Hybrid Photonic Antennae Based on Mesoporous Silica Frameworks

This contribution describes design, preparation and physico-chemical characterization of a new photo-stable hybrid antenna based on mesoporous SBA-15 silica. Concepts of host-guest chemistry are applied in such a way that one or more photoactive guest molecules are incorporated into the silica channels and on the outer surface, acting as energy harvesting and transferring units. The presented composite system be-haves as efficient Förster resonance energy transfer (FRET) pair and shows high photoluminescence and stability towards photodegradation, representing an important step forward in the search for new efficient materials with opto-electronic applications. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3549

Hybrid Photonic Antennae Based on Mesoporous Silica Frameworks

This contribution describes design, preparation and physico-chemical characterization of a new photo-stable hybrid antenna based on mesoporous SBA-15 silica. Concepts of host-guest chemistry are applied in such a way that one or more photoactive guest molecules are incorporated into the silica channels and on the outer surface, acting as energy harvesting and transferring units. The presented composite system be-haves as efficient Förster resonance energy transfer (FRET) pair and shows high photoluminescence and stability towards photodegradation, representing an important step forward in the search for new efficient materials with opto-electronic applications. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3549

Enhancement of the luminescence properties of Eu (III) containing paramagnetic saponite clays

In this study, 1,10-phenanthroline molecules were introduced in the interlayer space of a paramagnetic synthetic saponite clay containing both Eu3+ and Gd3+ ions in structural positions. Two samples with different loading of phenanthroline dye were prepared. The resulting hybrid materials possessed improved optical emission properties due to an efficient antenna effect from the phenanthroline to the Eu3+ centers; this effect was demonstrated to be higher than the metal-to-metal Gd3+-Eu3+ energy transfer previously studied. Insights on the relaxometric properties in aqueous solution of the solids after incorporation of the antenna groups were also obtained through NMR relaxometric analyses

DTPA-Functionalized silica-based monoliths for the removal of transition and lanthanide ions from aqueous phase

Transition and rare-earth metals are essential raw materials used in a wide range of technological applications; moreover, their consumption is often associated with high production of wastes­. Therefore, their recycling and recovery from end-of-life products or metal-contaminated aqueous environments is of considerable importance from a circular economy perspective. In our study, synthetic mesoporous silica monoliths, obtained by sol-gel synthesis[1] and functionalized with chelating groups are used for the recovery of metal ions from aqueous matrices (MONO-DTPA). The monoliths were characterized using a multi-technique approach and were tested in the recovery of paramagnetic Gd3+, Cu2+ and Co2+ ions from aqueous solutions, using 1H-NMR relaxometry to evaluate their uptake performance in real time and in simple conditions[2]. Detailed information on the kinetics of the capture process was also extrapolated. Finally, the possibility to regenerate the solid sorbents was evaluated. The modified silica monoliths were able to recover an appreciable amount of both di- and trivalent metal ions. The best results were obtained in the case of Cu2+ after 24 hours of contact, with a recovered amount of 0.29 mmol/g corresponding to 18.48 mg/g (Fig. 1, A). The capture performance of MONO-DTPA has been shown to be superior to that of natural or synthetic materials commonly used for metal ion removal (Fig 1, B). [1] V. Miglio, C. Zaccone, C. Vittoni, I. Braschi, E. Buscaroli, G. Golemme, L. Marchese and C. Bisio, Molecules 2021, 26, 1316 [2] S. Marchesi, S. Nascimbene, M. Guidotti, C. Bisio and F. Carniato, Dalton Trans. 2022, 51, 4502–4509

Water diffusion modulates the cest effect on Tb(III)-mesoporous silica probes

The anchoring of lanthanide(III) chelates on the surface of mesoporous silica nanoparticles (MSNs) allowed their investigation as magnetic resonance imaging (MRI) and chemical exchange saturation transfer (CEST) contrast agents. Since their efficiency is strongly related to the interaction occurring between Ln-chelates and \u201cbulk\u201d water, an estimation of the water diffusion inside MSNs channels is very relevant. Herein, a method based on the exploitation of the CEST properties of TbDO3A-MSNs was applied to evaluate the effect of water diffusion inside MSN channels. Two MSNs, namely MCM-41 and SBA-15, with different pores size distributions were functionalized with TbDO3A-like chelates and polyethylene glycol (PEG) molecules and characterized by HR-TEM microscopy, IR spectroscopy, N2 physisorption, and thermogravimetric analysis (TGA). The different distribution of Tb-complexes in the two systems, mainly on the external surface in case of MCM-41 or inside the internal pores for SBA-15, resulted in variable CEST efficiency. Since water molecules diffuse slowly inside silica channels, the CEST effect of the LnDO3A-SBA-15 system was found to be one order of magnitude lower than in the case of TbDO3A-MCM-41. The latter system reaches an excellent sensitivity of ca. 55 \ub1 5 \ub5M, which is useful for future theranostic or imaging applications

