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Reducing the dark current of photodetectors is an important strategy for enhancing the detection sensitivity, but hampered by the manufacturing cost due to the need for controlling the complex material composition and processing intricate interface. This study reports a new single-component photochromic semiconductor, [(HDMA)4(Pb3Br10)(PhSQ)2]n (1, HDMA = dimethylamine cation, PhSQ = 1-(4-sulfophenyl)-4,4'-bipyridinium), by introducing a redox-active monosubstituted viologen zwitterion into inorganic semiconducting skeleton. It features yellow to green coloration after UV irradiation with the sharply dropping intrinsic conductivity of 14.6-fold, and the photodetection detection sensitivity gain successfully doubles. The reason of decreasing conductivity originates from the increasing the band gap of the inorganic semiconducting component and formation of Frenkel excitons with strong Coulomb interactions, thereby decreasing the concentration of thermally excited intrinsic carriers.
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One of the difficulties limiting covalent organic frameworks (COFs) from becoming excellent adsorbents is their stacking/aggregation architectures owing to poor morphology/structure control during the synthesis process. Herein, an inorganic-organic nanoarchitectonics strategy to synthesize the MXene/COF heterostructure (Ti3 C2 Tx /TAPT-TFP) is developed by the assembly of ß-ketoenamine-linked COF on the Ti3 C2 Tx MXene nanosheets. The as-prepared Ti3 C2 Tx /TAPT-TFP retains the 2D architecture and high adsorption capacity of MXenes as well as large specific surface area and hierarchical porous structure of COFs. As a proof of concept, the potential of Ti3 C2 Tx /TAPT-TFP for solid-phase microextraction (SPME) of trace organochlorine pesticides (OCPs) is investigated. The Ti3 C2 Tx /TAPT-TFP based SPME method achieves low limits of detection (0.036-0.126 ng g-1 ), wide linearity ranges (0.12-20.0 ng g-1 ), and acceptable repeatabilities for preconcentrating trace OCPs from fruit and vegetable samples. This study offers insights into the potential of constructing COF or MXene-based heterostructures for the microextraction of environmental pollutants.
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AIM: This study aimed to understand the morphological effects of (in)organic additives on microbially induced calcium carbonate precipitation (MICP). METHODS AND RESULTS: MICP was monitored in real time in the presence of (in)organic additives: bovine serum albumin (BSA), biofilm surface layer protein A (BslA), magnesium chloride (MgCl2), and poly-l-lysine. This monitoring was carried out using confocal microscopy to observe the formation of CaCO3 from the point of nucleation, in comparison to conditions without additives. Complementary methodologies, namely scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction, were employed to assess the visual morphology, elemental composition, and crystalline structures of CaCO3, respectively, following the crystals' formation. The results demonstrated that in the presence of additives, more CaCO3 crystals were produced at 100 min compared to the reaction without additives. The inclusion of BslA resulted in larger crystals than reactions containing other additives, including MgCl2. BSA induced a significant number of crystals from the early stages of the reaction (20 min) but did not have a substantial impact on crystal size compared to conditions without additives. All additives led to a higher content of calcite compared to vaterite after a 24-h reaction, with the exception of MgCl2, which produced a substantial quantity of magnesium calcite. CONCLUSIONS: The work demonstrates the effect of several (in)organic additives on MICP and sets the stage for further research to understand additive effects on MICP to achieve controlled CaCO3 precipitation.
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Carbonato de Calcio , Sporosarcina , Carbonato de Calcio/metabolismo , Cloruro de Magnesio/metabolismo , Sporosarcina/metabolismo , Precipitación Química , Microscopía Electrónica de RastreoRESUMEN
In recent years, there has been a challenging interest in developing low-cost biopolymeric materials for wastewater treatment. In the present work, new adsorbents, based on different types of chitosan (commercial, commercial chitin-derived chitosan and chitosan synthesized from shrimp shell waste) and inorganic-organic composites have been evaluated for copper ions removal. The efficacy of the synthesis of chitosan-based composite beads has been determined by studying various characteristics using several techniques, including FTIR spectroscopy, X-ray diffraction, porosimetry (N2 adsorption), and scanning electron microscopy (SEM). Adsorption kinetics was performed using different adsorption models to determine the adsorption behavior of the materials in the aqueous media. For all composite beads, regardless of the type of chitosan used, good capacity to remove copper ions from simulated waters was observed (up to 17 mg/g), which proves that the new materials hold potential for heavy metal retention. However, the adsorption efficiency was influenced by the type of chitosan used. Thus, for the series where commercial chitosan (CC) was used, the removal efficiency was approximately 29%; for the series with chitosan obtained from commercial chitin (SC), the removal efficiency was approximately 34%; for the series with chitosan enriched with CaCO3 (SH), the removal efficiency was approximately 52%.
