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1.
Nucleic Acids Res ; 51(2): 908-918, 2023 01 25.
Artículo en Inglés | MEDLINE | ID: mdl-36583341

RESUMEN

Polyribosomes, the groups of ribosomes simultaneously translating a single mRNA molecule, are very common in both, prokaryotic and eukaryotic cells. Even in early EM studies, polyribosomes have been shown to possess various spatial conformations, including a ring-shaped configuration which was considered to be functionally important. However, a recent in situ cryo-ET analysis of predominant regular inter-ribosome contacts did not confirm the abundance of ring-shaped polyribosomes in a cell cytoplasm. To address this discrepancy, here we analyzed the cryo-ET structure of polyribosomes in diluted lysates of HeLa cells. It was shown that the vast majority of the ribosomes were combined into polysomes and were proven to be translationally active. Tomogram analysis revealed that circular polyribosomes are indeed very common in the cytoplasm, but they mostly possess pseudo-regular structures without specific inter-ribosomal contacts. Although the size of polyribosomes varied widely, most circular polysomes were relatively small in size (4-8 ribosomes). Our results confirm the recent data that it is cellular mRNAs with short ORF that most commonly form circular structures providing an enhancement of translation.


Asunto(s)
Biosíntesis de Proteínas , Ribosomas , Humanos , Células HeLa , Polirribosomas/metabolismo , Ribosomas/genética , Ribosomas/metabolismo , ARN Mensajero/metabolismo , Conformación Molecular
2.
Inorg Chem ; 63(22): 10099-10102, 2024 Jun 03.
Artículo en Inglés | MEDLINE | ID: mdl-38768193

RESUMEN

The homogeneous high-entropy wolframite-type solid solution (Mn1/5Co1/5Ni1/5Cu1/5Cd1/5)WO4 was prepared by solid-state reaction at 1000 °C. Elongated "crystals" were grown from the Na2WO4 flux, but their strongly broadened powder X-ray diffraction patterns indicated partial dissolution. Nevertheless, successive annealing of the homogeneous solid solution for 3-4 h at 800, 700, and 600 °C did not bring any sign of dissolution. Thus, the material is kinetically stable at low temperatures although thermodynamically unstable. The long-range antiferromagnetic order was established at TN ∼ 24.8 K. Based on magnetization and specific heat measurements, a magnetic phase diagram was built, demonstrating the presence of an additional field-induced phase. In contrast to the parent MnWO4, no dielectric anomaly has been found down to 2 K.

3.
Inorg Chem ; 63(11): 5012-5019, 2024 Mar 18.
Artículo en Inglés | MEDLINE | ID: mdl-38438970

RESUMEN

The concept of high-entropy oxides has triggered extensive research of this novel class of materials because their numerous functional properties are usually not mere linear combinations of those of the components. Here, we introduce the new series of compositionally complex honeycomb-layered magnets Na3-xLixT2SbO6 (T = Cu1/3Ni1/3Co1/3). An unusual feature of the system is its nonmonotonous dependences of the monoclinic lattice parameters b and ß on x. Rietveld refinement of the crystal structures of the Na and Li end members reveals apparent Sb-T site inversion in the former and considerable Li-Cu site inversion in the latter. The materials are characterized by measurements of specific heat Cp, magnetization M, and ac and dc magnetic susceptibility χ. Na3T2SbO6 exhibits sharp long-range antiferromagnetic order (TN = 10.2 K) preceded by noticeable correlation effects at elevated temperatures. The magnetic phase diagram of Na3T2SbO6 is established. Introduction of Li, just at x = 0.8, destroys AFM order, resulting in spin-cluster glass behavior attributed to Li/Cu inversion, with TG growing with x to 10.4 K at x = 3.

4.
Inorg Chem ; 63(11): 5199-5207, 2024 Mar 18.
Artículo en Inglés | MEDLINE | ID: mdl-38447157

RESUMEN

New nitrosonium manganese(II) nitrate, (NO)Mn6(NO3)13, has been synthesized and structurally characterized. In the temperature range of 45-298 K, the crystal is hexagonal (centrosymmetric sp. gr. P63/m). Mn2+ ions are assembled into tubes along axis c with both NO3- filling and coating. The nitrosonium cation is located in the framework cavity and is disordered by a 3-fold axis. At the temperature TS1 = 190 K, a structural phase transition related to the libration of the intertube NO3 group and a small variation of Mn polyhedron is observed. Moreover, the anomalies in physical properties of (NO)Mn6(NO3)13 allow suggesting that ordering of NO+ units occurs at low temperatures. The antiferromagnetic ordering in this compound is preceded by the formation of a short-range correlation regime at about 25 K and takes place in two steps at TN1 = 12.0 K and TN2 = 8.4 K.

