David G. Calatayud

Highly photoactive anatase nanoparticles obtained using trifluoroacetic acid as an electron scavenger and morphological control agent

Fluorine species adsorbed on the surface of TiO2 anatase nanoparticles improve their photocatalytic performance by reducing the recombination rate of photogenerated electrons and holes. Trifluoroacetic acid (TFAA) has been recently proposed as a promising harmless substitute for hydrofluoric acid (HF) in preparing fluorine-modified anatase with good scavenger properties. However the photocatalytic performance of the TiO2 nanoparticles also depends on their specific morphology, by which the number and type of crystal facets, which remain exposed, are determined. A comprehensive study is presented in this contribution which for the first time describes the role of TFAA in stabilizing the highly photoactive {001} TiO2 facets. Furthermore, by reducing the amount of water incorporated into the reaction medium, a simple one-step synthesis method is also proposed that allows the preparation of TFAA-modified anatase nanoparticles with specific morphology and selected stabilized facets, eventually yielding a semiconductor material with excellent photocatalytic properties.

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 TiO2 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.

Fluorescence-Lifetime Imaging and Super-Resolution Microscopies Shed Light on the Directed- and Self-Assembly of Functional Porphyrins onto Carbon Nanotubes and Flat Surfaces

Abstract Functional porphyrins have attracted intense attention due to their remarkably high extinction coefficients in the visible region and potential for optical and energy‐related applications. Two new routes to functionalised SWNTs have been established using a bulky ZnII‐porphyrin featuring thiolate groups at the periphery. We probed the optical properties of this zinc(II)‐substituted, bulky aryl porphyrin and those of the corresponding new nano‐composites with single walled carbon nanotube (SWNTs) and coronene, as a model for graphene. We report hereby on: i) the supramolecular interactions between the pristine SWNTs and ZnII‐porphyrin by virtue of π–π stacking, and ii) a novel covalent binding strategy based on the Bingel reaction. The functional porphyrins used acted as dispersing agent for the SWNTs and the resulting nanohybrids showed improved dispersibility in common organic solvents. The synthesized hybrid materials were probed by various characterisation techniques, leading to the prediction that supramolecular polymerisation and host–guest functionalities control the fluorescence emission intensity and fluorescence lifetime properties. For the first time, XPS studies highlighted the differences in covalent versus non‐covalent attachments of functional metalloporphyrins to SWNTs. Gas‐phase DFT calculations indicated that the ZnII‐porphyrin interacts non‐covalently with SWNTs to form a donor–acceptor complex. The covalent attachment of the porphyrin chromophore to the surface of SWNTs affects the absorption and emission properties of the hybrid system to a greater extent than in the case of the supramolecular functionalisation of the SWNTs. This represents a synthetic challenge as well as an opportunity in the design of functional nanohybrids for future sensing and optoelectronic applications.

Synthesis, radiolabelling and in vitro imaging of multifunctional nanoceramics

Abstract Molecular imaging has become a powerful technique in preclinical and clinical research aiming towards the diagnosis of many diseases. In this work, we address the synthetic challenges in achieving lab‐scale, batch‐to‐batch reproducible copper‐64‐ and gallium‐68‐radiolabelled metal nanoparticles (MNPs) for cellular imaging purposes. Composite NPs incorporating magnetic iron oxide cores with luminescent quantum dots were simultaneously encapsulated within a thin silica shell, yielding water‐dispersible, biocompatible and luminescent NPs. Scalable surface modification protocols to attach the radioisotopes 64Cu (t1/2=12.7 h) and 68Ga (t1/2=68 min) in high yields are reported, and are compatible with the time frame of radiolabelling. Confocal and fluorescence lifetime imaging studies confirm the uptake of the encapsulated imaging agents and their cytoplasmic localisation in prostate cancer (PC‐3) cells. Cellular viability assays show that the biocompatibility of the system is improved when the fluorophores are encapsulated within a silica shell. The functional and biocompatible SiO2 matrix represents an ideal platform for the incorporation of 64Cu and 68Ga radioisotopes with high radiolabelling incorporation.

