A novel and convenient approach to functionalized pyrroles is presented, based on Pd-catalyzed oxidative heterocyclization-alkoxycarbonylation of readily available N-Boc-1-amino-3-yn-2-ols. Reactions were carried out in alcoholic solvents at 80-100 °C and under 20 atm (at 25 °C) of a 4:1 mixture of CO-air, in the presence of the PdI2-KI catalytic system (2-5 mol % of PdI2, KI/PdI2 molar ratio = 10). In the case of N-Boc-1-amino-3-yn-2-ols 3, bearing alkyl or aryl substituents, the carbonylation reaction led to a mixture of Boc-protected and N-unsubstituted pyrrole-3-carboxylic esters 4 and 5, respectively. This mixture could be conveniently and quantitatively converted into deprotected pyrrole-3-carboxylic esters 5 by a simple basic treatment. In the case of diastereomeric (3RS,4RS)- and (3RS,4SR)-N-Boc-3-amino-2-methyldec-5-yn-4-ol (syn-3f and anti-3f, respectively, whose relative configuration was determined by X-ray crystallographic analysis), no particular difference was observed in the reactivity of the two diastereomers between them and with respect to the diastereomeric mixture (3S,4S) + (3S,4R).Interestingly, N-Boc-2-alkynyl-1-amino-3-yn-2-ols 6, bearing an additional alkynyl substituent ? to the hydroxyl group, spontaneously underwent N-deprotection under the reaction conditions and regioselective water addition to the alkynyl group at C-3 of the corresponding pyrrole-3-carboxylic ester derivative, thus directly affording highly functionalized pyrrole derivatives 7 in one step.

This paper presents a general methodology for processing bioclimatic data in the temporal domain. Two different methods are used to assess the presence of temporal trends in the time-series of bioclimatic indices at each mea- surement station. A preliminary stage checks for the statistical homogeneity in the data set and for the presence of serial autocorrelation in the data, applying the proper methods to remove these effects. The methodology has been applied to a case study in Apulia, Italy, using the popular De Martonne index as a bioclimatic indicator.

This paper presents a general methodology for processing bioclimatic data in the spatial domain whose main goal is to derive indications related to the moisture/dryness level of a region and provide water management authorities with information about its irrigation requirements. The methodology uses point-scale measurements of weather related data to perform a detailed analysis of the spatial behavior of the corresponding bioclimatic indicators at the continuous regional scale. The proposed methodology, although more demanding in terms of computation resources, gives more accurate results than standard approximate approaches available in current GIS packages. This methodology has been applied to a particular case study using the well known De Martonne index as a bioclimatic indicator.

A research study was conducted on a coastal irrigated agricultural area of southern Italy to assess the risks of aquifer degradation likely resulting from the intensive groundwater pumping from individual farm wells andreduced aquifer recharge. Information were collected both from farmers and delivery system's operators during a survey conducted in 2012 revealing that farmers depend mainly on groundwater with the aim to achieve flexible irrigation management as opposed to the rigid rotational delivery service of surface water supply provided by the local water management agency. The study area is intensively farmed by small land-holding growers with high-value micro-irrigated horticultural crops. Our team appraised the soil and aquifer degradation hazards using a simplified procedure for environmental risk assessment that allowed identifying the risk-generating processes, evaluating the magnitude of impacts, and estimating the overall risks significance. We also collected the stakeholders' perceptions on agricultural water management and use through field interviews, whereas parallel investigations revealed significant aquifer salinity increase during the recent years. As a final step, some preliminary risk mitigation options were appraised by exploring the growers' response to possible changes of irrigation deliveries by the water management agency. The present study integrated multi-annual observations, data interpretation, and modelling efforts, which jointly enabled the analysis of complex water management scenarios and the development of informed decisions.

This paper presents a software package for the automatic processing of bioclimatic data in the space and time domains whose final goal is to provide land and water management authorities with reliable information about the moisture/dryness level of a region and its water requirements. The current state of development of package is reported, presenting an example of application of the program to a specific case study.