5.
Retina ; 44(8): 1387-1393, 2024 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-38484089

RESUMEN

PURPOSE: To evaluate the efficacy and safety of photodynamic therapy (PDT) with chlorin E6 in chronic central serous chorioretinopathy. METHODS: In this single-center retrospective cohort study, all patients received standard PDT with 6 mg of chlorin E6 (Fotoran E6) for each m 2 of body surface area with 50 J/cm 2 fluence and a treatment time of 83 seconds. The changes in central retinal thickness, subfoveal choroidal thickness, and best-corrected visual acuity were evaluated at the end of the follow-up. The main outcome measure was the presence of subretinal fluid at 3 months after PDT. RESULTS: Thirty-nine eyes (32 men and 7 women, 43.7 ± 10.0 years) were included. In total, 50 PDT sessions were performed. At 3 months of follow-up, 31 of 39 (79.5%) study eyes showed complete resolution of subretinal fluid. The mean follow-up period after PDT was 15.3 ± 7.8 months. At the end of the follow-up, a complete resolution of subretinal fluid was observed in 32 of 39 (82.7%) eyes. The mean change in central retinal thickness, subfoveal choroidal thickness, and best-corrected visual acuity at the end of the follow-up was -139.7 ± 136.4 µ m, -66.8 ± 36.2 µ m, and -0.05 ± 0.08 logMAR, respectively ( P < 0.001). Neither systemic nor ocular adverse events were observed, nor were local reactions seen. CONCLUSION: Standard PDT with chlorin E6 is an effective and safe option in the management of chronic central serous chorioretinopathy and may be considered as an alternative to the standard PDT with Visudyne.


Asunto(s)
Coriorretinopatía Serosa Central , Clorofilidas , Angiografía con Fluoresceína , Fotoquimioterapia , Fármacos Fotosensibilizantes , Porfirinas , Tomografía de Coherencia Óptica , Agudeza Visual , Humanos , Coriorretinopatía Serosa Central/tratamiento farmacológico , Coriorretinopatía Serosa Central/diagnóstico , Coriorretinopatía Serosa Central/fisiopatología , Masculino , Femenino , Fotoquimioterapia/métodos , Porfirinas/uso terapéutico , Estudios Retrospectivos , Adulto , Agudeza Visual/fisiología , Fármacos Fotosensibilizantes/uso terapéutico , Fármacos Fotosensibilizantes/efectos adversos , Persona de Mediana Edad , Enfermedad Crónica , Resultado del Tratamiento , Estudios de Seguimiento , Fondo de Ojo
6.
Angew Chem Int Ed Engl ; 63(3): e202316719, 2024 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-38054955

RESUMEN

A novel vanadium hydroxide-phosphate, NH4 VPO4 OH, was synthesized hydrothermally in V2 O5 -NH4 H2 PO4 -citric acid system at 230 °C. It was characterized by XRD, TG-DSC, SEM-EDX, FTIR and NMR spectroscopy. NH4 VPO4 OH is isostructural with NH4 GaPO4 OH and features edge-sharing chains of VO6 octahedra. These chains running along [010] direction of the unit cell are connected by phosphate tetrahedra to form infinite layers parallel to the (100) plane. Ammonium cations are embedded between the heteropolyhedral layers. According to the thermodynamic and NMR measurements supported by the first-principles calculations, NH4 VPO4 OH presents a rare case of Haldane spin system with spin S=1 based on V3+ ions.

