Phosphineoxide-Chelated Europium(III) Nanoparticles for Ceftriaxone Detection

The present work demonstrates the optimization of the ligand structure in the series of bis(phosphine oxide) and β-ketophosphine oxide representatives for efficient coordination of Tb3+ and Eu3+ ions with the formation of the complexes exhibiting high Tb3+- and Eu3+-centered luminescence. The analysis of the stoichiometry and structure of the lanthanide complexes obtained using the XRD method reveals the great impact of the bridging group nature between two phosphine oxide moieties on the coordination mode of the ligands with Tb3+ and Eu3+ ions. The bridging imido-group facilitates the deprotonation of the imido- bis(phosphine oxide) ligand followed by the formation of tris-complexes. The spectral and PXRD analysis of the separated colloids indicates that the high stability of the tris-complexes provides their safe conversion into polystyrenesulfonate-stabilized colloids using the solvent exchange method. The red Eu3+-centered luminescence of the tris-complex exhibits the same specificity in the solutions and the colloids. The pronounced luminescent response on the antibiotic ceftriaxone allows for sensing the latter in aqueous solutions with an LOD value equal to 0.974 μM

Single Excited Dual Band Luminescent Hybrid Carbon Dots-Terbium Chelate Nanothermometer

The report introduces hybrid polyelectrolyte-stabilized colloids combining blue and green-emitting building blocks, which are citrate carbon dots (CDs) and [TbL]+ chelate complexes with 1,3-diketonate derivatives of calix[4]arene. The joint incorporation of green and blue-emitting blocks into the polysodium polystyrenesulfonate (PSS) aggregates is carried out through the solvent-exchange synthetic technique. The coordinative binding between Tb3+ centers and CD surface groups in initial DMF solutions both facilitates joint incorporation of [TbL]+ complexes and the CDs into the PSS-based nanobeads and affects fluorescence properties of [TbL]+ complexes and CDs, as well as their ability for temperature sensing. The variation of the synthetic conditions is represented herein as a tool for tuning the fluorescent response of the blue and green-emitting blocks upon heating and cooling. The revealed regularities enable developing either dual-band luminescent colloids for monitoring temperature changes within 25–50 °C through double color emission or transforming the colloids into ratiometric temperature sensors via simple concentration variation of [TbL]+ and CDs in the initial DMF solution. Novel hybrid carbon dots-terbium chelate PSS-based nanoplatform opens an avenue for a new generation of sensitive and customizable single excited dual-band nanothermometers

1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

The present review is aimed at highlighting outlooks for cyclophanic 1,3-diketones as a new type of versatile ligands and building blocks of the nanomaterial for sensing and bioimaging. Thus, the main synthetic routes for achieving the structural diversity of cyclophanic 1,3-diketones are discussed. The structural diversity is demonstrated by variation of both cyclophanic backbones (calix[4]arene, calix[4]resorcinarene and thiacalix[4]arene) and embedding of different substituents onto lower or upper macrocyclic rims. The structural features of the cyclophanic 1,3-diketones are correlated with their ability to form lanthanide complexes exhibiting both lanthanide-centered luminescence and magnetic relaxivity parameters convenient for contrast effect in magnetic resonance imaging (MRI). The revealed structure–property relationships and the applicability of facile one-pot transformation of the complexes to hydrophilic nanoparticles demonstrates the advantages of 1,3-diketone calix[4]arene ligands and their complexes in developing of nanomaterials for sensing and bioimaging

Single Excited Dual Band Luminescent Hybrid Carbon Dots-Terbium Chelate Nanothermometer