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Quitosano , Contaminantes Químicos del Agua , Quitosano/química , Cobre , Concentración de Iones de Hidrógeno , Quitina/química , Adsorción , Agua , Cinética , Iones , Contaminantes Químicos del Agua/análisisRESUMEN
High-performance and temperature-resistant lithium-ion batteries (LIBs), which are able to operate at elevated temperatures (i.e., >60 °C) are highly demanded in various fields, especially in military or aerospace exploration. However, their applications were impeded by the poor electrochemical performance and unsatisfying safety issues, which was induced by the severe side reactions between electrolytes and electrodes at high temperatures. Herein, with the synergetic effects of solvation chemistry and functional additive in the elaborately designed weakly solvating electrolyte, a unique robust organic/inorganic hetero-interphase, composed of gradient F, B-rich inorganic components and homogeneously distributed Si-rich organic components, was successfully constructed on both cathodes and anodes, which would effectively inhibit the constant decomposition of electrolytes and dissolution of transition metal ions. As a result, both cathodes and anodes, without compromising their low-temperature performance, operate at temperatures ≥100 â, with excellent capacity retentions of 96.1 % after 500 cycles and 93.5% after ≥200 cycles, respectively, at 80 â. Ah-level LiCoO2||graphite full cells with a cut-off voltage of 4.3 V also exhibited superior temperature-resistance with a capacity retention of 89.9% at temperature as high as 120 â. Moreover, the fully charged pouch cells exhibited highly enhanced safety, demonstrating their potentials in practical applications at ultrahigh temperatures.
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Sodium metal battery is supposed to be a propitious technology for high-energy storage application owing to the advantages of natural abundance and low cost. Unfortunately, the uncontrollable dendrite growth critically hampers its practical implementation. Herein, an inorganic/organic hybrid layer of NaF/CF/CC on the surface of Na foil (IOHL-Na) is designed and synthesized through the in situ reaction of polyvinylidene fluoride (PVDF) and metallic sodium. This protective layer possesses satisfactory Young's modulus, good kinetic property, and sodiophilicity, which can distinctly stabilize Na metal anode. As a result, the symmetric IOHL-Na cell achieves a lifespan of 770 h at 1 mAh cm-2 /1 mA cm-2 in carbonate electrolyte. The assembled full battery of IOHL-Na||Na3 V2 (PO4 )3 delivers a high discharge capacity of 85 mAh g-1 at 10 C after 600 cycles under ambient temperature. Furthermore, the IOHL-Na||Na3 V2 (PO4 )3 cell still can steadily operate at 10 C for 600 cycles at 55 °C. And when testing at an ultralow temperature of -40 °C, the full cell achieves 40 mAh g-1 at 0.5 C with a prolonged lifespan of 450 cycles. This work offers a new approach to protect the metal sodium anode without dendrite growth under wide temperatures.
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Surfactants are functional molecules utilized in various situations. The self-assembling property of surfactants enables several molecular arrangements that can be employed to build up nanometer-sized architectures. This is beneficial in the construction of functional inorganic-organic hybrids holding the merits of both inorganic and organic components. Among several surfactants, bolaamphiphile surfactants with two hydrophilic heads are effective, as they have multiple connecting or coordinating sites in one molecule. Here, a functional polyoxotungstate inorganic anion was successfully hybridized with a bolaamphiphile to form single crystals with anisotropic one-dimensional alignment of polyoxotungstate. Keggin-type metatungstate ([H2W12O40]6-, H2W12) was employed as an inorganic anion, and 1,12-dodecamethylenediammonium (C12N2) derived from 1,12-dodecanediamine was combined as an organic counterpart. A simple and general ion-exchange reaction provided a hybrid crystal consisting of H2W12 and C12N2 (C12N2-H2W12). Single crystal X-ray structure analyses revealed a characteristic honeycomb structure in the C12N2-H2W12 hybrid crystal, which is possibly effective for the emergence of conductivity due to the dissociative protons of C12N2.
