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2.
J Homosex ; 70(4): 754-778, 2023 Mar 21.
Artículo en Inglés | MEDLINE | ID: mdl-34762015

RESUMEN

Sexualized drug use is a form of sexual practice that resists risk-based discourses (otherwise referred to as "radical sex practices") and is reportedly common among gay, bisexual and other men who have sex with men (GBMSM). With the growth of online technologies, the use of hookup apps has also increased. We refer to men's use of drugs, apps, and sex form as "wired sex" that forms what post-structuralist theorists Deleuze and Guattari described as an assemblage. Perspectives of the health and social service providers who work directly with GBMSM has not been explored. This research project involved a critical discourse analysis of 13 semi-structured interviews with service providers in Canada to understand their perspectives and interactions with wired sex assemblages. We identified several themes reflecting the social and political effects of wired sex assemblages and discuss the implications of these effects on services provision with GBMSM.


Asunto(s)
Infecciones por VIH , Minorías Sexuales y de Género , Trastornos Relacionados con Sustancias , Masculino , Humanos , Homosexualidad Masculina , Infecciones por VIH/epidemiología , Conducta Sexual , Bisexualidad , Trastornos Relacionados con Sustancias/epidemiología , Trastornos Relacionados con Sustancias/terapia
3.
Can Commun Dis Rep ; 49(11-12): 457-464, 2023 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-38504878

RESUMEN

Background: In 2018, the Public Health Agency of Canada (PHAC) published a systematic review to calculate the risk of sexual transmission of human immunodeficiency virus (HIV) in the context of antiretroviral therapy (ART). In 2022, PHAC commissioned the Canadian Agency for Drugs and Technologies in Health (CADTH) to conduct a rapid review of evidence published since 2017. We undertook a meta-analysis of relevant studies from these two reviews. Methods: Studies from the rapid review that adequately assessed exposure (HIV viral load) and outcome (HIV seroconversion) were included and assessed for risk of bias (RoB) and certainty of evidence. Results were pooled to estimate the risk of HIV transmission per 100 person-years. Results: Three studies from the rapid review were eligible for inclusion and one was excluded after RoB assessment. In the remaining studies examining risk among people living with HIV who take ART and maintain a suppressed viral load (fewer than 200 copies/mL, measured every 4-6 months), no sexual transmissions of HIV were observed. The pooled incidence estimate based on these studies, and one from the 2018 PHAC review, was zero transmissions/100 person-years (95% CI: 0.00-0.10). No studies in the rapid review provided data on the risk of sexual transmission of HIV in situations of varying levels of viral load. Conclusion: This update highlights the consistency of evidence since the 2018 PHAC review. There remains no evidence of HIV transmission to sexual partners when a person living with HIV is on ART and maintains a suppressed viral load.

4.
Chem Rev ; 122(18): 14405-14439, 2022 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-35969894

RESUMEN

Fluorine is known to be a key element for various components of batteries since current electrolytes rely on Li-ion salts having fluorinated ions and electrode binders are mainly based on fluorinated polymers. Metal fluorides or mixed anion metal fluorides (mainly oxyfluorides) have also gained a substantial interest as active materials for the electrode redox reactions. In this review, metal fluorides for cathodes are considered; they are listed according to the dimensionality of the metal fluoride subnetwork. The synthesis conditions and the crystal structures are described; the electrochemical properties are briefly indicated, and the nature of the electron transport agent is noted. We stress the crucial importance of the elaboration processes to induce the presence of cation disorders, of anion substitutions (mainly F-/O2- or F-/OH-) or vacancies. Finally, we show that an accurate structural characterization is a key step to enable enhanced material performances to overcome several lasting roadblocks, namely the large irreversible capacity and poor energy efficiency that are frequently encountered.

