RESUMEN
We fabricated porous particles incorporating sugars (mannitol, sucrose, or dextran) and fenofibrate nanoparticles (FNPs) by using spray-freeze-drying (SFD). The type of sugar significantly influenced the pore architecture of the resulting SFD particles. Rapid freezing of droplets containing dextran produced ice encapsulation within a dextran matrix, forming porous dextran particles. In the presence of FNPs, the particle size (approximately 4 µm) and pore volume (0.3 cm3/g) of SFD dextran were barely affected. In contrast, SFD particles derived from mannitol and sucrose exhibited denser structures with a lower pore volume than dextran. SFD mannitol incorporating FNPs produced porous structures. FNPs containing surfactant and polymer, which reduced surface tension and increased viscosity, promoted the formation of small droplets with a polymeric structure and porous particles with a relatively sharp size distribution with a median around 5 µm. FNPs were uniformly distributed in SFD dextran, which featured large pore structures, whereas in SFD mannitol, the Raman signal of FNPs was more broadly distributed across the powder samples. Both morphologies contributed to enhancing the FNP dispersibility within a redispersed suspension of SFD particles. FNPs in SFD mannitol and dextran matrices maintained their particle size distribution from before SFD, showing no aggregation upon redispersion. Dextran formed a highly porous network irrespective of the presence of FNPs, whereas mannitol tended to alter the particle attributes upon FNP inclusion. In conclusion, SFD particles derived from dextran and mannitol might help to increase FNP dispersibility by increasing the formation of porous architectures.
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We synthesized a perovskite-type RbNbO3 at 1173 K and 4 GPa from non-perovskite RbNbO3 and investigated its crystal structure and properties towards ferroelectric material design. Single-crystal X-ray diffraction analysis revealed an orthorhombic cell in the perovskite-type structure (space group Amm2, no. 38) with a = 3.9937(2) Å, b = 5.8217(3) Å, and c = 5.8647(2) Å. This non-centrosymmetric space group is the same as the ferroelectric BaTiO3 and KNbO3 but with enhanced distortion. Structural transition from orthorhombic to two successive tetragonal phases (Tetra1 at 493 K, Tetra2 at 573 K) was observed, maintaining the perovskite framework before reverting to the triclinic ambient phase at 693 K, with no structural changes between 4 and 300 K. The first transition is similar to that of KNbO3, whereas the second to Tetra2, marked by c-axis elongation and a significant cp/ap ratio jump (from 1.07 to 1.43), is unique. This distortion suggests a transition similar to that of PbVO3, where an octahedron's oxygen separates along the c-axis, forming a pyramid. Ab initio calculations simulating negative pressure like thermal expansion predicted this phase transition (cp/ap = 1.47 at -1.2 GPa), aligning with experimental findings. Thermal analysis revealed two endothermic peaks, with the second transition entailing a greater enthalpy change and volume alteration. Strong second harmonic generation signals were observed across Ortho, Tetra1, and Tetra2 phases, similar to BaTiO3 and KNbO3. Permittivity increased during the first transition, although the second transition's effects were limited by thermal expansion-induced bulk sample collapse. Perovskite-type RbNbO3 emerges as a promising ferroelectric material.
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The structural parameters of yttrium chromium tetra-boride YCrB4 were refined based on single-crystal X-ray diffraction data. YCrB4 is ortho-rhom-bic, having a space group of type Pbam (No. 55) and with lattice parameters of a = 5.9425â (2), b = 11.4831â (4), c = 3.4643â (1)â Å. The Y and Cr atoms are located at Wyckoff 4h sites (x, y, 0) and B atoms at the Wyckoff 4g sites (x, y, 1/2). The first structural investigation of YCrB4 was performed using a single crystalline sample [Kuz'ma, (1970 â¸). Kristallografiya. 15, 372-374]. The present study successfully refined all the positional and atomic displacement parameters of the Y, Cr, and B atoms.
