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1.
Inorg Chem ; 61(46): 18476-18485, 2022 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-36343162

RESUMO

NaGaS2 is a newly discovered compound that has already shown great promise for a variety of applications because of its layered structure and ion exchange properties. In this work, crystalline NaGaS2 has been synthesized by an alternative method to what has been previously published, namely, by mechanochemistry, either by a direct one-step process or by a two-step process. In the one-step process, crystalline NaGaS2 is directly formed by milling sodium sulfide Na2S and gallium(III) sulfide Ga2S3. However, an amorphous material is present in majority together with the crystalline phase. In the two-step process, amorphous NaGaS2 is first obtained by mechanical milling and then heated above its glass transition temperature to obtain a glass-ceramic mainly composed of crystalline NaGaS2. For the two-step process, changes of the local atomic-level structure in amorphous NaGaS2 and after crystallization were analyzed by high-field solid-state nuclear magnetic resonance (NMR) spectroscopy as well as by X-ray total scattering and pair distribution function (PDF) analysis. Based on quantitative analysis on the 23Na NMR spectra, modifying the annealing treatment can promote the formation of the crystalline phase up to a molar fraction of 83.8%.

2.
J Phys Chem Lett ; 13(40): 9390-9395, 2022 Oct 13.
Artigo em Inglês | MEDLINE | ID: mdl-36190798

RESUMO

The very strong negative thermal expansion in the porous aluminophosphate AlPO4-17 with a hexagonal erionite structure was tuned by the insertion of oxygen molecules at high pressure. The structure of the oxygen-filled material was determined in situ at high pressure by synchrotron, single-crystal X-ray diffraction. The thermal expansion of this material was measured precisely at 0.38 GPa by synchrotron X-ray powder diffraction. Whereas the overall volume thermal expansion only exhibits a small change with respect to empty AlPO4-17 at ambient pressure, the expansion along the a direction decreases almost to zero and the expansion along c increases by a factor of 7. Such highly anisotropic thermal expansion properties are of great interest for mechanical and optical applications as in two directions the dimensions of the material are extremely stable, whereas a very strong linear negative thermal expansion of -2.2 × 10-5 K-1 is observed in the perpendicular direction. Guest insertion is thus a very powerful tool for tuning the thermal expansion properties of porous materials.

3.
J Phys Chem Lett ; : 6919-6926, 2022 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-35867700

RESUMO

While HgTe nanocrystals (NCs) in the mid-infrared region have reached a high level of maturity, their far-infrared counterparts remain far less studied, raising the need for an in-depth investigation of the material before efficient device integration can be considered. Here, we explore the effect of temperature and pressure on the structural, spectroscopic, and transport properties of HgTe NCs displaying an intraband absorption at 10 THz. The temperature leads to a very weak modulation of the spectrum as opposed to what was observed for strongly confined HgTe NCs. HgTe NC films present ambipolar conduction with a clear prevalence of electron conduction as confirmed by transistor and thermoelectric measurements. Under the application of pressure, the material undergoes phase transitions from the zinc blende to cinnabar phase and later to the rock salt phase which we reveal using joint X-ray diffraction and infrared spectroscopy measurements. We discuss how the pressure existence domain of each phase is affected by the particle size.

4.
ACS Nano ; 16(2): 2901-2909, 2022 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-35107969

RESUMO

The crystal structure of atomically defined colloidal II-VI semiconductor nanoplatelets (NPLs) induces the self-assembly of organic ligands over thousands of square nanometers on the top and bottom basal planes of these anisotropic nanoparticles. NPLs curl into helices under the influence of the surface stress induced by these ligands. We demonstrate the control of the radii of NPL helices through the ligands described as an anchoring group and an aliphatic chain of a given length. A mechanical model accounting for the misfit strain between the inorganic core and the surface ligands predicts the helices' radii. We show how the chirality of the helices can be tuned by the ligands anchoring group and inverted from one population to another.