7.
Chemphyschem ; 24(15): e202300111, 2023 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-37191070

RESUMEN

A new family of compounds ACu7 TeO4 (SO4 )5 Cl (A=Na, K, Rb, Cs) isostructural to mineral Nabokoite (K species) was synthesized by solid state and gas transport reactions in sealed ampoules and characterized in measurements of magnetization and specific heat in a wide temperature range. These complex compounds are of the utmost interest as a testing playground to study the properties of quasi-two-dimensional magnets with a square kagome lattice geometry. A quantum ground state of such a corner-sharing network is a spin liquid. Unlike idealized grid analyzed in numerous models, the square kagome lattice in nabokoites is wavy and distorted being composed of versatile triangles. Moreover, it contains "excessive" decorating magnetic ions, which makes magnetism of these objects even more complicated. The interaction of these decorating ions through virtual excitations of the square kagome lattice is accompanied by the formation of a long-range magnetic order coexisting with the spin liquid.

8.
Inorg Chem ; 62(35): 14180-14190, 2023 Sep 04.
Artículo en Inglés | MEDLINE | ID: mdl-37595259

RESUMEN

ortho-Pyrovanadate (or ortho-diorthovanadate) K2Mn23+Mn2+O(OH)(VO4)(V2O7) synthesized hydrothermally crystallizes in the orthorhombic space group Pnma with a = 17.9155(5), b = 5.8940(2), c = 10.9971(3) Å, V = 1161.23(6) Å3, and Z = 4. Its crystal structure features linear chains of edge-sharing Mn3+O6 octahedra with every second pair of Mn3+O6 octahedra condensed with a Mn2+O6 octahedron on one side of a chain in a sawtooth pattern so that each sawtooth chain consists of a triangular trimer. These sawtooth chains, running parallel to the b axis and linked by the VO4 and V2O7 groups, form a framework with channels populated by K atoms. The new compound is a structural analogue of the mineral zoisite Ca2Al3O(OH)(SiO4)(Si2O7), showing a striking example of very different chemical compositions. K2Mn3O(OH)(VO4)(V2O7) undergoes a phase transition into an ordered antiferromagnetic (AFM) state at TN = 14.4 K, which was detected by high-frequency electron spin resonance as well as by both specific heat Cp and Fisher's specific heat d(χT)/dT measurements. However, this phase transition was not detected by magnetic susceptibility measurements. The origin of this puzzling observation was resolved by evaluating the spin exchanges of K2Mn3O(OH)(VO4)(V2O7), which revealed that each triangular trimer is a ferromagnetically coupled cluster, and the observed ordering involves an AFM ordering between the ferromagnetic (FM) clusters. This ordering is shrouded in magnetic susceptibility measurements due to the susceptibility contributions from the individual FM triangular trimers even below TN. We showed that the magnetic susceptibility of K2Mn3O(OH)(VO4)(V2O7) between ∼30 K and room temperature is satisfactorily described by an AFM chain made up of ferromagnetically coupled triangular clusters, as described by a few spin-exchange parameters.

9.
Retina ; 43(11): 2019-2026, 2023 11 01.
Artículo en Inglés | MEDLINE | ID: mdl-37487237

RESUMEN

PURPOSE: To study the status of retinal pigment epithelium in nonexudative and active choroidal neovascularization (CNV) in neovascular age-related macular degeneration. METHODS: Only treatment-naïve neovascular age-related macular degeneration patients were enrolled in this prospective case-control study, including 17 eyes with nonexudative CNV (6 males and 11 females, 74.9 ± 10.0 years) and 28 eyes with active CNV (8 males and 20 females, 69.3 ± 6.8 years). All patients received a comprehensive ophthalmic examination, optical coherence tomography, dark-field scanning laser ophthalmoscopy, and fundus autofluorescence. The status of the retinal pigment epithelium was assessed with ImageJ software as the brightness of the CNV region on transillumination optical coherence tomography, dark-field scanning laser ophthalmoscopy, and fundus autofluorescence images. Choroidal neovascularization vessel density was measured based on optical coherence tomography angiography. RESULTS: The brightness of CNV region in nonexudative CNV was statistically significantly lower than in active CNV with both optical coherence tomography transillumination ( P = 0.004) and dark-field scanning laser ophthalmoscopy ( P = 0.0015). No difference in brightness of the CNV region between nonexudative and active CNV was found based on fundus autofluorescence ( P = 0.44). The vessel density of nonexudative CNV was statistically significantly higher than that of active CNV with a median value of 64.5% (95% confidential interval [CI] 53.4-79.0%) and 55.3% (95% CI 52.2-60.0%), respectively ( P = 0.05). CONCLUSION: Multimodal imaging revealed substantial alteration of the retinal pigment epithelium in active CNV but not in nonexudative CNV which correlates with the higher vessel density of nonexudative CNV.


