Carbon Dots from Citric Acid and its Intermediates Formed by Thermal Decomposition

Thermal decomposition of citric acid is one of the most common synthesis methods for fluorescent carbon dots; the reaction pathway is, however, quite complex and the details are still far from being understood. For instance, several intermediates form during the process and they also give rise to fluorescent species. In the present work, the formation of fluorescent C-dots from citric acid has been studied as a function of reaction time by coupling infrared analysis, X-ray photoelectron spectroscopy, liquid chromatography/mass spectroscopy (LC/MS) with the change of the optical properties, absorption and emission. The reaction intermediates, which have been identified at different stages, produce two main emissive species, in the green and blue, as also indicated by the decay time analysis. C-dots formed from the intermediates have also been synthesised by thermal decomposition, which gave an emission maximum around 450 nm. The citric acid C-dots in water show short temporal stability, but their functionalisation with 3-aminopropyltriethoxysilane reduces the quenching. The understanding of the citric acid thermal decomposition reaction is expected to improve the control and reproducibility of C-dots synthesis.     

Infrared and X-ray simultaneous spectroscopy: a novel conceptual beamline design for time resolved experiments

Many physical/chemical processes such as metal–insulator transitions or self-assembly phenomena involve correlated changes of electronic and atomic structure in a wide time range from microseconds to minutes. To investigate these dynamic processes we not only need a highly brilliant photon source in order to achieve high spatial and time resolution but new experimental methods have to be implemented. Here we present a new optical layout for performing simultaneous or concurrent infrared and X-ray measurements. This approach may indeed return unique information for example the interplay between structural changes and chemical processes occurring in the investigated sample. A beamline combining two X-ray and IR beams may really take advantage of the unique synchrotron radiation properties: the high brilliance and the broad spectrum. In this contribution we will describe the conceptual layout and the expected performance of a complex system designed to collect IR and X-ray radiation from the same bending magnet on a third-generation synchrotron radiation ring. If realized, this beamline will enable time-resolved spectroscopy experiments offering new scientific opportunities at the frontiers of science.     

Time-resolved infrared spectroscopy as an in situ tool to study the kinetics during self-assembly of mesostructured films

Rapid scan time-resolved infrared spectroscopy has been used to investigate in situ the kinetics of the chemical processes involved in the formation of self-assembled mesostructured films. The experiments have been done in transmission mode on films cast on a diamond disk using an infrared microscope. Two specific materials have been studied: silica and titania mesoporous films templated by a triblock copolymer surfactant (Pluronic F-127). The time dependence of solvent evaporation and condensation of the chemical species have been clearly observed. Different stages in the film formation have been identified, which support well the general theory of self-assembly. The in situ FTIR spectroscopy using time-resolved rapid scan has proven to be a very effective tool for in situ analysis of film formation from a liquid phase.     

Ordered Mesostructured Silica Films: Effect of Pore Surface on its Sensing Properties

An electrochemical resistive-type sensor device, with a mesoporous silica thin film as sensitive membrane, has been developed and characterised. The silica film has been obtained via evaporation-induced self-assembly (EISA) using a tri-block copolymer (Pluronic F-127) as templating agent. It has been deposited by dip-coating on a silicon substrate with metallic interdigitated electrodes. Fast, reversible and reproducible electrical responses to relative humidity changes have been observed for the sensor device. The conduction mechanism has been related to chemical properties, structural order and surface morphology of the porosity in the silica film, confirming the dependence on the film preparation method and overall the importance of calcination temperature.     

Optical Limiting Devices Based on C60 Derivatives in Sol-Gel Hybrid Organic-Inorganic Materials

A guest-host solid state device based on hybrid organic-inorganic materials and fullerene derivatives has been fabricated for optical limiting applications. Different 3-glycidoxypropyltrimethoxysilane derived hybrid matrices have been synthesized to increase the optical limiting performances. These matrices have shown high laser damage fluences, low light scattering, good transmittance in the visible range and allowed to deposit 10–100 m thick films per single layer. The C₆₀ derivatives have been functionalized with Si tri-alkoxide terminal groups and have reached a final concentration in the solid matrix up to 2 × 10^–2 M·l^–1. A multilayer system with a bottleneck structure has been developed to optimize a laser protection device.     