5.
Proc Natl Acad Sci U S A ; 118(12)2021 03 23.
Artículo en Inglés | MEDLINE | ID: mdl-33723041

RESUMEN

Single-molecule force spectroscopy is a powerful tool for studying protein folding. Over the last decade, a key question has emerged: how are changes in intrinsic biomolecular dynamics altered by attachment to µm-scale force probes via flexible linkers? Here, we studied the folding/unfolding of α3D using atomic force microscopy (AFM)-based force spectroscopy. α3D offers an unusual opportunity as a prior single-molecule fluorescence resonance energy transfer (smFRET) study showed α3D's configurational diffusion constant within the context of Kramers theory varies with pH. The resulting pH dependence provides a test for AFM-based force spectroscopy's ability to track intrinsic changes in protein folding dynamics. Experimentally, however, α3D is challenging. It unfolds at low force (<15 pN) and exhibits fast-folding kinetics. We therefore used focused ion beam-modified cantilevers that combine exceptional force precision, stability, and temporal resolution to detect state occupancies as brief as 1 ms. Notably, equilibrium and nonequilibrium force spectroscopy data recapitulated the pH dependence measured using smFRET, despite differences in destabilization mechanism. We reconstructed a one-dimensional free-energy landscape from dynamic data via an inverse Weierstrass transform. At both neutral and low pH, the resulting constant-force landscapes showed minimal differences (∼0.2 to 0.5 kBT) in transition state height. These landscapes were essentially equal to the predicted entropic barrier and symmetric. In contrast, force-dependent rates showed that the distance to the unfolding transition state increased as pH decreased and thereby contributed to the accelerated kinetics at low pH. More broadly, this precise characterization of a fast-folding, mechanically labile protein enables future AFM-based studies of subtle transitions in mechanoresponsive proteins.


Asunto(s)
Microscopía de Fuerza Atómica/métodos , Modelos Moleculares , Pliegue de Proteína , Proteínas/química , Concentración de Iones de Hidrógeno , Fenómenos Mecánicos , Microscopía de Fuerza Atómica/instrumentación , Imagen Individual de Molécula
6.
Proc Natl Acad Sci U S A ; 118(12)2021 03 23.
Artículo en Inglés | MEDLINE | ID: mdl-33723050

RESUMEN

Multiple gram-negative bacteria encode type III secretion systems (T3SS) that allow them to inject effector proteins directly into host cells to facilitate colonization. To be secreted, effector proteins must be at least partially unfolded to pass through the narrow needle-like channel (diameter <2 nm) of the T3SS. Fusion of effector proteins to tightly packed proteins-such as GFP, ubiquitin, or dihydrofolate reductase (DHFR)-impairs secretion and results in obstruction of the T3SS. Prior observation that unfolding can become rate-limiting for secretion has led to the model that T3SS effector proteins have low thermodynamic stability, facilitating their secretion. Here, we first show that the unfolding free energy ([Formula: see text]) of two Salmonella effector proteins, SptP and SopE2, are 6.9 and 6.0 kcal/mol, respectively, typical for globular proteins and similar to published [Formula: see text] for GFP, ubiquitin, and DHFR. Next, we mechanically unfolded individual SptP and SopE2 molecules by atomic force microscopy (AFM)-based force spectroscopy. SptP and SopE2 unfolded at low force (Funfold ≤ 17 pN at 100 nm/s), making them among the most mechanically labile proteins studied to date by AFM. Moreover, their mechanical compliance is large, as measured by the distance to the transition state (Δx‡ = 1.6 and 1.5 nm for SptP and SopE2, respectively). In contrast, prior measurements of GFP, ubiquitin, and DHFR show them to be mechanically robust (Funfold > 80 pN) and brittle (Δx‡ < 0.4 nm). These results suggest that effector protein unfolding by T3SS is a mechanical process and that mechanical lability facilitates efficient effector protein secretion.