Asunto(s)
Neovascularización Coroidal , Degeneración Macular , Masculino , Femenino , Humanos , Persona de Mediana Edad , Anciano , Anciano de 80 o más Años , Epitelio Pigmentado de la Retina , Proyectos Piloto , Estudios de Casos y Controles , Angiografía con Fluoresceína , Neovascularización Coroidal/diagnóstico , Tomografía de Coherencia Óptica , Degeneración Macular/diagnóstico , Imagen Multimodal
10.
Int J Mol Sci ; 24(10)2023 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-37239879

RESUMEN

In response to adverse environmental factors, Escherichia coli cells actively produce Dps proteins which form ordered complexes (biocrystals) with bacterial DNA to protect the genome. The effect of biocrystallization has been described extensively in the scientific literature; furthermore, to date, the structure of the Dps-DNA complex has been established in detail in vitro using plasmid DNA. In the present work, for the first time, Dps complexes with E. coli genomic DNA were studied in vitro using cryo-electron tomography. We demonstrate that genomic DNA forms one-dimensional crystals or filament-like assemblies which transform into weakly ordered complexes with triclinic unit cells, similar to what is observed for plasmid DNA. Changing such environmental factors as pH and KCl and MgCl2 concentrations leads to the formation of cylindrical structures.


Asunto(s)
Proteínas de Escherichia coli , Escherichia coli , Escherichia coli/genética , Escherichia coli/metabolismo , Proteínas de Unión al ADN/metabolismo , ADN/química , ADN Bacteriano/metabolismo , Proteínas de Escherichia coli/genética , Proteínas de Escherichia coli/metabolismo , Proteínas Bacterianas/metabolismo , Proteínas de la Membrana Bacteriana Externa/genética
11.
Inorg Chem ; 61(33): 13034-13046, 2022 Aug 22.
Artículo en Inglés | MEDLINE | ID: mdl-35947773

RESUMEN

A tetravalent-substituted cobalt ludwigite Co2.5Ge0.5BO5 has been synthesized using the flux method. The compound undergoes two magnetic transitions: a long-range antiferromagnetic transition at TN1 = 84 K and a metamagnetic one at TN2 = 36 K. The sample-oriented magnetization measurements revealed a fully compensated magnetic moment along the a- and c-axes and an uncompensated one along the b-axis leading to high uniaxial anisotropy. A field-induced enhancement of the ferromagnetic correlations at TN2 is observed in specific heat measurements. The DFT+GGA calculation predicts the spin configuration of (↑↓↓↑) as a ground state with a magnetic moment of 1.37 µB/f.u. The strong hybridization of Ge(4s, 4p) with O (2p) orbitals resulting from the high electronegativity of Ge4+ is assumed to cause an increase in the interlayer interaction, contributing to the long-range magnetic order. The effect of two super-superexchange pathways Co2+-O-B-O-Co2+ and Co2+-O-M4-O-Co2+ on the magnetic state is discussed.

12.
Inorg Chem ; 61(12): 4879-4886, 2022 Mar 28.
Artículo en Inglés | MEDLINE | ID: mdl-35298134

RESUMEN

We synthesized single crystals of Na0.55Ni6(OH)3(H0.61PO4)4 (I) and polycrystals of (Na, Ni)0.64Ni5.68(OH)3(H0.67PO4)4 (II) with ellenbergerite-like structures using the hydrothermal method. The phases crystallize in the hexagonal space group P63mc with the following unit cell parameters: a = 12.5342(1) Å, c = 4.9470(1) Å, and V = 673.08(2) Å3 for I; a = 12.4708(2) Å, c = 4.9435(2) Å, and V = 665.82(2) Å3 for II; and Z = 2. Their crystal structures are based on a 3D framework built from NiO6 octahedra and PO4 tetrahedra. The difference between I and II lies in the way the structural channels are filled along the [001] direction. These channels accommodate segments of Na- and (Na, Ni)-centered chains of face-sharing octahedra in the structures I and II, respectively. The magnetic susceptibility χ and the specific heat Cp evidence pronounced low-dimensional magnetic behavior at elevated temperatures and the formation of the weakly ferromagnetic long-range order at TNI = 61 K and TNII = 63 K. Analysis of the χ(T) data within both chain and dimer spin models allows the estimation of the leading exchange interaction parameters in the compounds under study.