The report introduces hybrid polyelectrolyte-stabilized colloids combining blue and green-emitting building blocks, which are citrate carbon dots (CDs) and [TbL]+ chelate complexes with 1,3-diketonate derivatives of calix[4]arene. The joint incorporation of green and blue-emitting blocks into the polysodium polystyrenesulfonate (PSS) aggregates is carried out through the solvent-exchange synthetic technique. The coordinative binding between Tb3+ centers and CD surface groups in initial DMF solutions both facilitates joint incorporation of [TbL]+ complexes and the CDs into the PSS-based nanobeads and affects fluorescence properties of [TbL]+ complexes and CDs, as well as their ability for temperature sensing. The variation of the synthetic conditions is represented herein as a tool for tuning the fluorescent response of the blue and green-emitting blocks upon heating and cooling. The revealed regularities enable developing either dual-band luminescent colloids for monitoring temperature changes within 25–50 °C through double color emission or transforming the colloids into ratiometric temperature sensors via simple concentration variation of [TbL]+ and CDs in the initial DMF solution. Novel hybrid carbon dots-terbium chelate PSS-based nanoplatform opens an avenue for a new generation of sensitive and customizable single excited dual-band nanothermometers

Complexes of Sodium Pectate with Nickel for Hydrogen Oxidation and Oxygen Reduction in Proton-Exchange Membrane Fuel Cells

A number of nickel complexes of sodium pectate with varied Ni2+ content have been synthesized and characterized. The presence of the proton conductivity, the possibility of the formation of a dense spatial network of transition metals in these coordination biopolymers, and the immobilization of transition ions in the catalytic sites of this class of compounds make them promising for proton-exchange membrane fuel cells. It has been established that the catalytic system composed of a coordination biopolymer with 20% substitution of sodium ions for divalent nickel ions, Ni (20%)-NaPG, is the leading catalyst in the series of 5, 15, 20, 25, 35% substituted pectates. Among the possible reasons for the improvement in performance the larger specific surface area of this sample compared to the other studied materials and the narrowest distribution of the vertical size of metal arrays were registered. The highest activity during CV and proximity to four-electron transfer during the catalytic cycle have also been observed for this compound

Molecular and Nano-Structural Optimization of Nanoparticulate Mn2+-Hexarhenium Cluster Complexes for Optimal Balance of High T1- and T2-Weighted Contrast Ability with Low Hemoagglutination and Cytotoxicity

The present work introduces rational design of nanoparticulate Mn(II)-based contrast agents through both variation of the μ3 (inner) ligands within a series of hexarhenium cluster complexes [{Re6(μ3-Q)8}(CN)6]4− (Re6Q8, Q = S2−, Se2− or Te2−) and interfacial decoration of the nanoparticles (NPs) K4−2xMnxRe6Q8 (x = 1.3 − 1.8) by a series of pluronics (F-68, P-123, F-127). The results highlight an impact of the ligand and pluronic for the optimal colloid behavior of the NPs allowing high colloid stability in ambient conditions and efficient phase separation under the centrifugation. It has been revealed that the K4−2xMnxRe6Se8 NPs and those decorated by F-127 are optimal from the viewpoint of magnetic relaxivities r1 and r2 (8.9 and 10.9 mM−1s−1, respectively, at 0.47 T) and low hemoagglutination activity. The insignificant leaching of Mn2+ ions from the NPs correlates with their insignificant effect on the cell viability of both M-HeLa and Chang Liver cell lines. The T1- and T2-weighted contrast ability of F-127–K4−2xMnxRe6Q8 NPs was demonstrated through the measurements of phantoms at whole body 1.5 T scanner

Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb³-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref>

The present work introduces the series of thiacalix[4]arenes (H4L) bearing different upper-rim substituents (R = H, Br, NO2) for rational design of ligands providing an antenna-effect on the NIR Yb3+-centered luminescence of their Yb3+ complexes. The unusual inclusive self-assembly of H3L− (Br) through Brπ interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb3+:2HL3−] leads to efficient sensitizing of the Yb3+ luminescence for H4L (Br, NO2), while poor sensitizing is observed for ligand H4L (H). X-ray analysis of the single crystal separated from the basified DMF solutions of YbCl3 and H4L(NO2) has revealed the transformation of the dimeric complexes into [4Yb3+:2L4−] ones with a cubane-like cluster structure. The luminescence characteristics of the complexes in the solutions reveal the peculiar antenna effect of H4L(R = NO2), where the triplet level at 567 nm (17,637 cm−1) arisen from ILCT provides efficient sensitizing of the Yb3+ luminescence

