Soft solution fluorine-free synthesis of anatase nanoparticles with tailored morphology

TiO2 nanoparticles with tailored morphology have been synthesized under exceptionally soft conditions. The strategy is based on the use of a non-aqueous alcoholic reaction medium in which water traces, coming either from the air (atmospheric water) or from an ethanol–water azeotropic mixture (ethanol 96%), are incorporated in order to accelerate hydrolysis of the Ti–precursor. Moreover, organic surfactants have been used as capping agents so as to tailor crystal growth in certain preferential directions. Combinations of oleic acid and oleylamine, which lead to the formation of another surfactant, dioleamide, are employed instead of fluorine-based compounds, thus increasing the sustainability of the process. As a result, TiO2 nanostructured hierarchical microspheres and individual nanoparticles with exposed high-energy facets can be obtained at atmospheric pressure and temperatures as low as 78 °C

A practical graphitic carbon nitride (g-C₃N₄)based fluorescence sensor for the competitive detection of trithiocyanuric acid and mercury ions

[EN] A fluorescent sensor for the detection of trithiocyanuric acid (TCA) and Hg was developed based on competitive interactions: non-covalent stacking between g-CN and TCA vs coordinative interaction between TCA and Hg. Electrostatic simulations were used to evaluate the interactions and help describe the detection mechanism. Moreover, normalized 2D fluorescence contour plots have been used to understand the fluorescence phenomenon. When TCA was added into a g-CN nanosheet solution free of Hg, TCA interacted with g-CN nanosheets via hydrogen bonding and π-π interactions, resulting in fluorescence quenching of the g-CN nanosheets. However, upon the addition of Hg, the fluorescence of the TCA-g-CN nanosheet hybrid system was restored, due to coordination of Hg with TCA through the S atoms, breaking the TCA-g-CN stacking interaction. Our results provide a new approach for the design of multifunctional nanosensors suitable for the detection of environmental pollutants.The present work is supported by the National Natural Science Foundation of China (No. 21607044), the Natural Science Foundation of Hebei Province (No. B2017502069) and the Fundamental Research Funds for the Central Universities (No. 2018MS113). All data sup-porting this study are provided as supplementary information accom-panying this paper. T.D.J. wishes to thank the Royal Society for a Wolfson Research Merit Award

Investigations into the reactivity of lithium indenyl with alpha diimines with chlorinated backbones and formation of related functional ligands and metal complexes

Reaction between lithium indenyl and a chlorine substituted alpha diimine of the form [{Cl(NPh)2}C)]2 unexpectedly yielded the corresponding NH rearranged derivative [PhN(H)C(C9H6)]2 (1) rather than the predicted symmetrical α-diimine. This compound 1 was characterised by 1H NMR, 13C{1H} NMR and mass spectrometry, and additionally by X-ray diffraction. It was found that 1 was the first indene-substituted and symmetric secondary amine which was also highly fluorescent in DMSO. The reactivity of 1 towards simple inorganic and organometallic transition metals precursors based on the MX2 fragments, where M = Group 10 metals and X = halides or methyl groups, has been investigated. Surprisingly, the reaction with [PtMe2(COD)] led to the coupling reaction between the indenyl groups incorporated at the C-C ligand backbone and a new ligand (2) was discovered, in an attempt to synthesise the metal-linked diamine. Single crystal X-ray diffraction studies confirm this compound 2 to feature coupled indenyl residues and delocalised C-C bonds in the solid state. Structural authentication by X-ray crystallography showed compound 2 to be a very rare example of flat and extended aromatic organic molecule and mass spectrometry, IR and NMR spectroscopy were carried out to gain further insight into the solid state and solution phase structures. Further experiments to synthesise analogues of [PhN(H)C(Ind)]2 aiming to shift a likely equilibrium in favour the imine tautomer, by introducing bulky ortho substituents onto the benzene ring (R = Me, iPr) showed the presence of the imine tautomer to be increasingly favoured in 1H NMR spectra, with an increase in the steric bulk of the ortho substituents. However, the enamine tautomer is still observed to a minor extent even with isopropyl substituents and yields of these desired compounds were low on steric grounds.</p

Self-Assembled Materials Incorporating Functional Porphyrins and Carbon Nanoplatforms as Building Blocks for Photovoltaic Energy Applications.

