Novel photocatalytic processes mediated by carbon nitride photocatalysis

The key to reduce the energy required for specific transformations in a selective manner is the employment of a catalyst, a very small molecular platform that decides which type of energy to use. The field of photocatalysis exploits light energy to shape one type of molecules into others, more valuable and useful. However, many challenges arise in this field, for example, catalysts employed usually are based on metal derivatives, which abundance is limited, they cannot be recycled and are expensive. Therefore, carbon nitrides materials are used in this work to expand horizons in the field of photocatalysis.Carbon nitrides are organic materials, which can act as recyclable, cheap, non-toxic, heterogeneous photocatalysts. In this thesis, they have been exploited for the development of new catalytic methods, and shaped to develop new types of processes. Indeed, they enabled the creation of a new photocatalytic synthetic strategy, the dichloromethylation of enones by dichloromethyl radical generated in situ from chloroform, a novel route for the making of building blocks to be used for the productions of active pharmaceutical compounds. Then, the ductility of these materials allowed to shape carbon nitride into coating for lab vials, EPR capillaries, and a cell of a flow reactor showing the great potential of such flexible technology in photocatalysis. Afterwards, their ability to store charges has been exploited in the reduction of organic substrates under dark conditions, gaining new insights regarding multisite proton coupled electron transfer processes. Furthermore, the combination of carbon nitrides with flavins allowed the development of composite materials with improved photocatalytic activity in the CO2 photoreduction.Concluding, carbon nitrides are a versatile class of photoactive materials, which may help to unveil further scientific discoveries and to develop a more sustainable future

Dichloromethylation of enones by carbon nitride photocatalysis

Small organic radicals are ubiquitous intermediates in photocatalysis and are used in organic synthesis to install functional groups and to tune electronic properties and pharmacokinetic parameters of the final molecule. Development of new methods to generate small organic radicals with added functionality can further extend the utility of photocatalysis for synthetic needs. Herein, we present a method to generate dichloromethyl radicals from chloroform using a heterogeneous potassium poly(heptazine imide) (K-PHI) photocatalyst under visible light irradiation for C1-extension of the enone backbone. The method is applied on 15 enones, with γ,γ-dichloroketones yields of 18–89%. Due to negative zeta-potential (−40 mV) and small particle size (100 nm) K-PHI suspension is used in quasi-homogeneous flow-photoreactor increasing the productivity by 19 times compared to the batch approach. The resulting γ,γ-dichloroketones, are used as bifunctional building blocks to access value-added organic compounds such as substituted furans and pyrroles

Energy and Structure of Hard-Sphere Bose Gases in three and two dimensions

The energy and structure of dilute gases of hard spheres in three dimensions is discussed, together with some aspects of the corresponding 2D systems. A variational approach in the framework of the Hypernetted Chain Equations (HNC) is used starting from a Jastrow wavefunction that is optimized to produce the best two--body correlation factor with the appropriate long range. Relevant quantities describing static properties of the system are studied as a function of the gas parameter $x=\rho a^d$ where $\rho$, $a$ and $d$ are the density, $s$--wave scattering length of the potential and dimensionality of the space, respectively. The occurrence of a maximum in the radial distribution function and in the momentum distribution is a natural effect of the correlations when $x$ increases. Some aspects of the asymptotic behavior of the functions characterizing the structure of the systems are also investigated.Comment: Proceedings of the QFS2004 conference in Trento. To appear in JLT

Single-particle vs. pair superfluidity in a bilayer system of dipolar bosons

We consider the ground state of a bilayer system of dipolar bosons, where dipoles are oriented by an external field in the direction perpendicular to the parallel planes. Quantum Monte Carlo methods are used to calculate the ground-state energy, the one-body and two-body density matrix, and the superfluid response as a function of the separation between layers. We find that by decreasing the interlayer distance for fixed value of the strength of the dipolar interaction, the system undergoes a quantum phase transition from a single-particle to a pair superfluid. The single-particle superfluid is characterized by a finite value of both the atomic condensate and the super-counterfluid density. The pair superfluid phase is found to be stable against formation of many-body cluster states and features a gap in the spectrum of elementary excitations.Comment: 4 figure

Peano Structures and the Semantics of Iteration

In this paper closure theory is applied in order to obtain a uniform semantical treatment of both primitive and general iteration. In particular, the theory of Peano algebras has been extended to algebraic structures to inductively define both primitive and general iterates as structure homomorphisms, i.e. as fixed points of iteration equations

Integrating geomechanical surveys and remote sensing for sea cliff slope stability analysis: the Mt. Pucci case study (Italy)