Asunto(s)
Fenómenos Fisiológicos Bacterianos , Proteínas Bacterianas/metabolismo , Sistemas de Secreción Tipo III/metabolismo , Proteínas Bacterianas/química , Bacterias Gramnegativas/fisiología , Bacterias Gramnegativas/ultraestructura , Microscopía de Fuerza Atómica , Estabilidad Proteica , Salmonella/fisiología , Salmonella/ultraestructura , Termodinámica
7.
Sci Total Environ ; 774: 145541, 2021 Jun 20.
Artículo en Inglés | MEDLINE | ID: mdl-33609844

RESUMEN

Leptospirosis is a waterborne zoonosis (60,000 infections and 1 million deaths annually). Knowledge about the disease in the urban context is surprisingly rare, especially in Africa. Here, we provide the first study of leptospires in waters within an African city. A simple centrifugation-based method was developed to screen waterborne leptospires from remote or poorly areas. Major ions, trace elements, stable isotopes and pathogenic Leptospira were then seasonally investigated in 193 water samples from three neighborhoods of Cotonou (Benin) with different socio-environmental and hydrographic characteristics. Firstly, no leptospire was detected in tap waters. Secondly, although surface contamination cannot be excluded, one groundwater well was found leptospire positive. Thirdly, pathogenic Leptospira mainly contaminated surface waters of temporary and permanent ponds (9.5% and 27.3% of total prevalence, respectively). Isotopic signatures suggest that leptospires occurred in pond waters formed at the beginning of the rainy season following low to moderate rainfall events. Nevertheless, Leptospira-containing waters possess physico-chemical characteristics that are similar to the spectrum of waters sampled throughout the three sites, thus suggesting that Cotonou waters are widely compatible with Leptospira survival. The frequent contact with water exposes Cotonou inhabitants to the risk of leptospirosis which deserves more attention from public health authorities.


Asunto(s)
Leptospira , Leptospirosis , Animales , Benin/epidemiología , Ciudades , Leptospirosis/epidemiología , Calidad del Agua
8.
Dalton Trans ; 49(24): 8186-8193, 2020 Jun 23.
Artículo en Inglés | MEDLINE | ID: mdl-32515454

RESUMEN

In our search for novel insertion compounds for Li-based batteries, we have identified a new mixed iron vanadium based Hexagonal Tungsten Bronze (HTB) type phase. Its synthesis involves two steps which consist first of preparing mixed metal hydrated fluoride Fe1.64V1.36F8(H2O)2 by a microwave assisted thermal process, followed by thermal treatment under air to obtain metastable HTB-(Fe0.55V0.45)F2.67(OH)0.33 hydroxyfluoride. 57Fe Mössbauer spectrometry demonstrates the presence of oxidation states Fe2+ and Fe3+ in Fe1.64V1.36F8(H2O)2 as opposed to only Fe3+ in HTB-(Fe0.55V0.47)F2.67(OH)0.33. Moreover, the Mössbauer spectra recorded at 77 K reveal that none of the compounds shows magnetic ordering owing to the presence of V3+ distributed over the crystallographic sites of Fe3+. Complementary X-ray spectroscopy and Rietveld refinement further confirm the successful synthesis of HTB-(Fe0.55V0.45)F2.67(OH)0.33. Electrochemically, the new HTB-(Fe0.55V0.45)F2.67(OH)0.33 shows a first discharge capacity of 181 mA h g-1 with 67% of this capacity remaining upon cycling. Unlike HTB-FeF2.66(OH)0.34, the structure remains stable after the first discharge confirming the positive effect of vanadium in the HTB network.

9.
Sociol Health Illn ; 41(3): 484-501, 2019 03.
Artículo en Inglés | MEDLINE | ID: mdl-30450606

RESUMEN

The advancements of "treatment as prevention" (TasP), "undetectable viral load" (UVL) and "pre-exposure prophylaxis" (PrEP) are redefining HIV prevention standards. Relying on the concept of biosociality, this article explores how gay men rally around, debate, and sometimes disagree about these emerging HIV prevention technologies. This article is based on data from the Resonance Project, a Canadian community-based research project. Twelve focus groups (totalling 86 gay and bisexual men) were held in three Canadian cities (Montreal, Toronto, Vancouver) in 2013-2014. Respondents view UVL and PrEP through the prism of their generational experience of HIV prevention. In this respect, biosocialities highlight an experiential dimension that is tied to the context of the HIV epidemic. The biosocialities of HIV prevention are also built around serological identities. However, our study shows the diversity of these positions. Analysis grounded in biosocialities is useful for better understanding how scientific information circulates, is made sense of, and generates debate among gay men.