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Tensoactivos , Conformación Molecular , Tensoactivos/químicaRESUMEN
The hybridization of inorganic and organic components is a promising strategy to build functional materials. Among several functions, luminescence is an important function which should be considered for practical usage. Inorganic-organic hybrid luminescent materials have been investigated as phosphors, sensors, and lasers. Organic luminescent centers such as dye molecules have often been hybridized with inorganic matrices. Polyoxometalate anions (POMs) are effective inorganic luminescent centers due to their luminescent properties and structural designability. However, most luminescent POM components are limited to lanthanide-based POMs. In this report, a photoluminescent inorganic-organic hybrid crystal based on a non-lanthanide POM was successfully synthesized as a single crystal. Anderson-type hexamolybdochromate ([CrMo6O18(OH)6]3-, CrMo6) anion exhibiting emission derived from Cr3+ was utilized with n-dodecylammonium ([C12H25NH3]+, C12NH3) surfactant cation to obtain a photoluminescent hybrid crystal. The grown single crystal of C12NH3-CrMo6 comprised a distinct layered structure consisting of inorganic CrMo6 layers and interdigitated C12NH3 layers. In the CrMo6 layers, the CrMo6 anions were associated with water molecules by hydrogen bonding to form a densely packed two-dimensional network. Steady-state and time-resolved photoluminescence spectroscopy revealed that the C12NH3-CrMo6 hybrid crystal exhibited characteristic emission from the CrMo6 anion. Preliminary lasing properties were also observed for C12NH3-CrMo6, which shows the possibility of using the C12NH3-CrMo6 hybrid crystal as an inorganic-organic hybrid laser.
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Elementos de la Serie de los Lantanoides , Osteomielitis , Polielectrolitos , Surfactantes Pulmonares , Tensoactivos , Aniones , Lipoproteínas , Rayos LáserRESUMEN
Bismuth-halide-based inorganic-organic hybrid materials (Bi-IOHMs) are desirable in luminescence-related applications due to their advantages such as low toxicity and chemical stability. Herein, two Bi-IOHMs of [Bpy][BiCl4(Phen)] (1, Bpy = N-butylpyridinium, Phen = 1,10-phenanthroline) and [PP14][BiCl4(Phen)]·0.25H2O (2, PP14 = N-butyl-N-methylpiperidinium), containing different ionic liquid cations and same anionic units, have been synthesized and characterized. Single-crystal X-ray diffraction reveals that compounds 1 and 2 crystallize in the monoclinic space group of P21/c and P21, respectively. They both possess zero-dimensional ionic structures and exhibit phosphorescence at room temperature upon excitation of UV light (375 nm for 1, 390 nm for 2), with microsecond lifetime (24.13 µs for 1 and 95.37 µs for 2). Hirshfeld surface analysis has been utilized to visually exhibit the different packing motifs and intermolecular interactions in 1 and 2. The variation in ionic liquids makes compound 2 have a more rigid supramolecular structure than 1, resulting in a significant enhancement in photoluminescence quantum yield (PLQY), that is, 0.68% for 1 and 33.24% for 2. In addition, the ratio of the emission intensities for compounds 1 and 2 shows a correlation with temperature. This work provides new insight into luminescence enhancement and temperature sensing applications involving Bi-IOHMs.
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Recently zero-dimensional (0-D) inorganic-organic metal halides (IOMHs) have become a promising class of optoelectronic materials. Herein, we report a new photoluminescent (PL) 0-D antimony(III)-based IOMH single crystal, namely [H2BPZ][SbCl5]·H2O (BPZ = benzylpiperazine). Photophysical characterizations indicate that [H2BPZ][SbCl5]·H2O exhibits singlet/triplet dual-band emission. Density functional theory (DFT) calculations suggest that [H2BPZ][SbCl5]·H2O has the large energy difference between singlet and triplet states, which might induce the dual emission in this compound. Temperature-dependent PL spectra analyses suggest the soft lattice and strong electron-phonon coupling in this compound. Thermogravimetric analysis shows that the water molecules in the lattice of the title crystal could be removed by thermal treatment, giving rise to a dehydrated phase of [H2BPZ][SbCl5]. Interestingly, such structural transformation is accompanied by a reversible PL emission transition between red light (630 nm, dehydrated phase) and yellow light (595 nm, water-containing phase). When being exposed to an environment with 77% relative humidity, the emission color of the dehydrated phase was able to change from red to yellow within 20 s, and the red emission could be restored after reheating. The red to yellow emission switching could be achieved in acetone with water concentration as low as 0.2 vol%. The reversible PL transition phenomenon makes [H2BPZ][SbCl5]·H2O a potential material for luminescent water-sensing.
