398 MSNCs with wurzite structure and concomitant transformation into lamellar rectangle assemblies with the organization of nanoclusters along the ⟨002⟩ direction. Further annealing of ZnTe F398 assembled lamellar rectangles leads to full organization of MSNCs in all directions and formation of larger ZnTe F444 NCs that spontaneously form ultrathin nanowires following an oriented attachment mechanism. The key step in control over the size distribution of ZnTe ultrathin nanowires is, in fact, the growth mechanism of ZnTe F398 MSNCs; namely, the step growth mechanism enables formation of more uniform nanowires compared to those obtained by continuous growth mechanism. High yield of ZnTe nanowires is achieved as a result of the wurzite structure of F398 precursor. Transient absorption (TA) measurements show that all three families possess ultrafast dynamics of photogenerated electrons, despite their different crystalline structures.

15.
Inorg Chem ; 54(10): 4644-51, 2015 May 18.
Artigo em Inglês | MEDLINE | ID: mdl-25910218

RESUMO

For the first time the polynuclear hydroxido-bridged platinum(IV) nitrato complexes with nuclearity higher than two were isolated from nitric acid solutions of [Pt(H2O)2(OH)4] and crystallized as supramolecular compounds of macrocyclic cavitands cucurbit[n]uril (CB[n], n = 6,8) and 18-crown-6 ether: [Pt4(µ3-OH)2(µ2-OH)4(NO3)10]·CB[6]·25H2O (I), [Pt6(µ3-OH)4(µ2-OH)6(NO3)12](NO3)2·CB[8]·50H2O (II), and [H3O⊂18-crown-6]2[Pt2(µ2-OH)2(NO3)8][Pt4(µ3-OH)2(µ2-OH)4(NO3)10] (III). The isolation of the compounds in the single crystalline state allows the determination of the structure of the tetranuclear and hexanuclear complexes [Pt4(µ3-OH)2(µ2-OH)4(NO3)10] and [Pt6(µ3-OH)4(µ2-OH)6(NO3)12](2+), which have been previously unknown in the solid state. Stability of Ptx(OH)y cores of the polynuclear nitrato complexes toward alkaline hydrolysis was verified by (195)Pt NMR spectroscopy. Analysis of (195)Pt NMR spectra of the compound III reveals that addition of every Pt(µ-OH)2Pt ring results in ∼260 ppm downfield shift relative to the mononuclear form, which allows the prediction of signal positions for complexes of higher nuclearity.

16.
Phys Rev E ; 110(2-1): 024501, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-39294967

RESUMO

Amber is a unique example of a fragile glass that has been extensively aged below its glass transition temperature, thus reaching a state that is not accessible under normal experimental conditions. We studied the medium-range order of Baltic amber by x-ray diffraction (XRD) at high pressures. The pressure dependences of the low-angle XRD intensity between 0 and 5 Å^{-1} were measured from 0 to 7.3 GPa by the energy-dispersive XRD. The first diffraction peak at 1.1 Å^{-1} and ambient pressure has a doublet structure consisting of the first sharp diffraction peak (FSDP) at 1.05 Å^{-1} and the second feature at 1.40 Å^{-1}. The peak position and the width of the FSDP increase as the pressure increases, while the intensity of the FSDP decreases. Below P_{0}=2.4 GPa, the rapid increase of the FSDP peak position was observed, while above P_{0}, the gradual increase was observed. Below P_{0}, voids and holes in a relatively low-density state are suppressed, whereas above P_{0}, the suppression becomes mild. Such a change suggests the crossover from the low- to high-density state at P_{0}. There is a close correlation between the pressure dependence of XRD and previously reported sound velocity results. The correlation between the mean-square fluctuation of the shear modulus on the nanometer scale and fragility in amber and other glass formers is also discussed.