An entry from the Cambridge Structural Database, the worlds repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

C27H36ClN2O9PS, monoclinic, C12/c1 (no. 15),a = 36.495(3) A?, b = 8.5574(4) A?, c = 20.487(4) A?, b = 101.18(2)°, V = 6276.8 A?3, Z = 8, Rgt(F) = 0.052, wRref(F2) = 0.125, T = 295 K.

A new ytterbium diphosphate HYbP2O7·5H2O has been synthesized and characterized by single crystal X-ray diffraction. The compound belongs to the monoclinic P21/c space group, and its unit cell dimensions are: a = 6.845(1), b = 8.739(2), c = 17.342(4) Å, ? = 90.61(2)°, V = 1037.3(4) Å3, Z = 4. The framework of this compound consists of layers, parallel to the ab plane, formed by HP2O7 groups and YbO7 polyhedra. They are interconnected by strong hydrogen bonds involving the acidic hydrogen and external oxygen atoms of adjacent diphosphate groups. This layer organization generates channels parallel to the a axis in which two crystallization water molecules are located. The remaining three water molecules complete the coordination sphere of the ytterbium cation. TG and DTA thermograms of the title compound show four decomposition steps, in the 298-1173 K temperature range, corresponding to the removal of the five crystallization water molecules and the acidic hydrogen. A mixture of monophosphate YbPO4 and ytterbium polyphosphate YbP3O9 is obtained at 1173 K. IR and Raman spectra of HYbP2O7·5H2O have also been investigated. Most of the IR bands are non-coincident with those observed in the Raman spectrum, as expected for a centrosymmetric crystal. The emission spectrum of 10 % Eu3+-doped HYbP2O7·5H2O was measured at room temperature and the Stark energy states of Eu3+ were calculated. The non-degenerate 5D0 -> 7F0 transition confirms the unicity of the crystallographic site occupied by the lanthanide cation.

Major concerns arise about marine pollution due to human and industrial activities. The quality of sensing system response depends upon the materials used to realize sensors. There are different techniques used for the purposes of this kind of research that makes easier to reveal main parameters such as: Temperature, salinity, waiving, wind, chlorophyll, oxygen, depth, etc. The paper presents an optical fiber sensor design using nanotechnology. The sensor will be used on floating buoys for autonomous marine detection. The sensor principle is based on photochromatography and to be realized using a waveguide for conducting light for multimodal approach.

The water retention curve has a key role for the hydraulic characterization of porous media. A new method, based on the differential evolution algorithm, for the determination of the characteristic parameters of several water retention models from the experimental data is proposed. We present the details of the method and its application to the calculation of water retention curves of soils. We show that our method can find the optimal model parameters without any prior information on the characteristics of the medium under investigation. The errors associated to the calculated parameters are evaluated through the random perturbation of the data.

The effective protection of the coastal ecosystem requires a detailed knowledge of the morphological evolution of the coastal environment. Several probabilistic models have been developed in the last decades to implement a reliable statistical forecasting of coastline dynamics. In this work, the non-linear Evolutionary Polynomial Regression (EPR) model has been used for the first time to evaluate the short-term dynamics of the shoreline from a set of measured shoreline positions in previous years. A comparison of the mean known shoreline positions with those predicted by the model, together with their confidence and prediction intervals, can be used to assess the reliability of the estimation by the EPR model.

Atmospheric deposition of pollutants is a major challenge for the environmental governance and management of cities. Different depositions could be harmful especially on ground and roads. In particular, in areas were industrial activities are located and/or significant car traffics occur, depositions on roads are harmful for all people especially for pregnant women who will be attacked as well as other people. The main effects are risks of breathing pathologies and possible cancer as a long-term consequence. The main objective of this research is to illustrate the latest achievements in terms of the use of titanium dioxide to be spread on a road as a cover film to neutralize pollutants as NOx, SOx, NH3, CO, dusts and aromatic substances. The removal is performed by means of a photocatalytic reaction. The nanoparticles play a key role in this process. The paper show some experimental and interesting results.