13.
Nanotechnology ; 33(25)2022 Mar 30.
Artículo en Inglés | MEDLINE | ID: mdl-35276689

RESUMEN

Currently, there is growing interest in wearable and biocompatible smart computing and information processing systems that are safe for the human body. Memristive devices are promising for solving such problems due to a number of their attractive properties, such as low power consumption, scalability, and the multilevel nature of resistive switching (plasticity). The multilevel plasticity allows memristors to emulate synapses in hardware neuromorphic computing systems (NCSs). The aim of this work was to study Cu/poly-p-xylylene(PPX)/Au memristive elements fabricated in the crossbar geometry. In developing the technology for manufacturing such samples, we took into account their characteristics, in particular stable and multilevel resistive switching (at least 10 different states) and low operating voltage (<2 V), suitable for NCSs. Experiments on cycle to cycle (C2C) switching of a single memristor and device to device (D2D) switching of several memristors have shown high reproducibility of resistive switching (RS) voltages. Based on the obtained memristors, a formal hardware neuromorphic network was created that can be trained to classify simple patterns.

14.
Optom Vis Sci ; 99(9): 687-691, 2022 09 01.
Artículo en Inglés | MEDLINE | ID: mdl-35678631

RESUMEN

SIGNIFICANCE: This is a case-control study showing changes in accommodation in eyes with acute central serous chorioretinopathy. We found that decreased accommodative amplitude in the affected eyes may indicate suppression of parasympathetic activity in those eyes as one of the pathophysiological mechanisms controlling choroidal thickness and perfusion. PURPOSE: This study aimed to evaluate the changes of accommodation in patients with acute central serous chorioretinopathy. METHODS: Patients with unilateral central serous chorioretinopathy, with and without foveal involvement, as well as patients after resolution of subretinal fluid and healthy age-matched controls were included. Accommodative amplitude was measured and compared between eyes with active or resolved central serous chorioretinopathy, fellow eyes of active central serous chorioretinopathy individuals, and eyes of controls. Correlation between accommodative amplitude and ocular and demographic parameters was calculated. RESULTS: Nineteen acute central serous chorioretinopathy patients (16 males and 3 females, 38.1 ± 5.1 years) and 17 age-matched controls (13 males and 4 females, 37.2 ± 5.4 years) were included. Accommodative amplitude in the study eyes of central serous chorioretinopathy patients was lower than that in the fellow unaffected eyes (1.25 ± 1.0 and 2.54 ± 0.94 D, respectively; P = .002) or in the eyes of healthy controls (2.41 ± 1.38 D, P = .002). In central serous chorioretinopathy eyes, after resolution of subretinal fluid or without foveal involvement, the median accommodative amplitude was lower than that in fellow eyes (1.6 [95% confidence interval, 0.83 to 1.75] and 2.7 D [95% confidence interval, 1.23 to 3.61], respectively; P = .004). No correlation was found between accommodative amplitude in affected central serous chorioretinopathy eyes and different parameters, except for age ( r = -0.47, P = .04). CONCLUSIONS: Acute central serous chorioretinopathy is associated with a substantial reduction of accommodative amplitude.


Asunto(s)
Coriorretinopatía Serosa Central , Enfermedad Aguda , Adulto , Estudios de Casos y Controles , Coriorretinopatía Serosa Central/diagnóstico , Coroides , Femenino , Angiografía con Fluoresceína , Humanos , Masculino , Estudios Retrospectivos , Líquido Subretiniano , Tomografía de Coherencia Óptica
15.
Int J Mol Sci ; 23(22)2022 Nov 10.
Artículo en Inglés | MEDLINE | ID: mdl-36430353

RESUMEN

Heat-up and hot-injection methods were employed to synthesize Ni nanoparticles (NPs) with narrow size distribution in the presence of hyperbranched pyridylphenylene polymer (PPP) as a stabilizing agent. It was shown that depending on the synthetic method, Ni NPs were formed either in a cross-linked polymer network or stabilized by a soluble hyperbranched polymer. Ni NPs were characterized by a combination of transmission electron microscopy (TEM), scanning TEM, thermogravimetric analysis, powder X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray analysis, and magnetic measurements. The architecture of polymer support was found to significantly effect Ni NPs characteristics and behavior. The Ni NPs demonstrated a high catalytic activity in a model Suzuki-Miyaura cross-coupling reaction. No significant drop in activity was observed upon repeated use after magnetic separation in five consecutive catalytic cycles. We believe that hyperbranched PPP can serve as universal platform for the controllable synthesis of Ni NPs, acting as highly active and stable catalysts.


