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We report the synthesis, structures, and magnetic investigations of two new octahedral dysprosium complexes, based on the original N-heterocyclic carbene (NHC) tridentate bis(phenoxide) ligand, of the respective formulas mer-[DyL(THF)2Cl] (1) and mer-[DyL(THF)3][BPh4] (2), where L = 1,3-bis(3,5-di-tert-butyl-2-oxidophenyl)-5,5-dimethyl-3,4,5,6-tetrahydropyrimidin-1-ium chloride and THF = tetrahydrofuran. The short Dy-O distances in the axial direction in association with the weak donor ability of the NHC moiety provide a suitable environment for slow relaxation of magnetization, overcoming the previous single-molecule magnets based on NHC ligands.
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Invited for the cover of this issue are Alexeyâ N. Bilyachenko, Joulia Larionova and co-workers at the Russian Academy of Sciences, the Peoples' Friendship University of Russia, and University of Montpellier. The image depicts lanthanide-based cage-like silsesquioxanes exhibiting magnetic and luminescence properties that could constitute a particularly interesting new family related to multifunctional nanomaterials. Read the full text of the article at 10.1002/chem.202003351.
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The synthesis, structure, magnetic, and luminescence properties investigations of four new cage-like lanthanide-based silsesquioxanes (Cat)2 [(PhSiO1.5 )8 (LnO1.5 )4 (O)(NO2.5 )6 (EtOH)2 (MeCN)2 ] (where Cat+ =Et4 N+ , PPh4 P+ and Ln3+ =Eu3+ , Tb3+ and (Ph4 P)4 [(PhSiO1.5 )8 (TbO1.5 )4 (O)2 (NO2.5 )8 ]â 10MeCN are reported. They present an unusual prism-like topology of cage architectures and lanthanide-characteristic emission, which makes them the first luminescent cage-like lanthanide silsesquioxanes. One of the Tb3+ -based cages presents a magnetic spin-flip transition.
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We report the postsynthetic functionalization of Prussian blue (PB) nanoparticles by two different luminophores (2-aminoanthracene and rhodamine B). We show that the photoluminescence properties of the fluorophores are modified by a confinement effect upon adsorption and demonstrate that such multifunctional nanosized systems could be used for in vitro imaging.
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Antracenos/química , Ferrocianuros/química , Colorantes Fluorescentes/química , Nanopartículas/química , Rodaminas/química , Adsorción , Línea Celular Tumoral , Colorantes Fluorescentes/síntesis química , Humanos , Microscopía FluorescenteRESUMEN
Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption.
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The synthesis, and magnetic and photoluminescence investigations of two bifunctional dysprosium complexes based on tridentate Schiff base ligands is reported. Magnetic investigations reveal a genuine single-molecule magnet (SMM) behavior, with out-of-phase signals up to 60â K, and tunable emission arising from the Schiff base ligands.
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Water dispersible cobalt ferrite nanoparticles, CoxFe3-xO4, of different size (4-10 nm) and various composition (0 ≤ x ≤ 1), functionalized with a rhamnose derivative were obtained and characterized by combining TEM, XRD and elemental analyses techniques. Magnetic properties of these systems were studied by SQUID magnetometry. A particular emphasis was given to the investigation of magnetocrystalline anisotropy and size effect on the heating abilities of the nanoparticles under the application of an alternating magnetic field.
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We report a new approach for the synthesis of multifunctional Au core@Prussian Blue analogous (PBA) shell nanoheterostructures that involves PBA shell growth on the surface of cyanide-stabilized gold nanoparticles. It permits the assembly of Au@KNiII [FeII (CN)6 ] core@shell and Au@KNiII [FeII (CN)6 ]@KNiII [CrIII (CN)6 ] core@shell@shell heterostructures with well-defined and size-controlled gold cores and PBA shells. These heterostructures exhibit tunable size- and shape-dependent magnetic and optical properties: (i)â the surface plasmon resonance band position and intensity mainly depend on the PBA shell thickness, and (ii)â the magnetic properties (the transition temperature, the coercivity, and magnetic regime) depend in a complex manner on the thickness as well as the particular morphology of the magnetic shell.
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The relative affinity of a series of Prussian Blue analogues presenting various chemical compositions for the adsorption of different gases, such as water vapor and hydrocarbons, was studied. The ability of Co[CoIII(CN)6]0.66·5.2H2O for the separation of hydrocarbons in a humid atmosphere was demonstrated.