The measurement of ultra-weak magnetic fields with nanometer-scale spatial resolution is a powerful tool for investigating several biological, chemical and physical systems. Among the available detectors, SQUIDs are the most sensitive magnetic field and flux detectors and are rapidly approaching the quantum sensitivity limit. To reach such sensing capability, technological advances in the fabrication of nanoscale SQUIDs with submicrometric loops are needed. In this work we present a novel process for the fabrication of nanoscale SQUIDs, based on superconducting vertical Nb nanoconstrictions. The fabrication process uses laser lithogra- phy to define the device geometry, focused ion beam to mill the top surface of the Nb in a nanometer-sized region across the width of the film and anodization to define the final thickness of the nanoconstriction and at the same time to embed the ion- implanted amorphous layer produced by the FIB milling step. A preliminary electrical characterization of nano-sized single Josephson junctions and SQUIDs fabricated with this process is also reported.

The variogram incorporates the basic information for the geostatistical analysis of spatial data, making it one of the most popular and widespread approaches for the evaluation and assessment of environmental data. Fitting an experimental variogram with a proper model, capable of catching the main characteristics of the sampled data, is a critical stage of spatial analysis. This stage is generally carried out using a semi-Automatic approach, with different levels of user's contribution. Once a model and the related starting parameter values have been defined, they can be refined using a trial-And-error strategy and the impact of such changes can be evaluated through several calibration indices. In this paper, we present an overview of the main indices used for the refinement of the variogram model parameters, highlighting the specific information provided by each of them together with a few heuristic strategies for driving the trial-And-error refinement process.

Environmental measurements need high accuracy and precision for delivering results necessary for authorities for making decisions. In particular, for water characterization, it is necessary to perform fast analysis in order to delivery immediate results, especially in online conditions. To do that, in some circumstances it is compulsory to accept deliberate low accuracy and precision as compromise for quick results. Approximate computing could be an innovating approach on the proviso that results should be realistic. This research illustrates findings regarding application of approximate computing in the field of spectroscopy measurements related to water characterization using an experimental instrumentation based on interferometry and spectroscopy.

Superconducting nanoconstrictions have been fabricated from narrow microstrips of Nb deposited by ultra- high vacuum DC sputtering. The thickness of the nanoconstriction has been defined with two different techniques, Ga+ Focused Ion Beam sculpting and Ar+ sputter etching, producing devices that behave as Josephson junctions. A detailed morphological and electrical characterization of the nanoconstrictions has been performed to compare the results obtained with the two techniques. The effect of the electrochemical anodization process used to passivate the film surface and the temperature dependence of critical currents of the devices have also been measured. Different device configurations, single junctions, small series arrays and nanoSQUIDs, have been fabricated, to evaluate the reproducibility and uniformity of the two fabrication processes.

The redesign of environmental monitoring networks is a field rich of practical applications, in particular in light of recent EU environmental directives. When dealing with an existing monitoring network reduction, the easiest approach is to search for redundancies among the monitoring locations (clusters of locations) and to remove the most useless of them on the basis of the values of some quantitative parameter. This approach could lose some important features of the existing network, thus reducing its informative content. To avoid such a risk, the results of the network optimization should undergo a retrospective analysis capable to verify, by assessing some independent statistical indices, the acceptability of the reduced configuration with respect to specific managerial issues. The case study presented in this work focuses on the optimal downsizing of a groundwater monitoring network located in the Southern part of Italy. The MSANOS optimization software has been used to select the locations to remove from the existing network, with the goal to sustainably balance maintenance costs and information loss. The investigated case is of particular interest for both the critical issues of the considered resource and the recognized importance of the groundwater monitoring in the European Water Framework Directive.

Calcium hydroxyapatite (CaHAp) was prepared in the presence of two alkylphosphonates, the tert-butyl phosphonic acid TBPOH and the 2-carboxyletylphosphonic acid 2-CEPA, by hydrothermal method at 120 degrees C for 15 h. The modification of hydroxyapatite by grafting organic moieties is confirmed by IR and NMR MAS ((1)H and (31)P) spectroscopy and chemical analysis. X-ray powder diffraction patterns show that the incorporation of organic moieties induces a significant loss of the material crystallinity and a clear increase of the unit cell lattice parameter a as function of 2-CEPA grafting rate. The specific surface area (SSA) increases with increasing phosphonate amount especially for 2-CEPA. All techniques show the lower reactivity of TBPOH due to the steric effects of tert-butyl, whereas the 2-CEPA with a linear chain and double acidic functions is more reactive and can replace the OH(-) groups of the apatitic structure.