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Calor , Hipertermia Inducida , Antimonio , Cloruros , Luminiscencia , HalógenosRESUMEN
A protonated and hydrated Dion-Jacobson-phase HSr2Nb3O10âyH2O was used to prepare two series of inorganic-organic derivatives containing non-covalently intercalated n-alkylamines and covalently grafted n-alkoxy groups of different lengths, as they are promising hybrid materials for photocatalytic applications. Preparation of the derivatives was carried out both under the conditions of standard laboratory synthesis and by solvothermal methods. For all the hybrid compounds synthesized structure, quantitative composition, a type of bonding between inorganic and organic parts as well as light absorption range were discussed using powder XRD, Raman, IR and NMR spectroscopy, TG, elemental CHN analysis, and DRS. It was shown that the inorganic-organic samples obtained contain approximately one interlayer organic molecule or group per proton of the initial niobate, as well as some amount of intercalated water. In addition, the thermal stability of the hybrid compounds strongly depends on the nature of the organic component anchoring to the niobate matrix. Although non-covalent amine derivatives are stable only at low temperatures, covalent alkoxy ones can withstand heat up to 250 °C without perceptible decomposition. The fundamental absorption edge of both the initial niobate and the products of its organic modification lies in the near-ultraviolet region (370-385 nm).
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The precise synthesis of miktoarm star polymers (MSPs) remains one of the great challenges in synthetic chemistry due to the difficulty in locating appropriate structural templates and polymer grafting/growing strategies with high selectivity and efficiency. Herein, ≈2â nm metal-organic polyhedra (MOPs), constructed from the coordination of isophthalic acid (IPA) and Cu2+ , are applied as templates for the precise synthesis of 24-arm MSPs for their unique logarithmic ligand-exchange dynamics. Six different polymers are prepared with IPA as an end group and they further coordinated with Cu2+ to afford the corresponding 24-arm star homo-polymers. MSPs can be obtained by mixing targeted homo-arm star polymers in solutions upon thermal annealing. The compositions of MSPs can be facilely and precisely tuned by the recipe of the star polymer mixtures used. Interestingly, the obtained MSPs can be sorted into homo-arm star polymers through a typical solvent extraction procedure. The hybridization and sorting process can be reversibly conducted through the cycle of thermal annealing and solvent treatment. The complex coordination framework not only opens new avenues for the facile and precise synthesis of MSPs and MOPs with hybrid functionalities, but also provides the capability to design sustainable polymer systems.
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Increasing attention has been devoted to studying perovskite-type multifunctional stimuli-responsive materials with multiple channel physical characteristics. However, it remains challenging to simultaneously achieve multifunction and regulate structural phase transition temperature in hybrid perovskites. Here, we report two three-dimensional organic-inorganic hybrid rare-earth double perovskite compounds, (HQ)2 RbEu(NO3 )6 (1, HQ=quinuclidium) and (4FHQ)2 RbEu(NO3 )6 (2, 4FHQ=4-fluoro-quinuclidium), which exhibit ferroelasticity, dielectric switch, and excellent photoluminescence response. The phase transition temperature of 2 increases 169â K compared with 1 through H/F substitution. This result is attributed to the H/F substitution inducing the generation of the Rb-F coordination bond between cations and anions. Meanwhile, the photoluminescence emission intensity of 2 shows no quench with the increase of temperature, in particular, the emission spectrum achieves fine regulation at high temperatures. This work provides a new solution for the realization of multi-functions and regulations of the properties based on hybrid perovskite materials with high critical temperatures.