5.
Chemosphere ; 287(Pt 2): 132139, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34509019

RESUMO

Long-term uranium mobility in tailings is an environmental management issue. The present study focuses on two U-enriched layers, surficial and buried 14.5 m, of the tailings pile of Cominak, Niger. The acidic and oxidizing conditions of the tailings pile combined with evapotranspiration cycles related to the Sahelian climate control U speciation. Uraninite, brannerite, and moluranite as well as uranophane are relict U phases. EXAFS spectroscopy, HR-XRD, and SEM/WDS highlight the major role of uranyl sulfate groups in uranium speciation. Uranyl phosphate neoformation in the buried layer (paleolayer) acts as an efficient trap for uranium.


Assuntos
Urânio , Níger , Fosfatos , Sulfatos , Óxidos de Enxofre , Urânio/análise
6.
ACS Nano ; 16(1): 271-284, 2022 01 25.
Artigo em Inglês | MEDLINE | ID: mdl-34963049

RESUMO

Magnetite and maghemite multicore nanoflowers (NFs) synthesized using the modified polyol-mediated routes are to date among the most effective nanoheaters in magnetic hyperthermia (MHT). Recently, magnetite NFs have also shown high photothermal (PT) performances in the most desired second near-infrared (NIR-II) biological window, making them attractive in the field of nanoparticle-activated thermal therapies. However, what makes magnetic NFs efficient heating agents in both modalities still remains an open question. In this work, we investigate the role of many parameters of the polyol synthesis on the final NFs' size, shape, chemical composition, number of cores, and crystallinity. These nanofeatures are later correlated to the magnetic, optical, and electronic properties of the NFs as well as their collective macroscopic thermal properties in MHT and PT to find relationships between their structure, properties, and function. We evidence the critical role of iron(III) and heating ramps on the elaboration of well-defined NFs with a high number of multicores. While MHT efficiency is found to be proportional to the average number of magnetic cores within the assemblies, the optical responses of the NFs and their collective photothermal properties depend directly on the mean volume of the NFs (as supported by optical cross sections numerical simulations) and strongly on the structural disorder in the NFs, rather than the stoichiometry. The concentration of defects in the nanostructures, evaluated by photoluminescence and Urbach energy (EU), evidence a switch in the optical behavior for a limit value of EU = 0.4 eV where a discontinuous transition from high to poor PT efficiency is also observed.


Assuntos
Compostos Férricos , Hipertermia Induzida , Compostos Férricos/química , Óxido Ferroso-Férrico , Fenômenos Magnéticos
7.
Angew Chem Int Ed Engl ; 60(16): 8803-8807, 2021 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-33496370

RESUMO

The [FeII (C6 F5 Tp)2 ] spin-crossover complex is an atypical molecular switch, which can be converted upon annealing between two archetypal spin-crossover behaviours: from an extremely gradual spin-crossover to a broad hysteretic spin-transition (of ca. 65 K). The hysteresis shows an uncommon "rounded shape" that is reproducible upon cycling temperature. In depth structural studies reveal a first crystal phase transition, which occurs upon melting and recrystallizing at high temperature. This first irreversible transition is associated with a radical change in the crystal packing. More importantly, the "rounded and broad" hysteretic transition is shown to occur in a non-cooperative SCO system and is associated with the occurrence of a symmetry-breaking phase transition that appears when roughly ca. 50 % of the SCO complexes are switched.

8.
Dalton Trans ; 50(2): 681-688, 2021 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-33332496

RESUMO

The use of solvothermal conditions has succesfully led to the preparation of heterometallic 1D coordination polymers from a co-bidentate-tridentate phenolato-oxamato ligand. The reaction of the N-(2-hydoxyphenyl)oxamic acid (ohpma) with acetate salts of transition metal ions at 80 °C has yielded the heterobimetallic [Cu(ohpma)M(OAc)(DMF)2] (M = Co (1); Mn (2)) and the heterotrimetallic [Cu(ohpma)Co0.57Mn0.43(OAc)(DMF)2] (3) chain compounds. Single-crystal and powder diffraction studies show that the polymers are isostructural. Magnetic studies suggest the existence of an inter-chain two-dimensional antiferromagnetic interaction taking place in compounds 1-3.