In the last century, the International System of Units (SI) changed its perspectives, evolving from an artifact-based system to a system mainly based on physical processes at the atomic level and fundamental constants. In particular, the discovery of the Josephson effect made available a quantum voltage standard. As an consequence, in the last decade the worldwide consistency of the representation and maintenance of the electrical units and the electrical measurements based on it has improved a hundredfold. The Josephson effect, together with the quantum Hall effect for the definition of a modern resistance standard, will certainly play a major role in the next modernization of the SI, when the kilogram, the last base unit still based on a physical artifact, will be linked to fundamental constants. Furthermore, the definition of a new SI is strictly linked to the technological issues for the realisation of new devices capable to reproduce the electrical units with quantum accuracy. The challenges faced by modern metrology, sensing and quantum electronics are directing the new generations of devices towards smaller dimensions and higher levels of integration. Taking into account this requirement, at INRIM we fabricate and characterize superconducting quantum devices for a wide range of applications. The devices are based on the overdamped Nb/Al-AlOx/Nb SNIS (Superconductor-Normal metal-Insulator-Superconductor) Josephson junctions and exploiting thin film technology to guarantee a good control of electrical parameters of junctions, a higher reproducibility of their currentvoltage response, and increasingly an accurate dimension control. The main objective of the current experimental activity is addressed on downscaling the junction size from the micro to the nanoscale, exploiting three different lithographic techniques: optical lithography to realize SNISs with a size resolution of the order of the microme- ter, electron beam lithography (EBL) at the submicrometer range and, lastly, a recently proposed mesoscopic tunnel junction nano-fabrication technique, based on focused ion beam (FIB). We report the fabrication process and the electrical characterisation of a 1 Volt binary-divider array based on 8192 overdamped SNIS Josephson junctions for the programmable Josephson Voltage Standard (PJVS) [1] and of a 3D nano-SQUID (Super- conducting Quantum Interference Device) [2] as a sensor for the detection of magnetic nanoparticles. Preliminary results on Nb-based nano-constrictions fabricated by FIB and anodisation will also be presented [3]. The effect of FIB exposure and anodization voltage on the superconducting transition temperature and on the temperature dependence of the resistance of the nano-constrictions has been investigated, as well as the behaviour of these constrictions as overdamped SNS-like Josephson junctions.[1] V. Lacquaniti, N. De Leo, M. Fretto, A. Sosso, F. Mueller, J. Kohlmann, Superconductor Sci. Technol. 24 (2011).[2] C. Grana

Monitoring networks are essential tools for the effective management of vulnerable or limited environmental resources. Cost and logistics constraints often suggest to reduce the number of monitoring sites while minimizing the loss of information determined by these changes. The problem can be rigorously addressed through the optimization of one or more objective functions that rep- resent the managerial goals associated to the network. However, the use of objective functions is based on assumptions that in practical cases can be inaccurate. To overcome this problem, we have developed a retrospective analysis procedure that validates the degree of acceptability of the optimal reduced configuration at a local and global level. The procedure has been applied to a case study in Apulia, Italy, finding that the optimal reduced network was unable to recover the measured values of the monitored parameter of two discarded locations, making it unable to accomplish its monitoring goals.

Nei Paesi più sviluppati - USA, Giappone e Germania su tutti - la ricerca viene considerata un settore strategico per lo sviluppo del Paese: qui non a caso il numero dei ricercatori e i fondi destinati alla ricerca sono cresciuti costantemente anche negli ultimi anni di crisi economica mondiale. In Italia si deve finalmente sviluppare una visione positiva che veda la ricerca come una occasione strategica per aumentare la competitività del Paese e rafforzarne l'economia, considerando i fondi destinati alla ricerca come un investimento e non un costo.Del resto siamo circondati da prodotti o servizi originati direttamente dalla ricerca, spesso in modo del tutto inaspettato. Esempi lampante sono internet e il world wide web che, nati per scopi militari o di pura e semplice comunicazione fra scienziati, sono diventati parte integrante ed inscindibile della nostra vita. Ma non serve andare così lontano: in realtà la maggior parte delle attività di ricerca scientifica possono avere ricadute più o meno immediate in termini di prodotti o di servizi, spesso basta solo trovare lo spunto o il partner industriale giusto.Ecco perché una maggiore interazione fra i due mondi si rivela assolutamente preziosa.