Asunto(s)
Antirretrovirales/administración & dosificación , Bisexualidad/psicología , Infecciones por VIH/prevención & control , Homosexualidad Masculina/psicología , Profilaxis Pre-Exposición/métodos , Minorías Sexuales y de Género/psicología , Adulto , Canadá , Investigación Participativa Basada en la Comunidad , Grupos Focales , Infecciones por VIH/virología , Humanos , Masculino , Persona de Mediana Edad , Grupos Raciales , Conducta de Reducción del Riesgo , Asunción de Riesgos , Responsabilidad Social , Carga Viral
10.
Sci Total Environ ; 612: 672-682, 2018 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-28866395

RESUMEN

Tritium background levels in various environmental compartments are deeply needed in particular to assess radiological impact, especially in river systems where most of releases from nuclear facilities are performed. The present study aims to identify the main environmental factors that influence tritium background levels in rivers at the regional scale. 41 samples were collected from 2014 to 2016 along 17 small rivers in the south of France. All were located out of the influence of direct releases from nuclear facilities. Tritiated water (HTO) concentrations measured in water samples ranged from 0.12±0.11 to 0.86±0.15BqL-1 and HTO concentrations in rains were modelled between 2015 and 2016 over the study period referring to time series acquired from 1963 to 2014 at Thonon-les-Bains monitoring station. The results of tritium concentrations in rivers studied present a significant variability and are more than twice lower than forecasted values in rain. Multiple linear regressions allowed identifying that HTO concentration in rains, watershed area and altitude were the main tested parameters that are linked to the variability of HTO concentrations in the studied rivers. Finally, HTO fluxes delivered to the Mediterranean Sea by French coastal rivers out of influence of nuclear releases were estimated. The results highlight that those account for around 1% of HTO exported while 99% are transferred by the nuclearized Rhone River.

11.
Biophys J ; 113(12): 2595-2600, 2017 Dec 19.
Artículo en Inglés | MEDLINE | ID: mdl-29132641

RESUMEN

Atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) is a powerful yet accessible means to characterize the unfolding/refolding dynamics of individual molecules and resolve closely spaced, transiently occupied folding intermediates. On a modern commercial AFM, these applications and others are now limited by the mechanical properties of the cantilever. Specifically, AFM-based SMFS data quality is degraded by a commercial cantilever's limited combination of temporal resolution, force precision, and force stability. Recently, we modified commercial cantilevers with a focused ion beam to optimize their properties for SMFS. Here, we extend this capability by modifying a 40 × 18 µm2 cantilever into one terminated with a gold-coated, 4 × 4 µm2 reflective region connected to an uncoated 2-µm-wide central shaft. This "Warhammer" geometry achieved 8.5-µs resolution coupled with improved force precision and sub-pN stability over 100 s when measured on a commercial AFM. We highlighted this cantilever's biological utility by first resolving a calmodulin unfolding intermediate previously undetected by AFM and then measuring the stabilization of calmodulin by myosin light chain kinase at dramatically higher unfolding velocities than in previous AFM studies. More generally, enhancing data quality via an improved combination of time resolution, force precision, and force stability will broadly benefit biological applications of AFM.


Asunto(s)
Microscopía de Fuerza Atómica/instrumentación , Diseño de Equipo , Oro
12.
J Am Chem Soc ; 139(29): 9867-9875, 2017 07 26.
Artículo en Inglés | MEDLINE | ID: mdl-28677396