9.
Angew Chem Int Ed Engl ; 59(39): 17272-17276, 2020 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-32568424

RESUMO

A key challenge in the design of magnetic molecular switches is to obtain bistability at room temperature. Here, we show that application of moderate pressure makes it possible to convert a paramagnetic FeIII 2 CoII 2 square complex into a molecular switch exhibiting a full dia- to paramagnetic transition: FeII CoIII ⇔ FeIII CoII . Moreover, the complex follows a rare behavior: the higher the pressure, the broader the magnetic hysteresis. Thus, the application of an adequate pressure allows inducing a magnetic bistability at room temperature with predictable hysteresis width. The structural studies at different pressures suggest that the pressure-enhanced bistability is due to the strengthening of intermolecular interactions upon pressure increase. An original microscopic Ising-like model including pressure effects is developed to simulate this unprecedented behavior. Overall, this study shows that FeCo complexes could be very sensitive piezo switches with potential use as sensors.

10.
Front Chem ; 7: 830, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31850318

RESUMO

The binary assembly DDA-{Mo132}/OA-γ-Fe2O3 (DDA = didodecyldimethylammonium, {Mo132} = [Mo132O372(CH3COO)30(H2O)72]42-, OA = oleic acid) constitutes one of the two examples in the literature of binary superlattices made of a mixing of nanocrystals and oxo-clusters. In a precedent work, we reported in details the preparation of such magnetic binary systems and studied the effect of the nature of the polyoxometalates (POMs) on the magnetic properties. In the present paper, we study the stability of this model binary assembly under heating at various temperatures. Indeed, especially if magnetic and/or transport properties are targeted, an annealing can be essential to change the phase of the nanocrystals in a more magnetic one and/or to desorb the organic capping of the nano-objects that can constitute an obstacle to the electronic communication between the nano-objects. We gave evidence that the maghemite organization in the binary assembly is maintained until 370°C under vacuum thanks to the presence of the POMs. This latter evolve in the phase MoO3, but still permits to avoid the aggregation of the nanocrystals as well as preserve their periodical arrangement. On the contrary, an assembly made of pure γ-Fe2O3 nanocrystals displays a clear aggregation of the nano-objects from 370°C, as attested by transmission and scanning electronic microscopies and confirmed by magnetic measurements. The stability of the magnetic nanocrystals in such POMs/nanocrystals assemblies opens the way to (i) the elaboration of new binary assemblies from POMs and numerous kinds of nanocrystals with a good control on the magnetic properties and to (ii) the investigation of new physical properties as exchange coupling, or magneto-transport in such systems.

11.
Inorg Chem ; 58(20): 14204-14211, 2019 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-31593448

RESUMO

By means of single-crystal X-ray diffraction, we give direct crystallographic evidence of a centrosymmetry breaking below TS = 200 K, concomitant with the onset of a commensurate structural modulation in the quadruple perovskite YMn3Mn4O12. This result, which explains the anomalously large thermal coefficient of the Y3+ ion in previously reported structural models, is attributed to the small size of the Y3+ ion, which causes its underbonding within the dodecahedral coordination polyhedron. The present data are consistent with a commensurate superstructure described by an I-centered pseudo-orthorhombic cell with polar Ia symmetry and a ≈ aF√2 = 10.4352(7) Å, b ≈ 2bF = 14.6049(9) Å, c ≈ cF√2 = 10.6961(7) Å, and ß = 90.110(3)°, where aF ≈ cF ≈ 7.45 Å, bF ≈ 7.34 Å, and ß ≈ 91° are the unit cell parameters of the I2/m structure observed at room temperature. Consistent with the above polar structure, at lower temperature, T* = 70 K, we observe in polycrystalline samples an anomaly of the direct current (DC) and alternating current (AC) magnetization, concomitant with the appearance of a net electric polarization, as indicated by pyrocurrent and dielectric constant measurements. These results, complemented by electrical transport measurements, suggest a magnetic ferroelectricity driven by short-range magnetic order in YMn3Mn4O12.

