Claudia Carlucci

New organic dyes based on a dibenzofulvene bridge for highly efficient dye-sensitized solar cells

Three novel organic dyes, coded TK1, TK2 and TK3, incorporating two donor moieties, cyanoacrylic acid as an acceptor/anchoring group, the dibenzofulvene core and an oligothiophene spacer in a 2D–π–A system, were designed, synthesized, and successfully utilized in dye-sensitized solar cells. The dye TK3, containing two thiophene rings as spacers, shows an IPCE action spectrum with a high plateau from 390 nm to 600 nm, increased open-circuit photovoltage by 40 mV and short-circuit photocurrent by 7.03 mA cm−1, with respect to TK1. Using CDCA as the co-adsorbent material, the Jsc of TK3 was increased to 14.98 mA cm−1 and a strong enhancement in the overall conversion efficiency (7.45%) was realized by TK3 compared to TK1 (1.08%), in liquid electrolyte-based DSSCs.

Fluorine–thiophene-substituted organic dyes for dye sensitized solar cells

Novel triphenylamine (TPA)-based organic dyes were synthesized and assessed for their performance in dye-sensitized solar cells (DSSCs). In the dyes considered the TPA group and the cyanoacetic acid have the role of electron-donor and -acceptor, respectively, whereas a thienyl–fluoro-phenyl-substituted was introduced as π-linker to improve the dye performance in DSSCs. Experimental characterizations empasize that the presence of electron withdrawing substituents in the linker close to the electron-acceptor moiety leads to a more efficient intramolecular photoinduced charge transfer. In fact, photovoltaic experiments reveal that the DSSCs based on the thienyl–o-fluoro-phenyl substituted dyes yield a better solar-energy-to-electricity conversion efficiency.

Enhanced Photocatalytic Activity of Pure Anatase Tio2 and Pt-Tio2 Nanoparticles Synthesized by Green Microwave Assisted Route

High-yield, rapid and facile synthesis of elongated pure anatase titania nanoparticles has been achieved through a nonaqueous microwave-based approach. The residual organics onto nanoparticles surfaces were completely removed through a new treatment under ozone flow, at room temperature in air. Such an ozone cleaning method revealed an effective inexpensive dry process of removing organic contaminants from nanoparticles surfaces. The TiO2 elongated nanoparticles having a length of 13.8 ± 5.5 nm and a diameter of 9.0 ±1.2 nm were characterized by powder X-Ray diffraction, transmission electron microscopy, selected area diffraction, BET surface area analyzer and FT-IR spectroscopy. Photocatalytic evaluation demonstrated that the as-synthesized ozone-cleaned TiO2 nanoparticles and TiO2 nanoparticles loaded with platinum possess excellent Rhodamine B performance with respect to both commercial spherical nanotitania P25 and P25 loaded with platinum. This could be attributed to the anatase phase purity, small size, large specific surface area and clean surfaces of the prepared nanoparticles.

Selective synthesis of TiO2 nanocrystals with morphology control with the microwave-solvothermal method

In this paper, a method to synthesize anatase TiO2 nanorods by hydrolysis of titanium(IV) isopropoxide (TTIP) in the presence of benzyl alcohol and acetic acid at 210 °C was tested. The novelty of the present approach relies on the evaluation of the shape-controlled synthesis of anatase TiO2 nanocrystals via a microwave-solvothermal method in 45 min. The different TiO2 nanocrystals were obtained by tuning the TTIP/acetic acid ratio under optimized synthetic conditions and were characterized in detail by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), micro Raman (together with microphotoluminescence) and FT-IR spectroscopies. The acetic acid coordinated on the nanocrystal surface was removed by the reduction of its carboxyl group via a “super-hydride reaction”, and the photocatalytic activity of bare TiO2 nanocrystals, under visible light irradiation, was also evaluated: the best performing TiO2 anatase nanocrystals exhibited a discrete photoactivity, completely degrading Rhodamine B solution in five hours.

Flow technology for organometallic-mediated synthesis

In this review recent examples on the use of flow technology for organometallic-mediated synthesis have been collected. The review focused on synthetic relevant processes and on flow techniques developed for handling reactive intermediates, and conduct synthetic steps difficult to perform using traditional “batch” chemistry.

Thiophene-based fluorescent probes with low cytotoxicity and high photostability for lysosomes in living cells.

BACKGROUND Selective imaging of lysosomes by fluorescence microscopy using specific fluorescent probes allows the study of biological processes and it is potentially useful also for diagnosis. Lysosomes are involved in numerous physiological processes, such as bone and tissue remodeling, plasma membrane repair, and cholesterol homeostasis, along with cell death and cell signaling. Despite the great number of dyes available today on the market, the search for new fluorescent dyes easily up-taken by cells, biocompatible and bearing bright and long-lasting fluorescence is still a priority. METHODS Two thiophene-based fluorescent dyes, TC1 and TC2, were synthetized as lysosome-specific probes. RESULTS The new dyes showed high selectivity for fluorescent staining and imaging of lysosomes and disclosed high photostability, low toxicity and pH insensitivity in the range 2-10. CONCLUSIONS The TC dyes exhibited high co-localization coefficients (>95%) and moderate quantum yields. They showed high biocompatibility and long-term retention, important features for biological applications. GENERAL SIGNIFICANCE The results of the present work disclose a new class of organic dyes with potential wide applications as specific and efficient lysosome probes in the study of various biological processes.