RESUMEN

Atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) is a powerful yet accessible means to characterize mechanical properties of biomolecules. Historically, accessibility relies upon the nonspecific adhesion of biomolecules to a surface and a cantilever and, for proteins, the integration of the target protein into a polyprotein. However, this assay results in a low yield of high-quality data, defined as the complete unfolding of the polyprotein. Additionally, nonspecific surface adhesion hinders studies of α-helical proteins, which unfold at low forces and low extensions. Here, we overcame these limitations by merging two developments: (i) a polyprotein with versatile, genetically encoded short peptide tags functionalized via a mechanically robust Hydrazino-Pictet-Spengler ligation and (ii) the efficient site-specific conjugation of biomolecules to PEG-coated surfaces. Heterobifunctional anchoring of this polyprotein construct and DNA via copper-free click chemistry to PEG-coated substrates and a strong but reversible streptavidin-biotin linkage to PEG-coated AFM tips enhanced data quality and throughput. For example, we achieved a 75-fold increase in the yield of high-quality data and repeatedly probed the same individual polyprotein to deduce its dynamic force spectrum in just 2 h. The broader utility of this polyprotein was demonstrated by measuring three diverse target proteins: an α-helical protein (calmodulin), a protein with internal cysteines (rubredoxin), and a computationally designed three-helix bundle (α3D). Indeed, at low loading rates, α3D represents the most mechanically labile protein yet characterized by AFM. Such efficient SMFS studies on a commercial AFM enable the rapid characterization of macromolecular folding over a broader range of proteins and a wider array of experimental conditions (pH, temperature, denaturants). Further, by integrating these enhancements with optical traps, we demonstrate how efficient bioconjugation to otherwise nonstick surfaces can benefit diverse single-molecule studies.


Asunto(s)
Proteínas/química , Concentración de Iones de Hidrógeno , Microscopía de Fuerza Atómica , Conformación Proteica en Hélice alfa , Temperatura
13.
Dalton Trans ; 46(11): 3761-3769, 2017 Mar 14.
Artículo en Inglés | MEDLINE | ID: mdl-28262874

RESUMEN

Pure tysonite-type Ce1-xSrxF3-x solid solutions for 0 ≤ x < 0.15 were prepared by a solid-state route at 900 °C. The cell parameters follow Vegard's laws for 0 ≤ x ≤ 0.10 and the solubility limit is identified (0.10 < xlimit < 0.15). For 0 ≤ x ≤ 0.05, the F2-(Ce,Sr) and F3-(Ce,Sr) bond distances into [Ce1-xSrxF](2-x)+ slabs strongly vary with x. This slab buckling is maximum around x = 0.025 and strongly affects the more mobile F1 fluoride ions located between the slabs. The 19F MAS NMR spectra show the occurrence of F1-F2,3 exchange at 64 °C. The fraction of mobile F2,3 atoms deduced from the relative intensity of the NMR resonance is maximum for Ce0.99Sr0.01F2.99 (22% at 64 °C) while this fraction linearly increases with x for La1-xAExF3-x (AE = Ba, Sr). The highest conductivity found for Ce0.975Sr0.025F2.975 (3 × 10-4 S cm-1 at RT, Ea = 0.31 eV) is correlated to the largest dispersion of F2-(Ce,Sr) and F3-(Ce,Sr) distances which induces the maximum sheet buckling. Such a relationship between composition, structural features and fluoride ion conductivity is extended to other tysonite-type fluorides. The key role of the difference between AE2+ and RE3+ ionic radii and of the thickness of the slab buckling is established and could allow designing new ionic conductors.