Carbon Nanotubes and Related Nanohybrids Incorporating Inorganic Transition Metal Compounds and Radioactive Species as Synthetic Scaffolds for Nanomedicine Design:Chapter Eight

Molecular imaging and applications of nanotechnology in health care are interlinked research areas that are currently of high strategic importance to Europe and worldwide. In this sense, there is great current interest in understanding behavior in cells for target-specific pharmaceuticals assembled for the early detection and therapy of diseases (ranging from cancer to cardiovascular and neurodegenerative diseases). To date, little is understood about the most effective way to assemble and deliver in a targeted manner multimodal contrast agents (here defined as “all in one” imaging probes incorporating metals and metal complexes leading to optical/radiopharmaceuticals and/or paramagnetic nanomaterials) necessary to achieve high-resolution images of processes taking place in cells and tissues, the mechanisms of their uptake in cells and tissues, and the effect that these functional imaging tools have on the targeted cells and tissues. In particular, limited information exists regarding the mechanisms of interactions between functional carbon nanomaterials as new inorganic material-based nanodiagnostics and therapeutic agents for imaging and therapy in diagnostic medicine and cells. A major aspect of this overview that has been virtually unexplored to date in current literature is to rationalize and evaluate the nature and strength of connections among different components of the probe, and to comment on the likely impact on the overall biological functionalities, which is necessary before evaluating their interactions with living systems. In this chapter, different and perhaps unconventional approaches to developing a test-informed protocol for constructing complete bioimaging probes (incorporating inorganic and organometallic transition metal complexes and carbon nanomaterial scaffolds) and testing their functionalities in cells are highlighted. Some approaches to testing and monitoring the delivery, cytotoxicity, and uptake of mechanisms of bioimaging probes assembled on single-walled carbon nanotube scaffolds into a variety of healthy and diseased cells of the complete probes are reviewed. These may be localized on the cells’ surface or inside the cells when derivatized with a targeting group or self-targeted (without a tagged targeting unit).

Encapsulation of cadmium selenide nanocrystals in biocompatible nanotubes: DFT calculations, X-ray diffraction investigations and confocal fluorescence imaging

Abstract The encapsulation of CdSe nanocrystals within single‐walled carbon nanotube (SWNT) cavities of varying dimensions at elevated temperatures under strictly air‐tight conditions is described for the first time. The structures of CdSe nanocrystals under confinement inside SWNTs was established in a comprehensive study, combining both experimental and DFT theoretical investigations. The calculated binding energies show that all considered polymorphs [(3:3), (4:4), and (4:2)] may be obtained experimentally. The most thermodynamically stable structure (3:3) is directly compared to the experimentally observed CdSe structures inside carbon nanotubes. The gas‐phase DFT‐calculated energy difference between “free” 3:3 and 4:2 structures (whereby 3:3 models a novel tubular structure in which both Cd and Se form three coordination, as observed experimentally for HgTe inside SWNT, and 4:2 is a motif derived from the hexagonal CuI bulk structure in which both Cd and Se form 4 or 2 coordination) is surprisingly small, only 0.06 eV per formula unit. X‐ray powder diffraction, Raman spectroscopy, high‐resolution transmission electron microscopy, and energy‐dispersive X‐ray analyses led to the full characterization of the SWNTs filled with the CdSe nanocrystals, shedding light on the composition, structure, and electronic interactions of the new nanohybrid materials on an atomic level. A new emerging hybrid nanomaterial, simultaneously filled and beta‐d‐glucan coated, was obtained by using pristine nanotubes and bulk CdSe powder as starting materials. This displayed fluorescence in water dispersions and unexpected biocompatibility was found to be mediated by beta‐d‐glucan (a biopolymer extracted from barley) with respect to that of the individual inorganic material components. For the first time, such supramolecular nanostructures are investigated by life‐science techniques applied to functional nanomaterial characterization, opening the door for future nano‐biotechnological applications.