Octahedral Cluster Complex of Molybdenum as Oil-Soluble Catalyst for Improving In Situ Upgrading of Heavy Crude Oil: Synthesis and Application

Heavy oil resources are attracting considerable interest in terms of sustaining energy demand. However, the exploitation of such resources requires deeper understanding of the processes occurring during their development. Promising methods currently used for enhancing heavy oil recovery are steam injection methods, which are based on aquathermolysis of heavy oil at higher temperatures. Regardless of its efficiency in the field of in situ upgrading of heavy oil, this technique still suffers from energy consumption and inefficient heat transfer for deeper reservoirs. During this study, we have developed a molybdenum-based catalyst for improving the process of heavy oil upgrading at higher temperature in the presence of water. The obtained catalyst has been characterized by a set of physico-chemical methods and was then applied for heavy oil hydrothermal processing in a high-pressure reactor at 200, 250 and 300 °C. The comparative study between heavy oil hydrothermal upgrading in the presence and absence of the obtained molybdenum-based oil soluble catalysts has pointed toward its potential application for heavy oil in situ upgrading techniques. In other words, the used catalyst was able to reduce heavy oil viscosity by more than 63% at 300 °C. Moreover, our results have demonstrated the efficiency of a molybdenum-based catalyst in improving saturates and light hydrocarbon content in the upgraded oil compared to the same quantity of these fractions in the initial oil and in the non-catalytically upgraded oil at similar temperatures. This has been explained by the significant role played by the used catalyst in destructing asphaltenes and resins as shown by XRD, elemental analysis, and gas chromatography, which confirmed the presence of molybdenum sulfur particles in the reaction medium at higher temperatures, especially at 300 °C. These particles contributed to stimulating hydrodesulphurization, cracking and hydrogenation reactions by breaking down the C-heteroatom bonds and consequently by destructing sphaltenes and resins into smaller fractions, leading to higher mobility and quality of the upgraded oil. Our results add to the growing body of literature on the catalytic upgrading of heavy oil in the presence of transition metal particles

Role of PSS-based assemblies in stabilization of Eu and Sm luminescent complexes and their thermoresponsive luminescence

The present work introduces self-assembled polystyrenesulfonate (PSS) molecules as soft nanocapsules for incorporation of Eu3+-Sm3+ complexes by the solvent exchange procedure. The high levels of Eu3+ - and Sm3+- luminescence of the complexes derives from the ligand-to-metal energy transfer, in turn, resulted from the complex formation of Eu3+ and Sm3+ ions with the three recently synthesized cyclophanic 1,3-diketones. The structural features of the ligands are optimized for the high thermal sensitivity of Eu3+- luminescence in DMF solutions. The PSS-nanocapsules (similar to 100 nm) provide both colloid and chemical stabilization of the ultrasmall (3-5 nm) nanoprecipitates of the complexes, although their luminescence spectra patterns and excited state lifetimes differ from the values measured for the complexes in DMF solutions. The specific concentration ratio of the Eu3+-Sm3+ complexes in the DMF solutions allows to tune the intensity ratio of the luminescence bands at 612 and 650 nm in the heterometallic Eu3+-Sm3+ colloids. The thermal sensitivity of the Eu3+- and Sm3+ luminescence of the complexes derives from the static quenching both in PSS-colloids and in DMF solutions, while the thermo-induced dynamic quenching of the luminescence is significant only in DMF solutions. The reversibility of thermo-induced luminescence changes of the Eu3+-Sm3+ colloids is demonstrated by six heating-cooling cycles. The DLS measurements before and after the six cycles reveal the invariance of the PSS-based capsule as the prerequisite for the recyclability of the temperature monitoring through the ratio of Eu-3(+)-to-Sm3+ luminescence