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This study focuses on the cation intercalation of structurally unique compounds synthesized from the partial dehydration and deprotonation of coordinated water molecules in hydrous materials. Partial dehydration can potentially result in hydrous materials with a porous nature, which maintains the parent structure of the material, and deprotonation causes oxidation in the hydrous materials. Li-intercalation experiments were conducted on the hydrous iron(II) phosphate mineral, vivianite (Fe2+3(PO4)2·8H2O), and its oxidized and partially dehydrated product, santabarbaraite. Vivianite comprises two-dimensional Fe3(PO4)2 sheets and coordinated water molecules. The oxidation progress of the Fe2+ of vivianite increased cathodic capacities up to 156 mA h g-1. The Li-intercalation reaction rate increased significantly owing to dehydration because the partial dehydration of vivianite created structural space for the diffusion of Li+. Furthermore, X-ray diffraction measurements revealed that Li intercalation did not cause the formation of byproducts.
RESUMEN
The structures of ammonium manganese(II) dialuminium tris-(phosphate) dihydrate, (NH4)MnAl2(PO4)3·2H2O, and ammonium nickel(II) dialuminium tris-(phosphate) dihydrate, (NH4)NiAl2(PO4)3·2H2O, were determined using single-crystal diffraction data. The structures of title compounds are isotypic to cobalt aluminophosphate, (NH4)CoAl2(PO4)3·2H2O (LMU-3) [Panz et al. (1998 â¸). Inorg. Chim. Acta, 269, 73-82], in which a three-dimensional network of vertex-sharing AlO5 and PO4 moieties delineate twelve-membered channels in which ammonium, NH4 +, and transition-metal cations (M = Mn2+ and Ni2+) reside as charge compensators for the anionic [Al2(PO4)3]3- aluminophosphate framework. In both structures, the N atom of the ammonium cation, the transition-metal ion and one of the P atoms lie on crystallographic twofold axes.
RESUMEN
Single crystals of Ir2S3 (diiridium trisulfide) and Rh2S3 (dirhodium trisulfide) were grown in evacuated silica-glass tubes using a chemical transport method and their crystal structures were determined by single-crystal X-ray diffraction analysis. These compounds have a unique sesquisulfide structure in which pairs of face-sharing octahedra are linked into a three-dimensional structure by further edge- and vertex-sharing. Ir2S3 and Rh2S3 had similar unit-cell parameters and bond distances. The atomic displacement parameter (MSD: mean-square displacement) of each atom in Ir2S3 was considerably smaller than that in Rh2S3. The Debye temperatures (ΘD) estimated from the observed MSDs for the Ir, S1 and S2 sites in Ir2S3 were 259, 576 and 546â K, respectively, and those for Rh, S1 and S2 in Rh2S3 were 337, 533 and 530â K, respectively. The bulk Debye temperature for Ir2S3 kashinite (576â K) was found to rank among the higher values reported for many known sulfides. The bulk Debye temperature for Rh2S3 bowieite (533â K) was lower than that for Ir2S3 kashinite, which crystallizes in the early sequences of mineral crystallization differentiation from the primitive magma in the Earth's mantle.
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Ice polymorphs show extraordinary structural diversity depending on pressure and temperature. The behavior of hydrogen-bond disorder not only is a key ingredient for their structural diversity but also controls their physical properties. However, it has been a challenge to determine the details of the disordered structure in ice polymorphs under pressure, because of the limited observable reciprocal space and inaccuracies related to high-pressure techniques. Here, we present an elucidation of the disordered structure of ice VII, the dominant high-pressure form of water, at 2.2 GPa and 298 K, from both single-crystal and powder neutron-diffraction techniques. We reveal the three-dimensional atomic distributions from the maximum entropy method and unexpectedly find a ring-like distribution of hydrogen in contrast to the commonly accepted discrete sites. In addition, total scattering analysis at 274 K clarified the difference in the intermolecular structure from ice VIII, the ordered counterpart of ice VII, despite an identical molecular geometry. Our complementary structure analyses robustly demonstrate the unique disordered structure of ice VII. Furthermore, these findings are related to proton dynamics, which drastically vary with pressure, and will contribute to an understanding of the structural origin of anomalous physical properties of ice VII under pressures.