Abstract. An integrated approach to the geomechanical characterization of coastal sea cliffs was applied at Mt. Pucci (Gargano promontory, Southern Italy) by performing field-based geomechanical investigations and remote geostructural investigations via a terrestrial laser scanner (TLS). The consistency of the integrated techniques allowed to achieve a comprehensive and affordable characterization of the main joint sets on the sea cliff slope. The observed joint sets were considered to evaluate the proneness of the slope to rock failures by attributing safety factor (SF) values to the topple- and wedge-prone rock blocks under three combined or independent triggering conditions: (a) hydrostatic water pressures within the joints, (b) seismic action, and (c) strength reduction due to weathering of the joint surfaces. The combined action of weathering and water pressures within the joints was also considered, resulting in a significant decrease in the stability. Furthermore, remote survey analyses via InfraRed Thermography (IRT) and Ground Based Synthetic Aperture Radar Interferometry (GBInSAR) were performed to evaluate the role of the surveyed joint sets in inducing instabilities in the Mt. Pucci sea cliff. The results from the remote surveys: (i) GBInSAR monitoring revealed permanent displacements coupled to cyclic daily displacements, these last ones detected in certain sectors of the cliff wall; (ii) the thermal images allowed us to identify anomalies that correspond well to the main joints and to the slope material released due to recent collapses

Conformational Studies by Dynamic NMR. 80. Cog-Wheel Effect in the Stereolabile Helical Enantiomers of Dimesityl Sulfoxide and Sulfone.

The 1H NMR solution spectra of the title compounds display anisochronous lines for the o-methyl substituents below -170 °C, due to the existence of two propeller-like M and P conformational enantiomers. The free energies of activation for the interconversion were determined to be 4.5 and 5.0 kcal mol -1, respectively, for dimesityl sulfoxide and dimesityl sulfone. Molecular mechanics calculations indicate that the enantiomerization process occurs via a correlated rotation (cog-wheel effect) entailing a one-ring flip (gear-meshing) pathway. 13C NMR (CP-MAS) spectra and X-ray diffraction show that these helical enantiomers are stable in the crystalline state

Ground state properties of a dilute homogeneous Bose gas of hard disks in two dimensions

The energy and structure of a dilute hard-disks Bose gas are studied in the framework of a variational many-body approach based on a Jastrow correlated ground state wave function. The asymptotic behaviors of the radial distribution function and the one-body density matrix are analyzed after solving the Euler equation obtained by a free minimization of the hypernetted chain energy functional. Our results show important deviations from those of the available low density expansions, already at gas parameter values $x\sim 0.001$. The condensate fraction in 2D is also computed and found generally lower than the 3D one at the same $x$.Comment: Submitted to PRA. 7 pages and 8 figure

Urban engineered slope collapsed in Rome on February 14th, 2018. Results from remote sensing monitoring

On February 14th, 2018, in the North-Western sector of the Municipality of Rome (Central Italy), in the framework of an excavation for building construction, a portion of a piling wall piling wall collapsed in an already densely urbanized area. Soil behind the collapsed piling wall slipped inside the excavation site dragging seven cars parked on one side of the road running parallel to the piling wall and affecting some residential buildings located on the opposite side of the road. Fortunately, no injuries were counted but the 22 families living in the buildings next to the damaged wall were evacuated. Following the piling wall collapse, the Civil Protection of Rome, thanks to the technical support of the Research Centre on Geological Risks (CERI) of the Sapienza University of Rome, started a continuous monitoring of the affected area through remote sensing techniques. In the first hours following the collapse, a Terrestrial Synthetic Aperture Radar Interferometer (TInSAR) and a terrestrial laser scanner (TLS) were installed with the aim to control the evolution of the process, to support the local authority to manage the associated residual risk, and to ensure the safety of workers during emergency operations. In this paper we discuss some of the results obtained by the monitoring of the involved area. Thanks to the comparisons between different surveys and the reconstruction of the pre-event geometries, the total volume involved in the failure was estimated around 850 m3. In addition, through the analysis of data acquired by the 18 multi-temporal TLS scans and the three and a half months of continuous TInSAR monitoring, the movement involving a portion of the filling material used for stabilization works was observed and described. Such movement, reaching a total displacement of about 270–300 mm, was monitored and reported in real time

Ferromagnetic transition of a two-component Fermi gas of Hard Spheres

We use microscopic many-body theory to analyze the problem of itinerant ferromagnetism in a repulsive atomic Fermi gas of Hard Spheres. Using simple arguments, we show that the available theoretical predictions for the onset of the ferromagnetic transition predict a transition point at a density ($k_F a \sim 1$) that is too large to be compatible with the universal low-density expansion of the energy. We present new variational calculations for the hard-sphere Fermi gas, in the framework of Fermi hypperneted chain theory, that shift the transition to higher densities ($k_F a \sim 1.8$). Backflow correlations, which are mainly active in the unpolarized system, are essential for this shift