12.
Dalton Trans ; 48(22): 7899-7909, 2019 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-31086883

RESUMO

The development of luminescent mechanochromic materials depends mainly on the possibility to rationally design them with the desired properties. Molecular copper iodide clusters constitute an unprecedented family of compounds exhibiting great changes of their luminescence properties upon mechanical stress. From previous studies, the mechanochromic properties of cubane [Cu4I4L4] (L = organic ligand) clusters have been attributed to modifications of cuprophilic interactions induced by mechanical solicitation. In this study, we ascertain our hypothesis by choosing to study the luminescence mechanochromism of a [Cu4I4(PPh3)4] cluster which presents two crystalline polymorphs exhibiting strikingly different Cu-Cu bond lengths. As forecasted, only one of these two polymorphs exhibits mechanochromic properties. Structural and optical characterization methods are reported along with structural characterization under controlled pressure allowing a precise analysis of the structural changes occurring under mechanical stress. In addition to confirming our mechanism based on enhancement of cuprophilic interactions under pressure, this study demonstrates the possibility of prediction of mechanochromic properties in the family of copper iodide compounds that constitutes a step further toward the rational design of stimuli-responsive materials.

13.
Nanoscale ; 11(11): 5102-5115, 2019 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-30839975

RESUMO

The nature of defects in ZnO smoke was studied at different stages of the material's history by combining photoluminescence (PL) and electron paramagnetic resonance (EPR) spectroscopy. In contrast to studies previously reported on ZnO nanopowders, high vacuum conditions (P < 10-5 mbar) have been applied during sample storage, handling and spectroscopic investigations. Two pairs of violet-PL/EPR signals (2.88 eV/ g = 1.956 and 2.80 eV/ g = 1.960) were observed in the as-synthesized ZnO powder and attributed to surface (dominant) and bulk zinc interstitials (Zni+). Upon annealing in O2-poor conditions, green-PL emission (2.41 eV) and EPR signal at g = 2.002 develop along with EPR signals specific of superoxide radicals (O2-). In the absence of any external O2 supply, the oxygen necessary for the creation of a notable amount of O2- is provided by the lattice of ZnO smoke, so that the green emission and its EPR counterpart are unambiguously assigned to singly charged oxygen vacancies (VO+). Annealing at high PO2 results in a broad PL emission (∼2.07 eV) without an EPR counterpart. This yellow emission was assigned to peroxide-like surface species (O22-). Overall, this study shows that the visible emissions in ZnO smoke nanopowders can range from violet, over green to yellow as a function of sample history and that the corresponding PL/EPR fingerprints can serve as guidelines for the recognition of defects in other ZnO types.