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The structure refinement and XANES study of two gold-silver-tellurides [Au1+xAgxTe2, krennerite (x = 0.11-0.13) and sylvanite (x = 0.29-0.31)] are presented and the structures are compared with the prototype structure of calaverite (x = 0.08-0.10). Whereas the latter is well known for being incommensurately modulated at ambient conditions, neither krennerite nor sylvanite present any modulation. This is attributed to the presence of relatively strong Te-Te bonds (bond distances < 2.9â Å) in the two minerals, which are absent in calaverite (bond distances > 3.2â Å). In both tellurides, trivalent gold occurs in slightly distorted square planar coordination, whereas monovalent gold, partly substituted by monovalent silver, presents a 2+2+2 coordination, corresponding to distorted rhombic bipyramids. The differentiation between bonding and non-bonding contacts is obtained by computation of the Effective Coordination Number (ECoN). The CHARge DIstribution (CHARDI) analysis is satisfactory for both tellurides but suggests that the Te-Te bond in the [Te3]2- anion is not entirely homopolar. Both tellurides can therefore be described as Madelung-type compounds, despite the presence of Te-Te in both structures.
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The crystal structures of the rare-earth (RE) trirhodium diborides praseo-dymium trirhodium diboride, PrRh3B2, neodymium trirhodium diboride, NdRh3B2, and samarium trirhodium diboride, SmRh3B2, were refined on the basis of single-crystal X-ray diffraction data. The crystal chemistry of RERh3B2 (RE: Pr, Nd, and Sm) compounds has previously been analyzed mainly on the basis of powder samples [Ku et al. (1980 â¸). Solid State Commun. 35, 91-96], and no structural investigation by single-crystal X-ray diffraction has been reported so far. The crystal structures of the three hexa-gonal RERh3B2 compounds are isotypic with that of CeRh3B2; RE, Rh and B sites are situated on special positions with site symmetry 6/mmm (Wyckoff position 1a), mmm (3g) and m2 (2c), respectively. In comparison with the previous powder X-ray study of hexa-gonal RERh3B2, the present redetermination against single-crystal X-ray data has allowed for the modeling of all atoms with anisotropic displacement parameters (ADPs). The ADPs of the Rh atom in each of the structures result in an elongated displacement ellipsoid in the direction of the stacking of the Rh kagomé-type layer. The features of obtained ADPs of atoms are discussed in relation to RERh3B2-type and analogous structures.
RESUMEN
The compositional difference between subducting slabs and their surrounding lower-mantle can yield the difference in incorporation mechanism of Fe and Al into bridgmanite between both regions, which should cause heterogeneity in physical properties and rheology of the lower mantle. However, the precise cation-distribution has not been examined in bridgmanites with Fe- and Al-contents expected in a mid-ocean ridge basalt component of subducting slabs. Here we report on Mg0.662Fe0.338Si0.662Al0.338O3 bridgmanite single-crystal characterized by a combination of single-crystal X-ray diffraction, synchrotron 57Fe-Mössbauer spectroscopy and electron probe microanalysis. We find that the charge-coupled substitution AMg2+ + BSi4+ â AFe3+(high-spin) + BAl3+ is predominant in the incorporation of Fe and Al into the practically eightfold-coordinated A-site and the sixfold-coordinated B-site in bridgmanite structure. The incorporation of both cations via this substitution enhances the structural distortion due to the tilting of BO6 octahedra, yielding the unusual expansion of mean
RESUMEN
Single crystals of Ni3Se2 (trinickel diselenide) and NiSe (nickel selenide) with stoichiometric chemical compositions were grown in evacuated silica-glass tubes. The chemical compositions of the single crystals of Ni3Se2 and NiSe were determined by scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM/EDS). The crystal structures of Ni3Se2 [rhombohedral, space group R32, a = 6.02813â (13), c = 7.24883â (16)â Å, Z = 3] and NiSe [hexagonal, space group P63/mmc, a = 3.66147â (10), c = 5.35766â (16)â Å, Z = 2] were analyzed by single-crystal X-ray diffraction and refined to yield R values of 0.020 and 0.018 for 117 and 85 unique reflections, respectively, with Fo > 4σ(Fo). R32 is a Sohncke type of space group where enantiomeric structures can exist; the single-domain structure obtained by the refinement was confirmed to be correct by a Flack parameter of -0.05â (2). The existence of Ni-Ni bonds was confirmed in both compounds, in addition to the Ni-Se bonds. The value of the atomic displacement parameter (mean-square displacement) of each atom in NiSe was larger than that in Ni3Se2. The larger amplitude of the atoms in NiSe corresponds to longer Ni-Se and Ni-Ni bond lengths in NiSe than in Ni3Se2. The Debye temperatures, θD, estimated from observed mean-square displacements for Ni and Se in Ni3Se2, were 322 and 298â K, respectively, while those for Ni and Se in NiSe were 246 and 241â K, respectively. The existence of large cavities in the structure and the weak bonding force are likely responsible for the brittle and soft nature of the NiSe crystal.