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A new family of bi-, tetra-, penta-, and hexanickel cagelike phenylsilsesquioxanes 1-6 was obtained by self-assembly and transmetalation procedures. Their crystal structures were established by single-crystal X-ray analysis, and features of crystal packing relevant to the network formation were studied by a topological analysis. Compounds 1, 2, and 4 are isolated architectures, while 3, 5, and 6 present extended 1D and 3D networks. The investigation of magnetic properties revealed the presence of ferro- (1 and 3-5) or antiferromagnetic (2 and 6) interactions between Ni(II) ions, giving rise in the most cases (1, 2, and 4-6) to the presence of a slow relaxation of the magnetization, which can originate from the spin frustration.
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Discovery of novel compounds capable of electrochemical ion intercalation is a primary step toward development of advanced electrochemical devices such as batteries. Although cyano-bridged coordination polymers including Prussian blue analogues have been intensively investigated as ion intercalation materials, the solid-state electrochemistry of the octacyanotungstate-bridged coordination polymer has not been investigated. Here, we demonstrate that an octacyanotungstate-bridged coordination polymer Tb(H2O)5[W(CN)8] operates as a Li(+)-ion intercalation electrode material. The detailed magnetic measurements reveal that the tunable amount of intercalated Li(+) ion in the solid-state redox reaction between paramagnetic [W(V)(CN)8](3-) and diamagnetic [W(IV)(CN)8](4-) in the framework enables the electrochemical control of different magnetic regimes. While the initial ferromagnetic long-range ordering is irreversibly lost upon lithium insertion, electrochemical switching between paramagnetic and short-range ordering regimes can be achieved.
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Tumor recurrence after the incomplete removal of a tumor mass inside brain tissue is the main reason that scientists are working to identify new strategies in brain oncologic therapy. In particular, in the treatment of the most malignant astrocytic tumor glioblastoma, the use of magnetic nanoparticles seems to be one of the most promising keys in overcoming this problem, namely by means of magnetic fluid hyperthermia (MFH) treatment. However, the major unknown issue related to the use of nanoparticles is their toxicological behavior when they are in contact with biological tissues. In the present study, we investigated the interaction of glioblastoma and other tumor cell lines with superparamagnetic iron-oxide nanoparticles covalently coated with a rhamnose derivative, using proper cytotoxic assays. In the present study, we focused our attention on different strategies of toxicity evaluation comparing different cytotoxicological approaches in order to identify the biological damages induced by the nanoparticles. The data show an intensive internalization process of rhamnose-coated iron oxide nanoparticles by the cells, suggesting that rhamnose moiety is a promising biocompatible coating in favoring cells' uptake. With regards to cytotoxicity, a 35% cell death at a maximum concentration, mainly as a result of mitochondrial damages, was found. This cytotoxic behavior, along with the high uptake ability, could facilitate the use of these rhamnose-coated iron-oxide nanoparticles for future MFH therapeutic treatments.
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Carcinógenos/toxicidad , Materiales Biocompatibles Revestidos/toxicidad , Daño del ADN/efectos de los fármacos , Dextranos/toxicidad , Nanopartículas de Magnetita/toxicidad , Ramnosa/toxicidad , Animales , Carcinógenos/química , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Materiales Biocompatibles Revestidos/química , Dextranos/química , Glioblastoma/tratamiento farmacológico , Humanos , Hipertermia Inducida , Nanopartículas de Magnetita/química , Ratones , Ratones Endogámicos BALB C , Especies Reactivas de Oxígeno/metabolismo , Ramnosa/químicaRESUMEN
A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage-like architectures have a unique type of molecular topology consisting of the hexairon oxo {Fe6 O19 } core surrounded in a triangular manner by three cyclic germoxanolates [PhGe(O)O]5 . This structural organization induces antiferromagnetic interactions between the FeIII ions through the oxygen atoms. Evaluated for this first time in catalysis, these compounds showed a high catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols.
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A heterometallic phenylsilsesquioxane [(PhSiO1,5)22(CoO)3(NaO0.5)6]â (EtOH)6â (H2O) 1 cage architecture of Co(II) ions in a triangular topology exhibits a slow dynamic behavior in its magnetization, induced by the freezing of the spins of individual molecules.