14.
Theranostics ; 9(5): 1288-1302, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30867831

RESUMO

Innovative synthesis routes revolutionized nanomaterial combination and design possibilities resulting in a new generation of fine-tuned nanoparticles featuring exquisite shape and constitution control. However, there is still room for improvement when it comes to the development of multi-functional nanoparticle agents merging a plurality of therapeutic functions to tackle tumors simultaneously by synergic mechanisms. Herein, we report the design of an optimized nanohybrid for cancer tri-therapy featuring a maghemite (γ-Fe2O3) nanoflower-like multicore nanoparticle conceived for efficient magnetic hyperthermia (MHT) and a spiky copper sulfide shell (IONF@CuS) with a high near-infrared (NIR) absorption coefficient suitable for photothermal (PTT) and photodynamic therapy (PDT). Methods: Spiky-like IONF@CuS nanohybrids were obtained through a straightforward and scalable water-based template sacrificial synthesis, which allows the shell shape control by tuning polyvinylpyrrolidone (PVP) concentration. A comprehensive characterization of nanohybrid size, shape and structural properties was carried out by combining complementary TEM, SEM, HR-TEM, EELS, XRD and NTA. The all-in-one therapeutic multi-functionality was assessed on cancer cells and on tumor-bearing nude mice. Results: Tests carried out on IONF@CuS nanohybrid aqueous dispersion demonstrated their impressive efficiency to convert light (conversion coefficient = 42 ± 6 %) and magnetic stimulation (SAR ~ 350 W g-1) into heat as well as to induce concurrent reactive oxygen species (ROS) formation upon laser irradiation. Such capabilities were further confirmed in cellular environment by in vitro tests and at the organism level by in vivo tests in a murine tumor model. Notably, complete tumor regression was obtained for the PTT mode at low Cu concentration. Overall, these results allowed determining windows of applicability for each therapy individually or in combination. Conclusions: Altogether, the obtained data evidence the successful synthesis of a unique tri-therapeutic nanoparticle featuring highly relevant assets for clinical translation such as reduced nanoparticle administered dose, reduced laser power exposure, reduced magnetic field frequency, and the possibility of serial heating cycles and therapy monitoring by photoacoustic (PA) and magnetic resonance imaging (MRI). Furthermore, the integration of the dual heating capability (MHT + PTT) with the PDT insult offers a unique asset to tackle tumors by multiple cytotoxic strategies in order to improve the therapeutic outcome in a broader spectrum of clinical conditions.


Assuntos
Antineoplásicos/administração & dosagem , Hipertermia Induzida/métodos , Magnetoterapia/métodos , Nanocompostos/administração & dosagem , Neoplasias/terapia , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/administração & dosagem , Animais , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Cobre/administração & dosagem , Compostos Férricos/administração & dosagem , Camundongos Nus , Resultado do Tratamento , Ensaios Antitumorais Modelo de Xenoenxerto
15.
Nano Lett ; 18(9): 5989-5995, 2018 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-30102550

RESUMO

Hexagonal Si allotropes are expected to enhance light absorption in the visible range as compared to common cubic Si with diamond structure. Therefore, synthesis of these materials is crucial for the development of Si-based optoelectronics. In this work, we combine in situ high-pressure high-temperature synthesis and vacuum heating to obtain hexagonal Si. High pressure is one of the most promising routes to stabilize these allotropes. It allows one to obtain large-volume nanostructured ingots by a sequence of direct solid-solid transformations, ensuring high-purity samples for detailed characterization. Thanks to our synthesis approach, we provide the first evidence of a polycrystalline bulk sample of hexagonal Si. Exhaustive structural analysis, combining fine-powder X-ray and electron diffraction, afforded resolution of the crystal structure. We demonstrate that hexagonal Si obtained by high-pressure synthesis correspond to Si-4H polytype (ABCB stacking) in contrast with Si-2H (AB stacking) proposed previously. This result agrees with prior calculations that predicted a higher stability of the 4H form over 2H form. Further physical characterization, combining experimental data and ab initio calculations, have shown a good agreement with the established structure. Strong photoluminescence emission was observed in the visible region for which we foresee optimistic perspectives for the use of this material in Si-based photovoltaics.

16.
Int J Pharm ; 548(1): 23-33, 2018 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-29936201

RESUMO

A new class of non-spherical particles was recently designed in our research group by mixing a polysaccharide grafted with fatty acids and α-cyclodextrin in water. Because their flat surfaces, and according to their size, particles are called micro- or nano-platelets. Here, we varied the composition of fatty acids grafted on chitosan (oleic acid, palmitic acid or stearic acid) and characterized platelet morphology. Transmission electron microscopy (TEM), cryogenic TEM, scanning electron microscopy, atomic force microscopy (AFM) and confocal laser scanning microscopy experiments showed that the platelets have a preferentially hexagonal shape with sharp edges, independently on alkyl chain grafted on chitosan. Furthermore, AFM topographic analysis of platelet surface showed parallel thin terraces with 12-14-nm height, suggesting a multi-layered structure alternating chitosan and fatty-acid/α-cyclodextrin inclusion complexes. We also revealed for the first time that a simple magnetic mixing of fatty acids with α-cyclodextrin in water results from solid inclusion complexes with a crystalline structural organization characterized by powder X-ray diffraction. Our results demonstrate that fatty acid/α-cyclodextrin interaction is the driving force for platelet formation.