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Growing international problem with pathogens acquiring resistance to antibiotics is the reason for the search for bactericidal substances against which microorganisms cannot become resistant. The aim of this study was to synthesize inorganic-organic nanohybrids and obtain materials with antimicrobial effects. Chitosan (CS) was deposited on nanocomposite carriers such as calcium oxide with titanium dioxide (CaO-TiO2), magnesium oxide with titanium dioxide (MgO-TiO2) and copper(II) oxide with titanium dioxide (CuO-TiO2). The efficiency of the process was examined at varying concentrations of chitosan and temperature. The parameters for nanohybrids synthesis were selected based on the highest amount of nano-chitosan deposited on the nanohybrids-for each carrier, the process conditions were as follows: chitosan solution at 5 g l-1and 20 °C. The materials were obtained using these parameters and were used for microbiological tests againstE. coliATCC 25922,S. aureusATCC 25923 andC. albicansATCC 10231. The growth inhibitory activity of the obtained materials was qualitatively defined. These results suggest that the synthesized nanohybrids and nanocomposites exhibit biostatic action. The material with the broadest effect was the CuO-TiO2-CS hybrid, which had biostatic properties against all tested strains at a minimal concentration of 1250µg ml-1. Further research is required to find eco-friendly, non-toxic, and more effective antimicrobials with a broad action to prevent the acquisition of resistance.
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Antiinfecciosos , Quitosano , Nanocompuestos , Nanopartículas , Antibacterianos/farmacología , Antiinfecciosos/farmacología , Quitosano/farmacología , Óxidos , Titanio/farmacologíaRESUMEN
Inorganic-organic hybrid nanoparticles formed by lanthanide-doped nanostructures and organic ligands have been intensively studied, which could greatly increase their photoluminescence performance as a result of the energy transfer process from organic ligands to Ln3+ ions. However, the photoluminescence intensity and excitation spectral width are still quite limited on coordinating with a single type of organic ligand. In this work, Eu3+ -doped LaF3 (LaF3 :Eu3+ ) nanoparticles were prepared using a hydrothermal method, and were then hybridized with benzoic acid and thenoyltrifluoroacetone to form the hybrid nanostructures. After that, the hybrid nanostructures were mixed with 2,2'-azobisisobutyronitrile and methyl methacrylate to prepare the composites. The sample obtained by hybridization and composite doping with 5% Eu3+ exhibited the best photoluminescence performance. The excitation peak width and luminescence intensity of the hybrid nanostructures were significantly increased. The excitation spectral width of the inorganic-organic mixed hybrid nanostructures was particularly enhanced, and covered the whole ultraviolet band region of solar light on Earth. The prepared composites exhibited good optical properties.
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The desire to harness solar energy to address current global environmental problems led us to investigate two-dimensional (2D) core-shell hybrid photocatalysts in the form of a 2D-TiO2-surfactant, mainly composed of fatty acids. The bulk products, prepared by two slightly different methods, consist of stacked host-guest hybrid sheets held together by van der Waals forces between alkyl carboxylate moieties, favoring the synergistic conjugation of the photophysical properties of the core and the hydrophobicity of the self-assembled surfactant monolayer of the shell. X-ray diffraction and the vibrational characteristics of the products revealed the influence of synthesis strategies on two types of supramolecular aggregates that differ in the core chemical structure, guest conformers of alkyl surfactant tails and type, and the bilayer and monolayer of the structure of nanocomposites. The singular ability of the TiO2 core to anchor carboxylate leads to commensurate hybrids, in contrast to both layered clay and layered double-hydroxide-based ion exchangers which have been previously reported, making them potentially interesting for modeling the role of fatty acids and lipids in bio-systems. The optical properties and photocatalytic activity of the products, mainly in composites with smaller bandgap semiconductors, are qualitatively similar to those of nanostructured TiO2 but improve their photoresponse due to bandgap shifts and the extreme aspect-ratio characteristics of two-dimensional TiO2 confinement. These results could be seen as a proof-of-concept of the potential of these materials to create custom-designed 2D-TiO2-surfactant supramolecular photocatalysts.