14.
Open Orthop J ; 10: 357-63, 2016.
Artículo en Inglés | MEDLINE | ID: mdl-27563365

RESUMEN

OBJECTIVES: The purpose of this study was to compare the intra-operative benefits and the clinical outcomes from kinematic or mechanical alignment for total knee arthroplasty (TKA) in patients undergoing revision of failed unicompartmental kneel arthroplasty (UKA) to TKA. METHODS: Ten revisions were performed with a kinematic alignment technique and 11 with a mechanical alignment. Measurements of the hip-knee-ankle angle (HKA), the lateral distal femoral angle (LDFA), and the medial proximal tibial angle (MPTA) were performed using long-leg radiographs. The need for augments, stems, and constrained inserts was compared between groups. Clinical outcomes were compared using the WOMAC score along with maximum distance walked as well as knee range of motion obtained prior to discharge. All data was obtained by a retrospective review of patient files. RESULTS: The kinematic group required less augments, stems, and constrained inserts than the mechanical group and thinner polyethylene bearings. There were significant differences in the lateral distal femoral angle (LDFA) and the medial proximal tibial angle (MPTA) between the two groups (p<0.05). The mean WOMAC score obtained at discharge was better in the kinematic group as was mean knee flexion. At last follow up of 34 months for the kinematic group and 58 months for the mechanical group, no orthopedic complications or reoperations were recorded. CONCLUSION: Although this study has a small patient cohort, our results suggest that kinematic alignment for TKA after UKA revision is an attractive method. Further studies are warranted.

15.
BMC Cancer ; 16: 498, 2016 07 19.
Artículo en Inglés | MEDLINE | ID: mdl-27430321

RESUMEN

BACKGROUND: The 2010 guidelines of the French National Cancer Institute (INCa) classify patients with endometrial cancer into three risk groups for lymph node invasion and recurrence on the basis of MRI and histological analysis of an endometrial specimen obtained preoperatively. The classification guides therapeutic choices, which may include pelvic and/or para-aortic lymphadenectomy. The purpose of this study was to evaluate the diagnostic performance of preoperative assessment to help identify intermediate- or high-risk patients requiring lymphadenectomy. METHODS: The study included all patients who underwent surgery for endometrial cancer between January 2010 and December 2013 at either Rennes University Hospital or Vannes Regional Hospital. The criteria for eligibility included a preoperative assessment with MRI and histological examination of an endometrial sample. A histological comparison was made between the preoperative and surgical specimens. RESULTS: Among the 91 patients who underwent a full preoperative assessment, the diagnosis of intermediate- or high-risk endometrial cancer was established by MRI and histology with a sensitivity of 70 %, specificity of 82 %, positive predictive value (PPV) of 87 %, negative predictive value (NPV) of 61 %, positive likelihood ratio (LR+) of 3.8 and negative likelihood ratio (LR-) of 0.3. The risk group was underestimated in 32 % of patients and overestimated in 7 % of patients. MRI underestimated endometrial cancer stage in 20 % of cases, while endometrial sampling underestimated the histological type in 4 % of cases and the grade in 9 % of cases. CONCLUSION: The preoperative assessment overestimated or underestimated the risk of recurrence in nearly 40 % of cases, with errors in lesion type, grade or stage. Erroneous preoperative risk assessment leads to suboptimal initial surgical management of patients with endometrial cancer.


Asunto(s)
Neoplasias Endometriales/diagnóstico por imagen , Endometrio/diagnóstico por imagen , Imagen por Resonancia Magnética/métodos , Cuidados Preoperatorios/métodos , Adulto , Anciano , Anciano de 80 o más Años , Neoplasias Endometriales/clasificación , Neoplasias Endometriales/cirugía , Endometrio/patología , Endometrio/cirugía , Femenino , Humanos , Escisión del Ganglio Linfático , Ganglios Linfáticos/patología , Metástasis Linfática , Persona de Mediana Edad , Recurrencia Local de Neoplasia , Estadificación de Neoplasias , Reproducibilidad de los Resultados , Estudios Retrospectivos , Medición de Riesgo/métodos , Medición de Riesgo/estadística & datos numéricos , Factores de Riesgo
16.
Nano Lett ; 15(10): 7091-8, 2015 Oct 14.
Artículo en Inglés | MEDLINE | ID: mdl-26421945

RESUMEN

Atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) is widely used to mechanically measure the folding and unfolding of proteins. However, the temporal resolution of a standard commercial cantilever is 50-1000 µs, masking rapid transitions and short-lived intermediates. Recently, SMFS with 0.7-µs temporal resolution was achieved using an ultrashort (L = 9 µm) cantilever on a custom-built, high-speed AFM. By micromachining such cantilevers with a focused ion beam, we optimized them for SMFS rather than tapping-mode imaging. To enhance usability and throughput, we detected the modified cantilevers on a commercial AFM retrofitted with a detection laser system featuring a 3-µm circular spot size. Moreover, individual cantilevers were reused over multiple days. The improved capabilities of the modified cantilevers for SMFS were showcased by unfolding a polyprotein, a popular biophysical assay. Specifically, these cantilevers maintained a 1-µs response time while eliminating cantilever ringing (Q ≅ 0.5). We therefore expect such cantilevers, along with the instrumentational improvements to detect them on a commercial AFM, to accelerate high-precision AFM-based SMFS studies.