Asunto(s)
Nanopartículas , Polímeros , Oxidación-Reducción , Catálisis , Nanopartículas/química , Microscopía Electrónica de Transmisión de Rastreo
16.
Int J Mol Sci ; 23(2)2022 Jan 12.
Artículo en Inglés | MEDLINE | ID: mdl-35054984

RESUMEN

Hydrogenation of levulinic acid (LA) obtained from cellulose biomass is a promising path for production of γ-valerolactone (GVL)-a component of biofuel. In this work, we developed Ru nanoparticle containing nanocomposites based on hyperbranched pyridylphenylene polymer, serving as multiligand and stabilizing matrix. The functionalization of the nanocomposite with sulfuric acid significantly enhances the activity of the catalyst in the selective hydrogenation of LA to GVL and allows the reaction to proceed under mild reaction conditions (100 °C, 2 MPa of H2) in water and low catalyst loading (0.016 mol.%) with a quantitative yield of GVL and selectivity up to 100%. The catalysts were successfully reused four times without a significant loss of activity. A comprehensive physicochemical characterization of the catalysts allowed us to assess structure-property relationships and to uncover an important role of the polymeric support in the efficient GVL synthesis.


Asunto(s)
Lactonas/química , Ácidos Levulínicos/química , Polímeros/química , Rutenio/química , Catálisis , Celulosa/química , Hidrogenación , Estructura Molecular , Análisis Espectral , Temperatura
17.
Int Ophthalmol ; 42(2): 435-442, 2022 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-34618286

RESUMEN

PURPOSE: To study interocular asymmetry in distribution of leaks in central serous chorioretinopathy (CSC). MATERIAL AND METHODS: Patients with unilateral CSC were included in this retrospective multicenter study. All patients received multimodal imaging. The prevalence of leaks within 1 disk diameter (DD) peripapillary area and the mean shortest distance between a leak and the optic disk edge was analyzed for the right and left eyes separately based on FA images. Clinical and morphological characteristics were collected and compared between eyes with a peripapillary leak and eyes with a leak elsewhere. RESULTS: In total, 152 eyes (77 right eyes and 75 left eyes) of 152 patients (128 males and 24 females) with a mean age of 45.2 ± 9.8 years were included. The mean distance from the leak to the edge of the optic disk was statistically significantly lower (p = 0.0003), and the prevalence of the leaks within the 1 DD-peripapillary area was higher in the left eye than in the right eye (32.1% versus 10.7%, respectively, p = 0.0017). The eyes with a peripapillary leak had a longer duration of the disease (p < 0.05), a wider area of retinal pigment epithelium alteration (p < 0.001), and a higher prevalence of outer retinal atrophy (p < 0.001) compared to the eyes with a leak elsewhere. CONCLUSION: The left eye showed closer location of the leak to the optic disk edge and higher prevalence of leaks within the peripapillary area. The cases with peripapillary leak commonly demonstrated characteristics of chronic CSC despite relative preservation of visual acuity.


Asunto(s)
Coriorretinopatía Serosa Central , Adulto , Coriorretinopatía Serosa Central/diagnóstico , Coroides , Femenino , Angiografía con Fluoresceína/métodos , Humanos , Masculino , Persona de Mediana Edad , Estudios Retrospectivos , Tomografía de Coherencia Óptica/métodos
18.
Inorg Chem ; 60(15): 11450-11457, 2021 Aug 02.
Artículo en Inglés | MEDLINE | ID: mdl-34264636