Assuntos
Quitosana/química , Ácidos Graxos/química , alfa-Ciclodextrinas/química , Interações Hidrofóbicas e Hidrofílicas
17.
Chem Sci ; 8(5): 3741-3749, 2017 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-28553532

RESUMO

The growth of crystals of aromatic compounds from water much depends on the nature of the water solubilizing functions that they carry. Rationalizing crystallization from water, and structure elucidation, of aromatic molecular and supramolecular systems is of general value across various fields of chemistry. Taking helical aromatic foldamers as a test case, we have validated several short polar side chains as efficient substituents to provide both solubility in, and crystal growth ability from, water. New 8-amino-2-quinolinecarboxylic acids bearing charged or neutral aminomethyl, carboxymethyl, sulfonic acid, or bis(hydroxymethyl)-methoxy side chains in position 4 or 5, were prepared on a multi gram scale. Fmoc protection of the main chain amine and suitable protections of the side chains ensured compatibility with solid phase synthesis. One tetrameric and five octameric oligoamides displaying these side chains were synthesized and shown to be soluble in water. In all cases but one, crystals were obtained using the hanging drop method, thus validating the initial design principle to combine polarity and rigidity. The only case that resisted crystallization appeared to be due to exceedingly high water solubility endowed by eight sulfonic acid functions. The neutral side chain did provide crystal growth ability from water but contributed poorly to solubility.

18.
Chembiochem ; 17(20): 1911-1914, 2016 10 17.
Artigo em Inglês | MEDLINE | ID: mdl-27472456

RESUMO

Quinoline-based oligoamide foldamers have been identified as a potent class of ligands for G-quadruplex DNA. Their helical structure is thought to target G-quadruplex loops or grooves and not G-tetrads. We report a co-crystal structure of the antiparallel hairpin dimeric DNA G-quadruplex (G4 T4 G4 )2 with tetramer 1-a helically folded oligo-quinolinecarboxamide bearing cationic side chains-that is consistent with this hypothesis. Multivalent foldamer-DNA interactions that modify the packing of (G4 T4 G4 )2 in the solid state are observed.


Assuntos
Amidas/química , DNA de Protozoário/química , Quadruplex G , Quinolinas/química , Cristalografia por Raios X , Ligantes , Modelos Moleculares , Conformação Molecular , Oxytricha/química
19.
Phys Chem Chem Phys ; 18(21): 14509-19, 2016 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-27223874

RESUMO

The quest for new sustainable iron-based positive electrode materials for lithium-ion batteries recently led to the discovery of a new family of compounds with the general formula Li2M(SO4)2 with M = transition metal, which presents monoclinic and orthorhombic polymorphs. In terms of electrochemical performances, although both Li2Fe(SO4)2 polymorphs present a similar potential of ∼3.8 V vs. Li(+)/Li(0), the associated electrochemical processes drastically differ in terms of polarization and reaction redox mechanisms. We herein provide an explanation to account for such a behavior. While monoclinic Li2Fe(SO4)2 directly transforms into Li1.0Fe(SO4)2 upon oxidation, the orthorhombic counterpart forms a distinct intermediate Li1.5Fe(SO4)2 phase leading to a two-step delithiation process involving an unequal depopulation of the two Li sites pertaining to the structure as deduced by neutron powder diffraction experiments and confirmed by both density functional theory and Bond Valence Energy Landscape calculations. Moreover, to access band gap information, both polymorphs are studied by UV/Vis spectroscopy. Lastly, the possibility of transforming the monoclinic phase to the orthorhombic phase under pressure is explored.

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