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The ability of a water-soluble, single-stranded ß-1,3/1,6-glucan (ssß-glucan), recovered by hydrothermal treatment, to enhance the solubility and membrane permeability of poorly water-soluble compounds was examined. As a poorly water-soluble model compound, quercetin (QUE) was used. The aqueous solubility of spray-dried particles (SDPs) of QUE/ssß-glucan was significantly enhanced compared with that of the untreated QUE powder and the physical mixture of QUE/ssß-glucan. Fourier-transform infrared spectra and small-angle X-ray scattering suggested strong interactions between ssß-glucan and QUE in the SDPs, which was attributable to QUE entrapment in the helical ssß-glucan structure. The amount of QUE infused into Caco-2 cells from QUE/ssß-glucan SDPs was 16-fold and 5-fold higher than the amount infused from untreated QUE powder and the physical mixture of QUE/ssß-glucan, respectively. These results showed that water-soluble ssß-glucan improved QUE dissolution and membrane permeability.
Asunto(s)
Permeabilidad de la Membrana Celular , Portadores de Fármacos/química , Solubilidad , beta-Glucanos/química , Antioxidantes/química , Antioxidantes/farmacología , Células CACO-2 , Supervivencia Celular/efectos de los fármacos , Liberación de Fármacos , Humanos , Microscopía Electrónica de Rastreo , Difracción de Polvo , Polvos/análisis , Polvos/química , Quercetina/química , Quercetina/farmacología , Dispersión del Ángulo Pequeño , Espectroscopía Infrarroja por Transformada de Fourier , Secado por Pulverización , Agua/química , Difracción de Rayos XRESUMEN
We successfully prepared folic acid (FA) nanoparticles with excellent dispersibility and photostability using a combination of bead milling and freeze-drying with transglycosylated naringin (Naringin-G), a newly developed transglycosylated food additive. Poly-vinyl pyrrolidon (PVP) was used for comparison with Naringin-G. Water dispersibility and photostability of the freeze-dried formulations were assessed. The dispersibility and physicochemical properties of nanoparticle formulations were evaluated using dynamic light scattering, powder X-ray diffraction (PXRD), and small-angle X-ray scattering (SAXS). Results indicated that the median particle size of FA in the slurry bead milled with Naringin-G decreased notably with time and fell below 100â¯nm after milling for 300â¯min. Further, FA nanoparticles with Naringin-G were stable without aggregation following re-dispersion of freeze-dried FA formulations in water. Contrarily, the addition of PVP did not prevent the aggregation of FA nanoparticles following re-dispersion of freeze-dried FA formulations. Solid structures of freeze-dried FA formulations with Naringin-G or PVP were assessed using PXRD and SAXS. PXRD patterns of all freeze-dried formulations highlighted broadening and weakening of peaks, indicating a decrease in FA crystallinity following bead milling, regardless of the additive concentration of Naringin-G and PVP. The scattering intensity profiles of FA formulations with PVP dramatically decreased after milling, whereas FA formulations with Naringin-G did not exhibit changes in SAXS patterns. FA formulations with Naringin-G registered faster enhancement in release rate than PVP in pHâ¯1.2 buffer solutions. The release rate of freeze-dried FA formulation with Naringin-G exhibited at least five-fold enhancement when compared to untreated FA. FA formulation with Naringin-G was stable to photodegradation under fluorescent light. Naringin-G prevented photodegradation of FA due to its antioxidant effect and scavenged radicals. These findings indicated that freeze-dried FA formulation with Naringin-G can improve its water-dispersibility and photodegradation due to the effectiveness of Naringin-G as a dispersant and cryoprotectant.