RESUMEN

A novel sodium bismuth oxo-cuprate phosphate chloride, Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77], containing square-kagomé layers of Cu2+ has been synthesized by hydrothermal techniques. The compound crystallizes in the tetragonal space group P4/nmm, a = 10.0176(4), c = 10.8545(6), Z = 2, V = 1089.3(1) Å3, R1 = 0.021, wR = 0.053, S = 1.32. Its composite crystal structure includes [O4Cu6Bi]7+ layers, which are formed by the clusters of oxygen-centered tetrahedra [OCu3Bi]. These positively charged two periodic fragments are intercalated in a negatively charged [CuNa6Cl3(PO4)4]7- matrix built by Na-centered polyhedra, PO4 tetrahedra, and CuO4Cl pyramids. The composite character of the crystal structure of Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77], as well as the way of its self-assembly, are discussed in close connection with the sulfohalite Na6ClF(SO4)2 salt. It is shown that the "host-guest" model of the formation of the tetragonal Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77] phase is due to the group-subgroup symmetry relation with the cubic crystal structure of mineral sulfohalite and is also supported by the crystallization condition in excess sodium chloride. The magnetic subsystem of Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77] is represented by a dense square-kagomé network of 2Cu1 and 4Cu2 ions, decorated with weakly bonded Cu3 ions. Measurements of magnetization and heat capacity indicate the absence of long-range order up to 2 K, which makes this compound a candidate for a highly demanded spin liquid.

19.
Inorg Chem ; 60(11): 8049-8061, 2021 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-34003006

RESUMEN

The unique family of coordination polymers [Ln4(OH)2(piv)10(H2O)2]∞ of 11 lanthanides (Ln = La-Er) has been prepared by a simple solution method based on controlled hydrolysis. The ribbon-like polymeric structure consisting of connected tetranuclear clusters and supported by pivalate ligands and a framework of H-bonds has been revealed by single-crystal X-ray diffraction. While the compounds demonstrate similar PXRD patterns and unit cell parameters, the joint single-crystal XRD and pair distribution function data suggest the significant local structure change along the lanthanide series. The compounds exist as two packing polymorphs (α and ß) with similar ribbon geometry, but different supramolecular arrangement of the ribbons. Dehydration of either polymorph does not disturb the tetranuclear core but leads to a translational symmetry loss along the ribbon and a transformation of the 3D-ordered crystal into a 2D-ordered mesostructure. Rehydration of the mesostructure leads to the ß polymorph (except La and Ce), allowing the deliberate switching between the polymorphs via dehydration-rehydration evidenced by means of powder X-ray diffraction, pair distribution function analysis, and density functional theory calculations. Ab initio calculations reveal significant magnetic anisotropy of Ln3+ ions with ferro- and antiferromagnetic interactions within tetranuclear [Ln4(OH)2(piv)10(H2O)2] species. Magnetic susceptibility measurements demonstrated antiferromagnetic coupling, slow magnetic relaxation for Dy, Ho, and Er complexes, and field-induced single-chain magnetism for the Dy compound.

20.
Inorg Chem ; 60(13): 9461-9470, 2021 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-34128644

RESUMEN

A novel modification of the KCoPO4, δ-phase has been prepared by hydrothermal synthesis at 553 K. The compound crystallizes in the orthorhombic system with the unit-cell parameters a = 8.5031(8), b = 10.2830(5), c = 54.170(4) Å. The crystal structure was determined based on synchrotron low-temperature single-crystal X-ray diffraction data obtained from an inversion twin in the space group P212121 and refined to R = 0.077 for 5156 reflections with I > 3σ(I). The δ-KCoPO4 possesses a new structure type which is based on a framework built from sharing vertices Co- and P-centered tetrahedra. The {CoPO4-}∞ construction of tetrahedra may be described as assembled from networks formed by two topologically diverse six-membered rings of tetrahedra stacked together through vertex-bridging contacts along the a axis. The ratio of the (UUUDDD) and (UUDUDD) rings, where (U) and (D) denote the orientation of the tetrahedra in the six-membered rings up and down relative to the plane grids, is equal to 5:1. The (UUDUDD) rings form bands parallel to the [010] direction each surrounded from both sides along the c axis by slabs of five ribbons width having alternative (UUUDDD) topology. Open in the [100] direction channels incorporate K+ ions; this structural feature permits to suppose ion-conductive and/or electrochemical properties of the title compound. The possible mechanism of the δ → γ phase transition is discussed on the basis of the crystal chemical analysis of the KCoPO4 polymorphs. The title compound orders magnetically at TN = 24.8 K.

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