As a primary goal, this review highlights the role of supramolecular interactions in the assembly of new sustainable materials incorporating functional porphyrins and carbon nanoplatforms as building blocks for photovoltaics advancements

Biocompatible Probes Based on Rare-Earth Doped Strontium Aluminates with Long-Lasting Phosphorescent Properties for In Vitro Optical IMAGING

In recent decades, the demand for biomedical imaging tools has grown very rapidly as a key feature for biomedical research and diagnostic applications. Particularly, fluorescence imaging has gained increased attention as a non-invasive, inexpensive technique that allows real-time imaging. However, tissue auto-fluorescence under external illumination, together with a weak tissue penetration of low wavelength excitation light, largely restricts the application of the technique. Accordingly, new types of fluorescent labels are currently being investigated and, in this search, phosphorescent nanoparticles promise great potential, as they combine the interesting size-dependent properties of nanoscale materials with a long-lasting phosphorescence-type emission that allows optical imaging well after excitation (so avoiding autofluorescence). In this work, core-shell structures consisting of SrAlO:Eu,Dy luminescent cores encapsulated within a biocompatible silica shell were prepared, showing a green persistent phosphorescence with an afterglow time of more than 1000 s. A high-energy ball milling procedure was used to reduce the size of the starting phosphors to a size suitable for cellular uptake, while the silica coating was produced by a reverse micelle methodology that eventually allows the excitation and emission light to pass efficiently through the shell. Confocal fluorescence microscopy using HeLa cancer cells confirmed the potential of the all-ceramic composites produced as feasible labels for in vitro optical imaging

Investigations into the reactivity of lithium indenyl with alpha diimines with chlorinated backbones and formation of related functional ligands and metal complexes

Reaction between lithium indenyl and a chlorine substituted alpha diimine of the form [{Cl(NPh)2}C)]2 unexpectedly yielded the corresponding NH rearranged derivative [PhN(H)C(C9H6)]2 (1) rather than the predicted symmetrical α-diimine. This compound 1 was characterised by 1H NMR, 13C{1H} NMR and mass spectrometry, and additionally by X-ray diffraction. It was found that 1 was the first indene-substituted and symmetric secondary amine which was also highly fluorescent in DMSO. The reactivity of 1 towards simple inorganic and organometallic transition metals precursors based on the MX2 fragments, where M = Group 10 metals and X = halides or methyl groups, has been investigated. Surprisingly, the reaction with [PtMe2(COD)] led to the coupling reaction between the indenyl groups incorporated at the C–C ligand backbone and a new ligand (2) was discovered, in an attempt to synthesise the metal-linked diamine. Single crystal X-ray diffraction studies confirm this compound 2 to feature coupled indenyl residues and delocalised C–C bonds in the solid state. Structural authentication by X-ray crystallography showed compound 2 to be a very rare example of flat and extended aromatic organic molecule and mass spectrometry, IR and NMR spectroscopy were carried out to gain further insight into the solid state and solution phase structures. Further experiments to synthesise analogues of [PhN(H)C(Ind)]2 aiming to shift a likely equilibrium in favour the imine tautomer, by introducing bulky ortho substituents onto the benzene ring (R = Me, iPr) showed the presence of the imine tautomer to be increasingly favoured in 1H NMR spectra, with an increase in the steric bulk of the ortho substituents. However, the enamine tautomer is still observed to a minor extent even with isopropyl substituents and yields of these desired compounds were low on steric grounds

Microwave-induced fast crystallization of amorphous hierarchical anatase microspheres

The fabrication of hierarchical anatase microspheres with potential photocatalytic properties eventually comprises a consolidation step in which a high degree of crystalline order is typically achieved through conventional electric heating treatments. This however entails a substantial reduction in the specific surface area and porosity of the powders, with the consequent deterioration in their photocatalytic response. Here, we have tested the employ of microwave heating as an alternative energy-saving sintering method to promote fast crystallization. The results obtained suggest that under the microwave radiation, the TiO(2) hierarchical structures can effectively crystallize in a drastically reduced heating time, allowing the specific surface area and the porosity to be kept in the high values required for an improved photocatalytic performance