Amine derivatives of alkoxides such as (3-aminopropyl)trimethoxysilane and (3-(2-aminoethyl)aminopropyl)trimethoxysilane are reagents in the sol−gel process and, at the same time, versatile ligands forming complexes with transition metal ions (e.g., Cu(II)). One of the major advantages of the sol−gel process is the possibility of preparing Cu(II) complexes in the interior of and on the surface of organically modified silicate xerogels. This paper compares Cu(II) complexes prepared in the interior of silica xerogels with those grafted and anchored onto the surface of such xerogels. Grafting and anchoring require prior preparation of supports with functionalized surfaces. In the former process Cu(II) ions are chemisorbed, and in the latter Cu(II) complexes are immobilized by a condensation reaction. The following spectroscopic results are presented:  FT-IR, optical absorption in the visible region, and electron paramagnetic resonance (EPR). The EPR studies are summarized in three identified models of the coordination sites on the modified silica xerogel surfaces. The materials studied are put forward as catalyst precursors.

This paper presents a spectroscopic characterization of Gd(2)(WO(4))(3):Ln(3+) (Ln=Eu, Pr, Tb and Dy). The luminescence and luminescence kinetics were measured under pressures up to 250 kbar. It was found that pressure quenches the luminescence of Pr(3+) and Tb(3+), whereas the emission of Eu(3+) and Dy(3+) was stable up to 250 kbar. This effect was related to a decrease in the ionization energy of Pr(3+) and Tb(3+) caused by pressure induced increase in energies of the Ln(2+) and Ln(3+) ions with respect to the band edges. Analysis of emission and excitation spectra allowed us to estimate the energies of the ground states of Ln(3+) and Ln(2+) with respect to the valence and conduction band edges of the Gd(2)(WO(4))(3) host. Differences between energies of the ground states of Ln(2+) and Ln(3+) have also been calculated.

In this paper, we described the synthesis procedure of TiO2@SiO2 core-shell modified with 3-(aminopropyl)trimethoxysilane (APTMS). The chemical attachment of Fmoc–glycine (Fmoc–Gly–OH) at the surface of the core-shell structure was performed to determine the amount of active amino groups on the basis of the amount of Fmoc group calculation. We characterized nanostructures using various methods: transmission electron microscope (TEM), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) to confirm the modification effectiveness. The ultraviolet-visible spectroscopy (UV-vis) measurement was adopted for the quantitative determination of amino groups present on the TiO2@SiO2 core-shell surface by determination of Fmoc substitution. The nanomaterials were functionalized by Fmoc–Gly–OH and then the fluorenylmethyloxycarbonyl (Fmoc) group was cleaved using 20% (v/v) solution of piperidine in DMF. This reaction led to the formation of a dibenzofulvene–piperidine adduct enabling the estimation of free Fmoc groups by measurement the maximum absorption at 289 and 301 nm using UV-vis spectroscopy. The calculations of Fmoc loading on core-shell materials was performed using different molar absorption coefficient: 5800 and 6089 dm3 × mol−1 × cm−1 for λ = 289 nm and both 7800 and 8021 dm3 × mol−1 × cm−1 for λ = 301 nm. The obtained results indicate that amount of Fmoc groups present on TiO2@SiO2–(CH2)3–NH2 was calculated at 6 to 9 µmol/g. Furthermore, all measurements were compared with Fmoc–Gly–OH used as the model sample.

First analysis of strong directional surface plasmon-coupled emission (SPCE) of ground-state formed intermolecular aggregates of Rhodamine 110 (R110) in silica nanofilms deposited on silver nanolayers is reported. Until now, the processes of energy transport and its trapping due to aggregate formation have not been studied in the presence of SPCE. A new approach to multicomponent systems with weakly and strongly fluorescent centers making use of fluorophore-surface plasmon interaction is presented. The analysis is based on comparison of experimental free-space emission spectra (F-SE), experimental SPCE with theoretical surface plasmon resonance spectra (SPR). It is shown that, due to the dispersion of SPCE, the detection of weak aggregate emission is straightforward if only the monomers and aggregates fluorescence spectra are somewhat spectrally shifted. SPCE studies confirmed the formation of weakly fluorescent higher order aggregates of R110 in silica films. The results indicate that the increase of energy transfer from monomers to aggregates is due to fluorophore-plasmon interaction.

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