Surface reactivity and in vitro toxicity on human bronchial epithelial cells (BEAS-2B) of nanomaterials intermediates of the production of titania-based composites

Titanium dioxide (TiO2) nanoparticles (NPs) are manufactured worldwide in large quantities for use in a wide range of applications. Evaluating the hazards associated with TiO2 NPs is crucial as it enables risk assessment related to human and environmental exposure. In this study the in vitro human toxicity of a set of TiO2 NPs modified with acetic, oleic and boric acids were studied in order to assess the hazard in view of a future scale-up of the synthesis. The surface reactivity of the powders under simulated solar illumination and in the dark has been evaluated by means of EPR spectroscopy. Human bronchial epithelial cells (BEAS-2B) have been chosen as a model for lung epithelium. Cytotoxicity has been assessed by measuring the cells membrane integrity by lactate dehydrogenase (LDH) assay, and the inflammatory response evaluated as nitric oxide (NO) and TNF-α production, and oxidative stress measured as intracellular reduced glutathione (GSH) levels, and induced lipoperoxidation. Aeroxide P25 was used for comparison. The results demonstrated a low photoreactivity and toxic effects lower than Aeroxide P25 of the nano-TiO2 powders, probably as a consequence of the presence of acidic moieties at the surface.

Exploiting structural and conformational effects for a site-selective lithiation of azetidines

Abstract Interest in molecular structures bearing four-membered heterocycles (FMHs) is growing due to the possibility to explore new regions of the chemical space and get new lead molecules. Our interest in the development of divergent synthesis of functionalized FMHs, prompted us to disclose factors affecting the reactivity of nitrogen-bearing FMHs towards metalating agents. Our investigations demonstrated that structural factors and conformational preferences need to be considered in planning a site-selective functionalization of azetidines. It will be showed how such factors could have pivotal importance in the reactivity of FMHs.

Properties of nanocrystals-formulated aluminosilicate bricks

In the present work, seven different types of nanocrystals were studied as additives in the formulation of aluminosilicate bricks. The considered nanocrystals consisted of anatase titanium dioxide (two differently shaped types), boron modified anatase, calcium carbonate (in calcite phase), aluminium hydroxide and silicon carbide (of two diverse sizes), which were prepared using different methods. Syntheses aim to give a good control over a particles size and shape. Anatase titania nanocrystals, together with the nano-aluminium hydroxide ones, were synthesized via microwave-assisted procedures, with the use of different additives and without the final calcination steps. The silicon carbide nanoparticles were prepared via laser pyrolysis. The nano-calcium carbonate was prepared via a spray drying technique. All of the nanocrystals were tested as fillers (in 0.5, 1 and 2 wt. % amounts) in a commercial aluminosilicate refractory (55 % Al2O3, 42 % SiO2). They were used to prepare bricks that were thermally treated at 1300 °C for 24 hours, according to the international norms. The differently synthesized nanocrystals were added for the preparation of the bricks, with the aim to improve their heat-insulating and/or mechanical properties. The nanocrystals-modified refractories showed variations in properties, with respect to the untreated aluminosilicate reference in heat-insulating performances (thermal diffusivities were measured by the “hot disk” technique). In general, they also showed improvements in mechanical compression resistance for all of the samples at 2 wt. %. The best heat insulation was obtained with the addition of nano-aluminium hydroxide at 2 wt. %, while the highest mechanical compression breaking resistance was found with nano-CaCO3 at 2 wt. %. These outcomes were investigated with complementary techniques, like mercury porosimetry for porosity, and Archimedes methods to measure physical properties like the bulk and apparent densities, apparent porosities and water absorption. The results show that the nano-aluminium hydroxide modified bricks were the most porous, which could explain the best heat-insulating performances. There is a less straightforward explanation for the mechanical resistance results, as they may have relations with the characteristics of the pores. Furthermore, the nanoparticles may have possible reactions with the matrix during the heat treatments.

Efficient, Green Non-Aqueous Microwave-Assisted Synthesis of Anatase TiO2 and Pt Loaded TiO2 Nanorods with High Photocatalytic Performance

A high-yield synthesis of pure anatase titania nanorods has been achieved through a nonaqueous microwave-based approach. The residual organics on nanoparticles surfaces were completely removed under ozone flow at room temperature in air. The TiO2 nanorods, with average lengths of 27.6 ± 5.8 nm and average diameters of 3.2 ± 0.4 nm, were characterized by powder X-Ray diffraction, transmission electron microscopy, selected area diffraction, BET surface area analysis and FT-IR spectroscopy. The photocatalytic performances of the as-synthesized TiO2 nanorods and platinum loaded TiO2 nanorods were implemented with respect to both commercial P25 and platinum loaded P25. Performance enhancements should be attributed to effects like differences in the adsorption capacity and in the separation efficiency of the photogenerated electrons-holes.