Hydrogeological characterization of peculiar Apenninic springs

Abstract. In the northern Apennines of Italy, springs are quite widespread over the slopes. Due to the outcropping of low-permeability geologic units, they are generally characterized by low-yield capacities and high discharge variability during the hydrologic year. In addition, low-flow periods (discharge lower than 1 Ls-1) reflect rainfall and snowmelt distribution and generally occur in summer seasons. These features strongly condition the management for water-supply purposes, making it particularly complex. The "Mulino delle Vene" springs (420 m a.s.l., Reggio Emilia Province, Italy) are one of the largest in the Apennines for mean annual discharge and dynamic storage and are considered as the main water resource in the area. They flow out from several joints and fractures at the bottom of an arenite rock mass outcrop in the vicinity of the Tresinaro River. To date, these springs have not yet been exploited, as the knowledge about the hydrogeological characteristics of the aquifer and their hydrological behaviour is not fully achieved. This study aims to describe the recharge processes and to define the hydrogeological boundaries of the aquifer. It is based on river and spring discharge monitoring and groundwater balance assessment carried out during the period 2012–2013. Results confirm the effectiveness of the approach, as it allowed the total aliquot of discharge of the springs to be assessed. Moreover, by comparing the observed discharge volume with the one calculated with the groundwater balance, the aquifer has been identified with the arenite slab (mean altitude of 580 m a.s.l.), extended about 5.5 km2 and located 1 km west of the monitored springs

Electron transfer in polyaromatic hydrocarbons and molecular carbon nanostructures

Planar and curved polycyclic aromatic hydrocarbons (PAHs) represent an interesting class of compounds with physical chemical properties particularly appealing, as good organic semiconductors and molecular model of larger carbon nano- structures. Investigation of the heterogeneous electron transfer in these systems lets to probe their electronic properties and the reactivity of the corresponding generated carbanions and carbocations that can form new bonds, thus leading to different carbon systems. A particular focus is on the intrinsically high reactivity of carbocations which induces a series of reactions building up new carbon–carbon bonds, thus allowing to enlarge the initial molecular unit into a nanostructure. This represents a new and convenient way to exploit the electro- chemically triggered reactivity into the synthesis of carbon nanostructured materials

DNA-based nanoswitches: insights into electrochemiluminescence signal enhancement

Electrochemiluminescence (ECL) is a powerful transduction technique that has rapidly gained importance as a powerful analytical technique. Since ECL is a surfaceconfined process, a comprehensive understanding of the generation of ECL signal at a nanometric distance from the electrode could lead to several highly promising applications. In this work, we explored the mechanism underlying ECL signal generation on the nanoscale using luminophore-reporter-modified DNA-based nanoswitches (i.e., molecular beacon) with different stem stabilities. ECL is generated according to the "oxidative-reduction" strategy using tri-n-propylamine (TPrA) as a coreactant and Ru(bpy)(3)(2+) as a luminophore. Our findings suggest that by tuning the stem stability of DNA nanoswitches we can activate different ECL mechanisms (direct and remote) and, under specific conditions, a "digital-like" association curve, i.e., with an extremely steep transition after the addition of increasing concentrations of DNA target, a large signal variation, and low preliminary analytical performance (LOD 22 nM for 1GC DNA-nanoswtich and 16 nM for 5GC DNA-nanoswitch). In particular, we were able to achieve higher signal gain (i.e., 10 times) with respect to the standard "signal-off" electrochemical readout. We demonstrated the copresence of two different ECL generation mechanisms on the nanoscale that open the way for the design of customized DNA devices for highly efficient dual-signal-output ratiometric-like ECL systems

Electrochemical Characterization and CO2 Reduction Reaction of a Family of Pyridazine-Bridged Dinuclear Mn(I) Carbonyl Complexes

Three recently synthesized neutral dinuclear carbonyl manganese complexes with the pyridazine bridging ligand, of general formula [Mn2(μ-ER)2(CO)6(μ-pydz)] (pydz = pyridazine; E = O or S; R = methyl or phenyl), have been investigated by cyclic voltammetry in dimethylformamide and acetonitrile both under an inert argon atmosphere and in the presence of carbon dioxide. This family of Mn(I) compounds behaves interestingly at negative potentials in the presence of CO2. Based on this behavior, which is herein discussed, a rather efficient catalytic mechanism for the CO2 reduction reaction toward the generation of CO has been hypothesized