Asunto(s)
Microscopía de Fuerza Atómica/métodos , Análisis Espectral/métodos
17.
Dalton Trans ; 44(45): 19625-35, 2015 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-26246328

RESUMEN

Pure tysonite La1-xBaxF3-x solid solutions for x < 0.15 were prepared by solid state synthesis in a platinum tube under an azote atmosphere with subsequent quenching for 0.07 ≤x < 0.15. The solid solutions were studied by X-ray, electron and neutron diffractions and by (19)F NMR and impedance spectroscopy. The evolution of the cell parameters obeying Vegard's rule was determined for 0 < x≤ 0.15 and atomic position parameters were accurately refined for x = 0.03, 0.07 and 0.10. The chemical pressure induced by large Ba(2+) cations leads to an increase of the unit cell parameters. Fluorine environment and mobilities are discussed on the basis of the results of neutron diffraction and (19)F solid state NMR. The F1 subnetwork is lacunar; fluorine exchange occurs according to the order: F1-F1 and F1-F2,3. 2D EXSY NMR spectra of La0.97Ba0.03F2.97 reveal, for the first time, a chemical exchange between F2 and F3 sites that requires two successive jumps. The ionic conductivity was evaluated from sintered pellets and different shaping methods were compared. The only structural features which could explain the conductivity maximum are a crossover together with a smaller dispersion of F1-F1,2,3 distances at x = 0.05-0.07.

18.
Dalton Trans ; 44(17): 7951-9, 2015 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-25826156

RESUMEN

The exploration of the FeF3/FeF2-Hamtetraz-HF system in dimethylformamide by solvothermal synthesis evidences two isostructural 3D hybrid fluoroferrates. They are prepared from the same starting mixture at two different synthesis temperatures: 120 °C for [Hdma]·(Fe4(II)Fe(III)F8(H2O)2(amtetraz)4) () and 140 °C for [Hdma]1.5·(Fe4.5(II)Fe0.5(III)F7(H2O)(HCOO)(amtetraz)4) (). Both compounds are characterized by single crystal X-ray diffraction, X-ray thermodiffraction, TGA analysis, Mössbauer spectrometry and SQUID magnetometry. They crystallize in the monoclinic system and are built from two distinct chains connected by aminotetrazolate anions. The first chain ∞(Fe(II)FN4) is common to and and can be found in numerous fluorides. In the second chain ∞(Fe3X12) (X = F, N, O), iron cations adopt both valence states Fe(ii)/Fe(iii). The hydrolysis of DMF implies the formation of a [Hdma](+) cation and a (HCOO)(-) anion. The presence of Fe(3+) in both phases is evidenced by (57)Fe Mössbauer spectrometry. The magnetic properties are studied and two transitions from a paramagnetic regime to a long range ordered state below 30 K and 5 K are identified.

20.
Acta Crystallogr C Struct Chem ; 70(Pt 5): 512-6, 2014 May.
Artículo en Inglés | MEDLINE | ID: mdl-24816024

RESUMEN

The title compound, (H3O)2NaAl3F12 [dihydronium sodium trialuminum(III) dodecafluoride], was obtained by solvothermal synthesis from the reaction of aluminium hydroxide, sodium hydroxide, 1,2,4-triazole and aqueous HF in ethanol at 463 K for 48 h. The structure consists of AlF6 octahedra organized in [AlF4(-)]n HTB-type sheets (HTB is hexagonal tungsten bronze) separated by H3O(+) and Na(+) cations.

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