Surprising Complexity of the [Gd(AAZTA)(H2O)2]- Chelate Revealed by NMR in the Frequency and Time Domains

Typically, Ln(III) complexes are isostructural along the series, which enables studying one particular metal chelate to derive the structural features of the others. This is not the case for [Ln(AAZTA)(H2O)x]- (x = 1, 2) systems, where structural variations along the series cause changes in the hydration number of the different metal complexes, and in particular the loss of one of the two metal-coordinated water molecules between Ho and Er. Herein, we present a 1H field-cycling relaxometry and 17O NMR study that enables accessing the different exchange dynamics processes involving the two water molecules bound to the metal center in the [Gd(AAZTA)(H2O)2]- complex. The resulting picture shows one Gd-bound water molecule with an exchange rate ∼6 times faster than that of the other, due to a longer metal-water distance, in accordance with density functional theory (DFT) calculations. The substitution of the more labile water molecule with a fluoride anion in a diamagnetic-isostructural analogue of the Gd-complex, [Y(AAZTA)(H2O)2]-, allows us to follow the chemical exchange process by high-resolution NMR and to describe its thermodynamic behavior. Taken together, the variety of tools offered by NMR (including high-resolution 1H, 19F NMR as a function of temperature, 1H longitudinal relaxation rates vs B0, and 17O transverse relaxation rates vs T) provides a complete description of the structure and exchange dynamics of these Ln-complexes along the series

Bifunctional Paramagnetic and Luminescent Clays Obtained by Incorporation of Gd3+and Eu3+Ions in the Saponite Framework

A novel bifunctional saponite clay incorporating gadolinium (Gd3+) and europium (Eu3+) in the inorganic framework was prepared by one-pot hydrothermal synthesis. The material exhibited interesting luminescent and paramagnetic features derived from the co-presence of the lanthanide ions in equivalent structural positions. Relaxometry and photoluminescence spectroscopy shed light on the chemical environment surrounding the metal sites, the emission properties of Eu3+, and the dynamics of interactions between Gd3+ and the inner-sphere water placed in the saponite gallery. The optical and paramagnetic properties of this solid make it an attractive nanoplatform for bimodal diagnostic applications

Magnetic and relaxation properties of vanadium(iv) complexes: an integrated H-1 relaxometric, EPR and computational study

We report a detailed study of the magnetic and relaxation properties of a series of oxovanadium(IV) complexes comprising the aqua ion [VO(H2O)5]2+ and [VO(ox)2]2- (ox = oxalate), [VO(nta)]- (nta = nitrilotriacetate), [VO(dtpa)] 3- (dtpa = diethylenetriaminepentaacetate) and [VO(acac)2] (acac = acetylacetonato) in solution. The complexes were characterized using continuous wave (X-band) and pulsed (Q-band) EPR measurements and 1H nuclear magnetic relaxation dispersion (NMRD) studies in the 0.01-120 MHz 1H Larmor frequency range. The 51V A-tensor parameters obtained from the analysis of EPR spectra are in good agreement with those obtained using theoretical calculations at the DFT and coupled-cluster levels (DLPNO-CCSD), while g-tensors were obtained with CASSCF/NEVPT2 calculations. EPR measurements reveal significant differences in the electronic Te1 and Te m relaxation times, with [VO(acac)2] showing a markedly different behaviour due to the trans coordination geometry. The NMRD profiles measured at different temperatures have contributions from both the outer- and inner-sphere mechanisms, with the latter showing contributions from the dipolar and scalar mechanisms. The rotational correlation times ( tR) obtained from the fitting of NMRD and EPR data are in good mutual agreement. The scalar mechanism depends on the hyperfine coupling constants of the coordinated water molecule Haiso, which were obtained from the fitting of the NMRD profiles and DFT calculations. Finally, the analysis of the data provided information on the exchange rate of coordinated water molecules, which display mean residence times of similar to 7-17 mu s at 298 K