17.
Cells ; 13(15)2024 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-39120266

RESUMO

Among all of the materials used in tissue engineering in order to develop bioequivalents, collagen shows to be the most promising due to its superb biocompatibility and biodegradability, thus becoming one of the most widely used materials for scaffold production. However, current imaging techniques of the cells within collagen scaffolds have several limitations, which lead to an urgent need for novel methods of visualization. In this work, we have obtained groups of collagen scaffolds and selected the contrasting agents in order to study pores and patterns of cell growth in a non-disruptive manner via X-ray computed microtomography (micro-CT). After the comparison of multiple contrast agents, a 3% aqueous phosphotungstic acid solution in distilled water was identified as the most effective amongst the media, requiring 24 h of incubation. The differences in intensity values between collagen fibers, pores, and masses of cells allow for the accurate segmentation needed for further analysis. Moreover, the presented protocol allows visualization of porous collagen scaffolds under aqueous conditions, which is crucial for the multimodal study of the native structure of samples.


Assuntos
Colágeno , Alicerces Teciduais , Microtomografia por Raio-X , Alicerces Teciduais/química , Microtomografia por Raio-X/métodos , Colágeno/química , Colágeno/metabolismo , Engenharia Tecidual/métodos , Animais , Água/química , Porosidade , Técnicas de Cultura de Células em Três Dimensões/métodos , Humanos
18.
Phys Rev Lett ; 110(7): 078304, 2013 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-25166416

RESUMO

Experimental and theoretical studies on the compositional dependence of stability and compressibility in lithiated cubic titania are presented. The crystalline-to-amorphous phase transition pressure increases monotonically with Li concentration (from ∼17.5 GPa for delithiated to no phase transition for fully lithiated cubic titania up to 60 GPa). The associated enhancement in structural stability is postulated to arise from a vacancy filling mechanism in which an applied pressure drives interstitial Li ions to vacancy sites in the oxide interior. The results are of significance for understanding mechanisms of structural response of metal oxide electrode materials at high pressures as well as emerging energy storage technologies utilizing such materials.

19.
Inorg Chem ; 52(18): 10532-41, 2013 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-23978261

RESUMO

The speciation of platinum(IV) ions in nitric acid (6-15.8 M) solutions of H2[Pt(OH)6] has been studied by (195)Pt NMR and Raman spectroscopy. Series of aqua-hydroxo-nitrato complexes [Pt(L)(x)(NO3)(6-x)] (L = H2O or OH(-); x = 0, ..., 6) were found to exist in such solutions. The pair additivity model of chemical shifts and statistical theory were used to assign signals in NMR spectra to particular [Pt(L)(x)(NO3)(6-x)] species. Mononuclear hexanitratoplatinates(IV) have been isolated in solid state in substantial yield as pyridinium salt (PyH)2[Pt(NO3)6] and characterized by single-crystal X-ray diffraction. Aging of the platinum nitric acid solutions for more than 5-6 h results in oligomerization of [Pt(L)(x)(NO3)(6-x)] species and the formation of oligonuclear aqua-hydroxo-nitrato complexes with OH(-) and NO3(-) bridging ligands. Oligomeric platinum(IV) complexes with two and four nuclei were unambiguously detected by NMR on (195)Pt -enriched samples. Oligomers with even higher nuclearity were also detected. Dimeric anions [Pt2(µ-OH)2(NO3)8](2-) have been isolated as single crystals of tetramethylammonium salt and characterized by X-ray diffraction.

20.
J Phys Condens Matter ; 35(26)2023 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-36990098

RESUMO

The amorphous selenium (a-Se) was studied via x-ray diffraction (XRD) under pressures ranging from ambient pressure up to 30 GPa at room temperature to study its high-pressure behavior. Two compressional experiments on a-Se samples, with and without heat treatment, respectively, were conducted. Contrary to the previous reports that a-Se crystallized abruptly at around 12 GPa, in this work we report an early partially crystallized state at 4.9 GPa before completing the crystallization at around 9.5 GPa based onin-situhigh pressure XRD measurements on the a-Se with 70 °C heat treatment. In comparison, crystallization pressure on another a-Se sample without thermal treatment history was observed to be 12.7 GPa, consistent with the previously reported crystallization pressure. Thus, it is proposed in this work that prior heat treatment of a-Se can result in an earlier crystallization under high pressure, which helps to understand the possible mechanism caused by the previous controversial reports on pressure induced crystallization behavior in a-Se.

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