Dinuclear Re(I) Complexes as New Electrocatalytic Systems for CO2 Reduction

A family of dinuclear tricarbonyl rhenium (I) complexes containing bridging 1,2-diazine ligand and halide anions as ancillary ligands and able to catalyze CO2 reduction is presented. Electrochemical studies show that the highest catalytic efficiency is obtained for the complex containing the 4,5-bipenthyl-pyridazine and iodide as ancillary halogen ligands. This complex gives rise to TOF=15 s−1 that clearly outperforms the values reported for the benchmark mononuclear Re(CO)3Cl(bpy) (11.1 s−1). The role of the substituents on the pyridazine ligand and the nature of the bridging halide ligands on the catalytic activity have been deeply investigated through a systematic study on the structure-properties relationship to understand the improved catalytic efficiencies of this class of complexes

Distribution in the brain and possible neuroprotective effects of intranasally delivered multi-walled carbon nanotubes

Carbon nanotubes (CNTs) are currently under active investigation for their use in several biomedical applications, especially in neurological diseases and nervous system injury due to their electrochemical properties. Nowadays, no CNT-based therapeutic products for internal use appear to be close to the market, due to the still limited knowledge on their fate after delivery to living organisms and, in particular, on their toxicological profile. The purpose of the present work was to address the distribution in the brain parenchyma of two intranasally delivered MWCNTs (MWCNTs 1 and a-MWCNTs 2), different from each other, the first being non electroconductive while the second results in being electroconductive. After intranasal delivery, the presence of CNTs was investigated in several brain areas, discriminating the specific cell types involved in the CNT uptake. We also aimed to verify the neuroprotective potential of the two types of CNTs, delivering them in rats affected by early diabetic encephalopathy and analysing the modulation of nerve growth factor metabolism and the effects of CNTs on the neuronal and glial phenotypes. Our findings showed that both CNT types, when intranasally delivered, reached numerous brain areas and, in particular, the limbic area that plays a crucial role in the development and progression of major neurodegenerative diseases. Furthermore, we demonstrated that electroconductive MWCNTs were able to exert neuroprotective effects through the modulation of a key neurotrophic factor and probably the improvement of neurodegeneration-related gliosis

Extremely fast triplet formation by charge recombination in a Nile Red/fullerene flexible dyad

A donor/acceptor dyad was obtained by linking Nile Red and fullerene to a calix[4]arene scaffold. The dyad was spectroscopically characterized, both with steady-state and ultrafast transient absorption experiments, as well as with electrochemical and spectroelectrochemical techniques. We demonstrate extremely fast and efficient formation of a long-lived excited triplet localized on the fullerene moiety in this system, occurring in about 80 ps in toluene and 220 ps in chloroform. The mechanism of this process is investigated and discussed. The spectroscopic and electrochemical characterization suggests the occurrence of electron transfer from Nile Red to fullerene, leading to the formation of a charge-separated state. This state lives very briefly and, because of the small interaction between the electron donor and acceptor, promotes a singlet/triplet state mixing, inducing charge recombination and efficient triplet formation

Insights into the mechanism of coreactant electrochemiluminescence facilitating enhanced bioanalytical performance

Electrochemiluminescence (ECL) is a powerful transduction technique with a leading role in the biosensing field due to its high sensitivity and low background signal. Although the intrinsic analytical strength of ECL depends critically on the overall efficiency of the mechanisms of its generation, studies aimed at enhancing the ECL signal have mostly focused on the investigation of materials, either luminophores or coreactants, while fundamental mechanistic studies are relatively scarce. Here, we discover an unexpected but highly efficient mechanistic path for ECL generation close to the electrode surface (signal enhancement, 128%) using an innovative combination of ECL imaging techniques and electrochemical mapping of radical generation. Our findings, which are also supported by quantum chemical calculations\ua0and spin trapping methods, led to the identification of a family of alternative branched amine coreactants, which raises the analytical strength of ECL well beyond that of present state-of-the-art immunoassays, thus creating potential ECL applications in ultrasensitive bioanalysis

Thiahelicene-based inherently chiral films for enantioselective electroanalysis

Chiral electroanalysis could be regarded as the highest recognition degree in electrochemical sensing, implying the ability to discriminate between specular images of an electroactive molecule, particularly in terms of significant peak potential difference. A groundbreaking strategy was recently proposed, based on the use of \u201cinherently chiral\u201d molecular selectors, with chirality and key functional properties originating from the same structural element. Large differences in peak potentials have been observed for the enantiomers of different chiral molecules, also of applicative interest, using different selectors, all of them based on atropisomeric biheteroaromatic scaffolds of axial stereogenicity. However, helicene systems also provide inherently chiral building blocks with attractive features. In this paper the enantiodiscrimination performances of enantiopure inherently chiral films obtained by electrooxidation of a thiahelicene monomer with helicoidal stereogenicity are presented for the first time. The outstanding potentialities of this novel approach are evaluated towards chiral probes with different chemical nature and bulkiness, in comparison with a representative case of the so far exploited class of inherently chiral selectors with axial stereogenicity. It is also verified that the high enantiodiscrimination ability holds as well for electron spins, as for atropisomeric selectors