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We present a new mononuclear half-sandwich complex, [Cp*Yb(DAD)(THF)]·C7H8 (1), based on a paramagnetic Yb(III) ion coordinated by diamagnetic Cp* and enediamido[2,6-Me2C6H3NCHâCHNC6H3Me2-2,6](2-) (DAD) ligands exhibiting field-induced single-ion-magnet behavior.
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Advanced nanostructured materials, such as gold nanoparticles, magnetic nanoparticles, and multifunctional materials, are nowadays used in many state-of-the-art biomedical application. However, although the engineering in this field is very advanced, there remain some fundamental problems involving the interaction mechanisms between nanostructures and cells or tissues. Here we show the potential of (1)H NMR in the investigation of the uptake of two different kinds of nanostructures, that is, maghemite and gold nanoparticles, and of a chemotherapy drug (Temozolomide) in glioblastoma tumor cells. The proposed experimental protocol provides a new way to investigate the general problem of cellular uptake for a variety of biocompatible nanostructures and drugs.
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Compuestos Férricos/metabolismo , Oro/metabolismo , Espectroscopía de Resonancia Magnética , Nanopartículas/metabolismo , Antineoplásicos Alquilantes/farmacocinética , Línea Celular Tumoral , Dacarbazina/análogos & derivados , Dacarbazina/farmacocinética , Glioblastoma/tratamiento farmacológico , Humanos , Espectroscopía de Resonancia Magnética/métodos , Ramnosa/metabolismo , TemozolomidaRESUMEN
Multifunctional molecular ferroelectrics are exciting materials synthesized using molecular chemistry concepts, which may combine a spontaneous electrical polarization, switched upon applying an electric field, with another physical property. A high-temperature ferroelectric material is presented that is based on a chiral Zn(2+) /Dy(3+) complex exhibiting Dy(3+) luminescence, optical activity, and magnetism. We investigate the correlations between the electric polarization and the crystal structure as well as between the low-temperature magnetic slow relaxation and the optical properties.
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The thermally stable Hofmann-type clathrate framework Ni(II)(pz)[Ni(II)(CN)4] (pz = pyrazine) was investigated for the efficient and reversible sorption of iodine (I2) in the gaseous phase and in solution with a maximum adsorption capacity of 1 mol of I2 per 1 mol of Ni(II)(pz)[Ni(II)(CN)4] in solution.
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Access to multifunctionality at the nanoscale requires the development of hybrid nanostructures that combine materials of different natures. In this line of thought, current research on coordination polymers is not only focusing on their synthesis at the nanoscale, but also on combining these polymers with other materials. According to a novel and rational approach, single-layer Au@Prussian blue analogue (PBA) and double-layer Au@PBA@PBA' core-shell nanoparticles (NPs) may be obtained through the growth of a cyano-bridged coordination network on the gold surface. The nanosized heterostructures combine the plasmonic optical properties of the gold core and the magnetic properties of the PBA shell. Whereas the single-layer nanoparticles are paramagnetic, the double-layer nanostructures display ferromagnetism; therefore, the overall structural motif may be considered as multifunctional. The developed synthetic concept also includes an easy access to hollow PBA NPs.
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In this work, we report on the synthesis and investigation of new hybrid multifunctional iron oxide nanoparticles (IONPs) coated by coumarin-bound copolymer, which combine magneto- or photothermal heating with luminescent thermometry. A series of amphiphilic block copolymers, including Coum-C11-PPhOx27-PMOx59 and Coum-C11-PButOx8-PMOx42 bearing luminescent and photodimerizable coumarin moiety, as well as coumarin-free PPhOx27-PMOx57, were evaluated for their utility as luminescent thermometers and for encapsulating spherical 26 nm IONPs. The obtained IONP@Coum-C11-PPhOx27-PMOx59 nano-objects are perfectly dispersible in water and able to provide macroscopic heating remotely triggered by an alternating current magnetic field (AMF) with a specific absorption rate (SAR) value of 240 W.g-1 or laser irradiation with a photothermal conversion efficiency of η = 68%. On the other hand, they exhibit temperature-dependent emission of coumarin offering the function of luminescent thermometer, which operates in the visible region between 20 °C and 60 °C in water displaying a maximal relative thermal sensitivity (Sr) of 1.53%·°C-1 at 60 °C.