Hydrolysis of uranium(VI) at variable temperatures (10-85 degrees C)

The hydrolysis of uranium(VI) in tetraethylammonium perchlorate (0.10 mol dm(-3) at 25 degrees C) was studied at variable temperatures (10-85 degrees C). The hydrolysis constants (*beta(n,m)) and enthalpy of hydrolysis (Delta H(n,m)) for the reaction mUO(2)(2+) + nH(2)O = (UO(2))(m)(OH)(n)((2m-n))+) + nH(+) were determined by titration potentiometry and calorimetry. The hydrolysis constants, *beta(1,1), *beta(2,2), and *beta(5,3), increased by 2-5 orders of magnitude as the temperature was increased from 10 to 85 degrees C. The enthalpies of hydrolysis, Delta H(2,2) and Delta H(5,3), also varied: Delta H(2,2) became more endothermic while Delta H(5,3) became less endothermic as the temperature was increased. The heat capacities of hydrolysis, Delta C(p(2,2)) and Delta C(p(5,3)), were calculated to be (152 +/- 43) J K(-1) mol(-1) and -(229 +/- 34) J K(-1) mol(-1), respectively. UV/Vis absorption spectra supported the trend that hydrolysis of U(VI) was enhanced at elevated temperatures. Time-resolved laser-induced fluorescence spectroscopy provided additional information on the hydrolyzed species at different temperatures. Approximation approaches to predict the effect of temperature were tested with the data from this study.     

A comparative FTIR study of thermal and photo-polymerization processes in hybrid sol-gel films

Controlling the organic polymerization in organic-inorganic hybrids is a key point in the development of new materials with high homogeneity of the nanostructure. The main difficulty is related with the achievement of a simultaneous control of the organic and inorganic network formation. Thermal and photocuring represent the main routes to form the organic chains when polymerizable organic groups are present in the hybrid materials. In the present work hybrid organic-inorganic films were synthesized from 3-methacryloxypropyltrimethoxysilane (MPTMS) cohydrolyzed with tetraethylorthosilicate (TEOS) and N-[(3-trimethoxysilyl)propyl]ethylenediamine (TMESPE) or 3-(triethoxysilyl)-propylamine (TESPA). This an example of basic catalyzed hybrid material with a polymerizable methacrylate functionality whose micro-structure is modified by the amine groups. FTIR spectroscopy was used to compare the effects of thermal or photo-induced polymerization on the materials. TESPA and TMESPE showed a different catalytic effect on the condensation of the inorganic network, with TMESPE the more efficient one. The presence of a more extended silica backbone reduced the curing efficiency in TMESPE derived samples. UV curing was also very effective in catalyzing the inorganic condensation of un-reacted species still present in the film after the deposition. A photo-induced polymerization of the inorganic side was observed in the hybrid films. Thermal polymerization in TMESPE films induces the reaction between the secondary amine and CO bonds in MPTMS, this reaction is, instead, not observed in films cured by UV radiation.     

Adsorption of monovalent and divalent cations on planar water-silica interfaces studied by optical reflectivity and Monte Carlo simulations

Adsorption on planar silica substrates of various monovalent and divalent cations from aqueous solution is studied by optical reflectivity. The adsorbed amount is extracted by means of a thin slab model. The experimental data are compared with grand canonical Monte Carlo titration simulations at the primitive model level. The surface excess of charge due to adsorbed cations is found to increase with pH and salt concentration as a result of the progressive dissociation of silanol groups. The simulations predict, in agreement with experiments, that the surface excess of charge from divalent ions is much larger than from monovalent ions. Ion-ion correlations explain quantitatively the enhancement of surface ionization by multivalent cations. On the other hand, the combination of experimental and simulation results strongly suggests the existence of a second ionizable site in the acidic region. Variation of the distance of closest approach between the ions and surface sites captures ion specificity of water-silica interfaces in an approximate fashion.     

An improved method for the determination of uranium isotopes in environmental samples by alpha-spectrometry

In order to improve the selectivity of the uranium isotopes determination in environmental samples, further studies have been carried out, including (1) interference of ²¹⁰Po with uranium isotope determination, (2) distribution coefficients of polonium between 5% TOPO in toluene and aqueous hydrochloric and nitric acids, (3) decontamination factor of uranium from polonium of the recommended procedure, and (4) leaching effect comparison of two different leaching procedures in a lichen sample. Based on the new findings, a more accurate extraction chromatographic/ a-spectroscopy method has been developed. For the method's validation, four kinds of reference materials supplied by the IAEA have been tested. It is observed that nearly all the ²³⁸U, ²³⁴U and ²³⁵U concentrations obtained are in good agreement with the recommended or information values, showing that the method can give reliable results. A comparison with existing uranium determination methods has also been made. It is concluded that due to involving preconcentration and chemical separation, the extraction chromatographic/a-spectroscopy method is a more selective, very sensitive and accurate, and low cost method. This revised version was published online in July 2006 with corrections to the Cover Date.