Particulate matters and ozone are often neglected as pollutant elements when people deal with widespread pollution. Particulate matters PM 10 , PM 2.5 , are produced by human activities namely industries and car traffic but also by natural activities like blowing wind from desert, volcanoes, etc... Ozone, instead, has a double consideration: it is beneficial as ozone layer in the upper atmosphere because it serves as natural filter to reduce UV rays that arrive at earth surface. But at ground level, high amounts of ozone, in terms of concentration are harmful for human health. The research presents the effect of wind in a transitional and seasonal period on particulate matters and ozone. The paper also illustrates the application of retarded differential functional equations or delayed differential functional equations for studying the effect of wind in pollution distribution.

We report here the synthesis of (Z)-5-(4-nitrobenzyliden)-3-N(2-ethoxyphenyl)-2-thioxo-thiazolidin-4-one (ARNO) compound. The crystal structure has been determined by X-ray diffraction. The compound crystallizes in the triclinic system with space group P (1) over bar and cell parameters: a = 9.1289(19), b = 9.3717(7), c = 12.136(3) , alpha = 102.133(11)A degrees, beta = 90.99(2)A degrees, gamma = 117.165(9)A degrees, V = 895.4(3) (3) and Z = 2. The structure has been refined to a final R = 0.05 for 2591 observed reflections. The refined structure was found to be significantly non planar. The molecule exhibits intermolecular hydrogen bond of type C-Ha <-O and C-Ha <-S. ab initio calculations were also were performed at Hartree-Fock and density functional theory levels. The full HF and DFT geometry optimization was carried out using LANL2DZ, 6-31G* and B3LYP/6-31+G** basis sets. The optimized geometry of the title compound was found to be consistent structure determined by X-ray diffraction. The minimum energy of geometrical structure is obtained by using level HF/LANL2DZ basis sets.

NbCl(5)center dot(N,N '-dicyclohexylurea) 1a owns a distorted octahedral structure due to intramolecular NH center dot center dot center dot Cl bonding. The unit cell contains four units which are intermolecularly NH center dot center dot center dot Cl and NH center dot center dot center dot N bonded. An extended intramolecular network of H-bonding (N-H center dot center dot center dot Cl, CH center dot center dot center dot Cl, CH center dot center dot center dot N) causes the 3D self assembling of the units. Upon addition of base, the HCl release from 1a is observed with the transfer to Nb of the O-atom of the carbonylic function of the starting urea which is converted into the relevant carbodiimide CyN=C=NCy 4. The latter is quantitatively released by adding an excess of NEt(3) at 308 K (py and DBU are less efficient) with formation of the known NbOCl(3)(NEt(3))(2), isolated in quantitative yield. Increasing the temperature leads to a loss in selectivity as the formed DCC undergoes further reactions. At 350 K, the isocyanate CyN=C=O has been isolated in 60% yield besides a mixture of Nb-complexes. DFT calculations have been coupled to IR and NMR experiments for characterizing possible reaction intermediates and the behaviour of 1a. Several other MCl(x) species (ScCl(3), YCl(3), LaCl(3), TiCl(4), TaCl(5), AlCl(3), SnCl(4)) have been shown to be able to co-ordinate DCU but not all of them promote the conversion of urea into DCC.

We have fabricated microstrips of Nb thin films by dc magnetron sputtering and lift-off. Focused ion beam (FIB) has been used to mill the surface of the films in a nanometer-sized region across the width of the strip. FIB has the side effect of implanting Ga+ ions on the exposed surface of Nb, damaging the film and modifying its superconducting properties. To overcome this problem, the surface of the FIB-milled Nb films has been passivated by anodization, including the damaged region of the strip into the oxidized layer. Anodization also allows for finely tuning the thickness of the nanoconstrictions after the milling process. We report here the effect of FIB exposure and anodization voltage on the superconducting transition temperature and on the temperature dependence of the resistance of the Nb nanoconstric- tions. We also show some preliminary results suggesting that these devices behave as overdamped SNS-like Josephson junctions.