Luigi Falciola

Relevance of electron transfer mechanism in electrocatalysis: the reduction of organic halides at silver electrodes

The mechanism of dissociative electron transfer (ET) to a series of organic chlorides has been investigated both at an inert electrode and at a catalytic surface such as Ag; electrocatalysis is important only when breaking of the carbon-halogen bond is concerted with the ET.

Novel N^C^N-cyclometallated platinum complexes with acetylide co-ligands as efficient phosphors for OLEDs

Two new cyclometallated platinum(II) complexes have been prepared that incorporate a terdentate N^C^N-coordinating ligand and a monodentate acetylide co-ligand. The complexes, namely [PtL3–CC–C6H3F2] and [PtL6–CC–C6H3F2] (where HL3 = 5-methyl-1,3-di(2-pyridyl)benzene; HL6 = 5-mesityl-1,3-di(2-pyridyl)benzene; H–CC–C6H3F2 = 3,5-difluorophenylacetylene), were prepared by ligand metathesis from the corresponding chloro complex PtLnCl. Both of the new complexes are intensely luminescent in solution, displaying quantum yields superior to PtLnCl. OLEDs have been prepared using the new compounds as phosphorescent emitters. Although both lead to efficient devices, the best electroluminescence quantum efficiencies are obtained with the derivative of HL6, having the mesityl group on the cyclometallated phenyl ring. The superior performance with this complex can be rationalised in terms of the greater steric hindrance that serves to reduce aggregate-induced quenching.

Electrochemically assisted deposition of transparent, mechanically robust TiO2 films for advanced applications

In recent years, titanium dioxide has received ever growing interest, thanks to its promising applications in numerous fields such as environmental remediation, H2 generation and photovoltaics. Here, transparent and mechanically robust TiO2 films are deposited by a simple and inexpensive electrochemically assisted procedure on various kinds of substrates, both conductive and nonconductive (e.g., glass slides or different metal laminas with variable surface roughness). The obtained films are uniform, crack-free and exhibit excellent chemical, mechanical, and electrochemical robustness. The obtained layers are compared to films prepared by a routine preparation technique, such as dip coating, showing much better morphological, optical, and conductive properties. The photo-activity of TiO2 can be exploited to obtain transparent spectroelectrochemical systems and to control the wetting features of the surface. Applications concerning the modulation of the wettability are presented with respect to both the antifogging and antistain properties. The photoelectrochemical properties of TiO2 films are exploited to activate a photoelectrochemical polymerization of polypyrrole onto an unconductive support. These materials are promising for numerous applications such as smart windows, antifogging mirrors, solar cells, and optically transparent electrodes.

3D Mass Spectrometry Imaging Reveals a Very Heterogeneous Drug Distribution in Tumors

Mass Spectrometry Imaging (MSI) is a widespread technique used to qualitatively describe in two dimensions the distribution of endogenous or exogenous compounds within tissue sections. Absolute quantification of drugs using MSI is a recent challenge that just in the last years has started to be addressed. Starting from a two dimensional MSI protocol, we developed a three-dimensional pipeline to study drug penetration in tumors and to develop a new drug quantification method by MALDI MSI. Paclitaxel distribution and concentration in different tumors were measured in a 3D model of Malignant Pleural Mesothelioma (MPM), which is known to be a very heterogeneous neoplasm, highly resistant to different drugs. The 3D computational reconstruction allows an accurate description of tumor PTX penetration, adding information about the heterogeneity of tumor drug distribution due to the complex microenvironment. The use of an internal standard, homogenously sprayed on tissue slices, ensures quantitative results that are similar to those obtained using HPLC. The 3D model gives important information about the drug concentration in different tumor sub-volumes and shows that the great part of each tumor is not reached by the drug, suggesting the concept of pseudo-resistance as a further explanation for ineffective therapies and tumors relapse.

Gene and protein expression in response to different growth temperatures and oxygen availability in Burkholderia thailandensis.

Burkholderia thailandensis, although normally avirulent for mammals, can infect macrophages in vitro and has occasionally been reported to cause pneumonia in humans. It is therefore used as a model organism for the human pathogen B. pseudomallei, to which it is closely related phylogenetically. We characterized the B. thailandensis clinical isolate CDC2721121 (BtCDC272) at the genome level and studied its response to environmental cues associated with human host colonization, namely, temperature and oxygen limitation. Effects of the different growth conditions on BtCDC272 were studied through whole genome transcription studies and analysis of proteins associated with the bacterial cell surface. We found that growth at 37°C, compared to 28°C, negatively affected cell motility and flagella production through a mechanism involving regulation of the flagellin-encoding fliC gene at the mRNA stability level. Growth in oxygen-limiting conditions, in contrast, stimulated various processes linked to virulence, such as lipopolysaccharide production and expression of genes encoding protein secretion systems. Consistent with these observations, BtCDC272 grown in oxygen limitation was more resistant to phagocytosis and strongly induced the production of inflammatory cytokines from murine macrophages. Our results suggest that, while temperature sensing is important for regulation of B. thailandensis cell motility, oxygen limitation has a deeper impact on its physiology and constitutes a crucial environmental signal for the production of virulence factors.