Asunto(s)
Flavanonas/química , Ácido Fólico/química , Nanopartículas/química , Crioprotectores , Estabilidad de Medicamentos , Ácido Fólico/farmacocinética , Liofilización , Tamaño de la Partícula , Procesos FotoquímicosRESUMEN
Study of arsenic (As) provides guidelines for the development of next-generation materials. We clarify the unique structure of the third crystalline polymorph of natural As (Pnm21-As) by crystallographical experiment and the electronic structure by first-principles computational method. The crystal structure of Pnm21-As is a novel structure in which the basic portions of semi-metalic grey-As and semi-conductor black-As are alternately arranged at the atomic level. For both covalent and van der Waals bonding, the contributions of sd and pd hybridizations are important. Van der Waals bonding characteristics and d orbital contributions can be varied by control of layer stacking. Total charges are clearly divided into positive and negative in the same elements for the grey-As and black-As portions, respectively, is of importance. The sequence in which one-dimensional electron donor and acceptor portions alternate in the layer will be the first description.
RESUMEN
Petzite, Ag3AuTe2, crystallizes in the space group I4132, which is a Sohncke type of space group where chiral crystal structures can occur. The structure refinement of petzite reported long ago [Frueh (1959). Am. Mineral. 44, 693-701] did not provide any information about the absolute structure. A new single-crystal X-ray diffraction refinement has now been performed on a sample from Lake View Mine, Golden Mile, Kalgoorlie, Australia, which has resulted in a reliable absolute structure [a Flack parameter of 0.05â (3)], although this corresponds to the opposite enantiomorph reported previously. The minimum Te-Te distance is 3.767â (3)â Å, slightly shorter than the van der Waals bonding distance, which suggests a weak interaction between the two chalcogens. XANES spectra near the Au and Te LIII edges suggest that the chemical-bonding character of Au in petzite is more metallic than in other gold minerals.
RESUMEN
A synchrotron X-ray diffraction study of a single crystal of titanomagnetite shows that the cation distribution of Fe2+, Fe3+ and Ti4+ is of the inverse-spinel type. The valence-difference contrast (VDC) method of resonant scattering was applied at a wavelength of λ = 1.7441â Å (E = 7.1085â keV) within the pre-edge of the Fe K absorption spectrum, utilizing the large difference in the real part of anomalous scattering factors, between -7.45 and -6.50, for Fe2+ and Fe3+, respectively. The most plausible atomic arrangement in Ti0.31Fe2.69O4 obtained from our analysis is [Fe3+1.00]A[Fe3+0.38Fe2+1.31Ti4+0.31]BO4, where A and B in an AB2O4-type structure correspond to the tetrahedral and octahedral sites, respectively. This result suggests that titanomagnetite has the complete inverse-spinel structure continuously from the end-member of magnetite, even in the case of relatively high Ti content. The physical properties may be described by the Néel model, which claims that Fe3+ preferentially occupies the tetrahedral site, within a Ti-poor half-region of the solid solution. Based on the ordering scheme the magnetic structure of titanomagnetite is considered to be analogous to that of magnetite. The combination of circularly polarized X-rays and a horizontal-type four-circle diffractometer used in this VDC technique has the advantage of increasing the experimental accuracy and freedom with the simultaneous reduction of experimental noise.