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Nanocompuestos , Tensoactivos , Catálisis , Ácidos Grasos , Nanocompuestos/química , Titanio/químicaRESUMEN
The pnictogen bond, a somewhat overlooked supramolecular chemical synthon known since the middle of the last century, is one of the promising types of non-covalent interactions yet to be fully understood by recognizing and exploiting its properties for the rational design of novel functional materials. Its bonding modes, energy profiles, vibrational structures and charge density topologies, among others, have yet to be comprehensively delineated, both theoretically and experimentally. In this overview, attention is largely centered on the nature of nitrogen-centered pnictogen bonds found in organic-inorganic hybrid metal halide perovskites and closely related structures deposited in the Cambridge Structural Database (CSD) and the Inorganic Chemistry Structural Database (ICSD). Focusing on well-characterized structures, it is shown that it is not merely charge-assisted hydrogen bonds that stabilize the inorganic frameworks, as widely assumed and well-documented, but simultaneously nitrogen-centered pnictogen bonding, and, depending on the atomic constituents of the organic cation, other non-covalent interactions such as halogen bonding and/or tetrel bonding, are also contributors to the stabilizing of a variety of materials in the solid state. We have shown that competition between pnictogen bonding and other interactions plays an important role in determining the tilting of the MX6 (X = a halogen) octahedra of metal halide perovskites in one, two and three-dimensions. The pnictogen interactions are identified to be directional even in zero-dimensional crystals, a structural feature in many engineered ordered materials; hence an interplay between them and other non-covalent interactions drives the structure and the functional properties of perovskite materials and enabling their application in, for example, photovoltaics and optoelectronics. We have demonstrated that nitrogen in ammonium and its derivatives in many chemical systems acts as a pnictogen bond donor and contributes to conferring stability, and hence functionality, to crystalline perovskite systems. The significance of these non-covalent interactions should not be overlooked, especially when the focus is centered on the rationale design and discovery of such highly-valued materials.
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Compuestos de Calcio , Óxidos , Compuestos de Calcio/química , Halógenos/química , Nitrógeno , Óxidos/química , TitanioRESUMEN
Theranostics (bifunction of therapeutics and diagnostics) has attracted increasing attention due to its efficiency that can reduce the physical and financial burden on patients. One of the promising materials for theranostics is calcium phosphate (CP) and it is biocompatible and can be functionalized not only with drug molecules but also with rare earth ions to show photoluminescence that is necessary for the diagnostic purpose. Such the CP-based hybrids are formed in vivo by interacting between functional groups of organic molecules and inorganic ions. It is of great importance to elucidate the interaction of CP with the photofunctional species and the drug molecules to clarify the relationship between the existing state and function. Well-designed photofunctional CPs will contribute to biomedical fields as highly-functional ormultifunctional theranostic materials at the nanoscales. In this review, we describe the hybridization between CPs and heterogeneous species, mainly focusing on europium(III) ion and methylene blue molecule as the representative photofunctional species for theranostics applications.
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Europio , Nanomedicina Teranóstica , Fosfatos de Calcio , Humanos , Iones , Azul de Metileno , Medicina de PrecisiónRESUMEN
Antibacterial photocatalytic therapy (APCT) is considered to be a potential treatment for administrating antibiotic-resistant bacteria. However, due to the low photocatalytic efficiency and weak ability to capture bacteria, it is not practically applied. In this work, an organic-metal oxide hybrid semiconductor heterostructure is fabricated for the photocatalytic generation of reactive oxygen species (ROS) to kill the drug-resistant bacteria. The organic semiconductor, perylene diimide (PDI), can self-assemble on Sn3 O4 nanosheets to form a "hook-and-loop" sticky surface that can capture bacteria, via large numbers of hydrogen bonding and π-π stacking interactions, which are not possible in inorganic semiconductors. This easy-to-fabricate hybrid semiconductor also possesses improved photocatalytic activity, which is owing to the formation of heterostructure that achieves full-spectrum absorption, and the reduction of the photocarrier recombination rate to produce more reactive oxygen species. It has a good promoting effect on the wounds of mice infected by Staphylococcus aureus. This work shows new ideas for fabricating smart full-spectrum inorganic-organic hybrid adhesive heterostructure photocatalysts for antibacterial photocatalytic therapy.
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Antibacterianos , Semiconductores , Animales , Antibacterianos/farmacología , Catálisis , Ratones , Especies Reactivas de Oxígeno , Staphylococcus aureusRESUMEN
Lacunary polyoxometalates (LPOMs) are key precursors for the synthesis of functional POMs. To date, reviews dedicated to behavioral studies of LPOMs often comprise the role of metal ions, including transition metal (TM) and rare earth (RE) ions, in extending and stability of high-nuclearity clusters. In contrast, the role of organic ligands in the structures and properties of lacunary-based hybrids has remained less explored. In this review, we focus on the role of organic fragments in the self-assembling process of POM-based architectures and discuss relationships between the nature and structure of organic ligand and properties such as the topology of hybrid inorganic-organic material in RE and TM-RE heterometallic derivatives of lacunary Keggin-type POMs. The effects of organic fragment in mixed ligand hybrids are also briefly reviewed.