Investigation and optimization of photocurrent transient measurements on nano-TiO2

Chronoamperometry with chopped light has been applied to commercial and homemade TiO2 nanopowders, both doped and undoped, to gain information on the charge recombination processes which take place in the oxide and affect its photocatalytic performance. The photocurrent transients can be attributed to photoinduced electron–hole separation, trapping, recombination, and scavenging. In order to evaluate what mainly affects the shape of the transients and the transient time constants (τ) which can be derived, the type and concentration of the electrolyte, the irradiation source (UV or visible light), and the presence of a hole acceptor (oxalate) were varied. The reproducibility of quantitative measurements was best when an inert electrolyte (NaClO4) has been employed under an N2-saturated atmosphere. Under these conditions, both Pr-TiO2 and N-TiO2 samples show a definitely higher τ than the undoped oxide, which indicates a slower recombination kinetics, both under UV and visible irradiation. Therefore, these are promising as photocatalysts.

New CNT/poly(brilliant green) and CNT/poly(3,4-ethylenedioxythiophene) based electrochemical enzyme biosensors.

A combination of the electroactive polymer poly(brilliant green) (PBG) or conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) with carbon nanotubes to obtain CNT/PBG and CNT/PEDOT modified carbon film electrodes (CFE) has been investigated as a new biosensor platform, incorporating the enzymes glucose oxidase (GOx) as test enzyme, alcohol oxidase (AlcOx) or alcohol dehydrogenase (AlcDH). The sensing parameters were optimized for all biosensors based on CNT/PBG/CFE, CNT/PEDOT/CFE platforms. Under optimized conditions, both GOx biosensors exhibited very similar sensitivities, while in the case of AlcOx and AlcDH biosensors, AlcOx/CNT/PBG/CFE was found to give a higher sensitivity and lower detection limit. The influence of dissolved O2 on oxidase-biosensor performance was investigated and was shown to be different for each enzyme. Comparisons were made with similar reported biosensors, showing the advantages of the new biosensors, and excellent selectivity against potential interferents was successfully demonstrated. Finally, alcohol biosensors were successfully used for the determination of ethanol in alcoholic beverages.

Ionization constants of o-phthalic acid and standard pH values of potassium hydrogen phthalate buffer solutions in glycerol + water solvent mixtures at normal and subzero temperatures

Determination of primary standards for pH measurements in glycerol + water solventmixtures has been carried out based on reversible emf measurements of the cellPt|H2|KHPh (mPS) + KCl (mCl)|AgCl|Ag|Ptwhere KHPh denotes the potassium hydrogen phthalate buffer solution of molalitymPS = 0.05 mol-kg−1, at glycerol mass fractions wG = 0.2 and 0.4, within thetemperature range −10 to 40°C. A multilinear regression procedure as a functionof electrolyte molality, glycerol mass fraction wG, and temperature T has beenapplied for the data processing leading to the values of primary standards pHPS.These can be represented by the following regression equationpHPS = (4.007037±0.001113) + (3.55844±0.01776)xG+(0.39622±0.01410)z + (4.3084±0.3377)z2− (50.66±10.53)xGz2 + (457.10±78.48)xG2z2where z = (T − 298.15)/298.15. Parallel values of the first ionization constantof o-phthalic acid (H2Ph; benzene-1,2-dicarboxylic acid, the parent acid of KHPh),which are essential for the above calculations, have been determined fromreversible emf measurements of the cellPt|H2|H2Ph (m1) + KHPh (m2) + KCl (m3)|AgCl|Ag|Ptover the range of solvent composition and temperatures mentioned above.

Electrochemical sensors cleaned by light: a proof of concept for on site applications towards integrated monitoring systems

The potential for on site applications of a SiO2–Ag NPs–TiO2 self-cleaning electrode was demonstrated. Dopamine was used both as the analyte and the fouling agent. Three different UV lamps (a powerful lamp (45 mW cm−2) for photocatalysis, a TLC lamp and a commercial LED torch) were studied. After fouling, total recovery of the electroanalytical performances was achieved upon a short irradiation performed directly in the solution of interest.

A Nanostructured Matrices Assessment to Study Drug Distribution in Solid Tumor Tissues by Mass Spectrometry Imaging

The imaging of drugs inside tissues is pivotal in oncology to assess whether a drug reaches all cells in an adequate enough concentration to eradicate the tumor. Matrix-Assisted Laser Desorption Ionization Mass Spectrometry Imaging (MALDI-MSI) is one of the most promising imaging techniques that enables the simultaneous visualization of multiple compounds inside tissues. The choice of a suitable matrix constitutes a critical aspect during the development of a MALDI-MSI protocol since the matrix ionization efficiency changes depending on the analyte structure and its physico-chemical properties. The objective of this study is the improvement of the MALDI-MSI technique in the field of pharmacology; developing specifically designed nanostructured surfaces that allow the imaging of different drugs with high sensitivity and reproducibility. Among several nanomaterials, we tested the behavior of gold and titanium nanoparticles, and halloysites and carbon nanotubes as possible matrices. All nanomaterials were firstly screened by co-spotting them with drugs on a MALDI plate, evaluating the drug signal intensity and the signal-to-noise ratio. The best performing matrices were tested on control tumor slices, and were spotted with drugs to check the ion suppression effect of the biological matrix. Finally; the best nanomaterials were employed in a preliminary drug distribution study inside tumors from treated mice.