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The Sr-Ge-O system has an earth-scientific importance as a potentially good low-pressure analog of the Ca-Si-O system, one of the major components in the constituent minerals of the Earth's crust and mantle. However, it is one of the germanate systems that has not yet been fully examined in the phase relations and structural properties. The recent findings that the SrGeO3 high-pressure perovskite phase is the first Ge-based transparent electronic conductor make the Sr-Ge-O system interesting in the field of materials science. In the present study, we have revealed the existence of a new high-pressure strontium germanate, SrGe2O5. Single crystals of this compound crystallized as a co-existent phase with SrGeO3 perovskite single crystals in the sample recovered in the compression experiment of SrGeO3 pseudowollastonite conducted at 6â GPa and 1223â K. The crystal structure consists of germanium-oxygen framework layers stacked along [001], with Sr atoms located at the 12-coordinated cuboctahedral site; the layers are formed by the corner linkages between GeO6 octahedra and between GeO6 octahedra and GeO4 tetrahedra. The present SrGe2O5 is thus isostructural with the high-pressure phases of SrSi2O5 and BaGe2O5. Comparison of these three compounds leads to the conclusion that the structural responses of the GeO6 and GeO4 polyhedra to cation substitution at the Sr site are much less than that of the SrO12 cuboctahedron to cation substitution at the Ge sites. Such a difference in the structural response is closely related to the bonding nature.
RESUMEN
A high-temperature single-crystal X-ray diffraction study of a synthetic PbTiO3 perovskite was carried out over the wide temperature range 298-928â K. A transition from a tetragonal (P4mm) to a cubic (Pm \bar 3 m) phase has been revealed near 753â K. In the non-centrosymmetric P4mm symmetry group, the difference in relative displacement between Pb and O along the c-axis is much larger than that between Ti and O. The Pb and Ti cations contribute sufficiently to polarization being shifted in the opposite direction compared with the shift of O atoms. Deviation from the linear changes in Debye-Waller factors and bonding distances in the tetragonal phases can be interpreted as a precursor phenomenon before the phase transition. Disturbance of the temperature factor Ueq for O is observed in the vicinity of the transition point, while Ueq values for Pb and Ti are continuously changing with increasing temperature. The O site includes the clear configurational disorder in the cubic phase. The polar local positional distortions remain in the cubic phase and are regarded as the cause of the paraelectricity. Estimated values of the Debye temperature ΘD for Pb and Ti are 154 and 467â K in the tetragonal phase and decrease 22% in the high-temperature phase. Effective potentials for Pb and Ti change significantly and become soft after the phase transition.
RESUMEN
Single crystals of the title compound, the post-perovskite-type CaIrO3 [calcium iridium(IV) trioxide], have been grown from a CaCl2 flux at atmospheric pressure. The crystal structure consists of an alternate stacking of IrO6 octa-hedral layers and CaO8 hendeca-hedral layers along [010]. Chains formed by edge-sharing of IrO6 octa-hedra (point-group symmetry 2/m..) run along [100] and are inter-connected along [001] by sharing apical O atoms to build up the IrO6 octa-hedral layers. Chains formed by face-sharing of CaO8 hendeca-hedra (point-group symmetry m2m) run along [100] and are inter-connected along [001] by edge-sharing to build up the CaO8 hendeca-hedral layers. The IrO6 octa-hedral layers and CaO8 hendeca-hedral layers are inter-connected by sharing edges. The present structure refinement using a high-power X-ray source confirms the atomic positions determined by Hirai et al. (2009 â¸) [Z. Kristallogr. 224, 345-350], who had revised our previous report [Sugahara et al. (2008 â¸). Am. Mineral. 93, 1148-1152]. However, the displacement ellipsoids of the Ir and Ca atoms based on the present refinement can be approximated as uniaxial ellipsoids elongating along [100], unlike those reported by Hirai et al. (2009 â¸). This suggests that the thermal vibrations of the Ir and Ca atoms are mutually suppressed towards the Irâ¯Ca direction across the shared edge because of the dominant repulsion between the two atoms.
RESUMEN
XANES (X-ray absorption near-edge structure) spectra of the Ti K-edges of ATiO3 (A = Ca and Sr), A2TiO4 (A = Mg and Fe), TiO2 rutile and TiO2 anatase were measured in the temperature range 20-900 K. Ti atoms for all samples were located in TiO6 octahedral sites. The absorption intensity invariant point (AIIP) was found to be between the pre-edge and post-edge. After the AIIP, amplitudes damped due to Debye-Waller factor effects with temperature. Amplitudes in the pre-edge region increased with temperature normally by thermal vibration. Use of the AIIP peak intensity as a standard point enables a quantitative comparison of the intensity of the pre-edge peaks in various titanium compounds over a wide temperature range.