Non-adiabatic Kohn-anomaly in a doped graphene monolayer

We compute, from first-principles, the frequency of the E2g, Gamma phonon (Raman G-band) of graphene, as a function of the charge doping. Calculations are done using i) the adiabatic Born-Oppenheimer approximation and ii) time-dependent perturbation theory to explore dynamic effects beyond this approximation. The two approaches provide very different results. While, the adiabatic phonon frequency weakly depends on the doping, the dynamic one rapidly varies because of a Kohn anomaly. The adiabatic approximation is considered valid in most materials. Here, we show that doped graphene is a spectacular example where this approximation miserably fails.Comment: 5 pages, 3 figures, Accepted by Phys. Rev. Let

An adaptive stigmergy-based system for evaluating technological indicator dynamics in the context of smart specialization

Regional innovation is more and more considered an important enabler of welfare. It is no coincidence that the European Commission has started looking at regional peculiarities and dynamics, in order to focus Research and Innovation Strategies for Smart Specialization towards effective investment policies. In this context, this work aims to support policy makers in the analysis of innovation-relevant trends. We exploit a European database of the regional patent application to determine the dynamics of a set of technological innovation indicators. For this purpose, we design and develop a software system for assessing unfolding trends in such indicators. In contrast with conventional knowledge-based design, our approach is biologically-inspired and based on self-organization of information. This means that a functional structure, called track, appears and stays spontaneous at runtime when local dynamism in data occurs. A further prototyping of tracks allows a better distinction of the critical phenomena during unfolding events, with a better assessment of the progressing levels. The proposed mechanism works if structural parameters are correctly tuned for the given historical context. Determining such correct parameters is not a simple task since different indicators may have different dynamics. For this purpose, we adopt an adaptation mechanism based on differential evolution. The study includes the problem statement and its characterization in the literature, as well as the proposed solving approach, experimental setting and results.Comment: mail: [email protected]

Polyhydroxyalkanoate (PHA): Review of synthesis, characteristics, processing and potential applications in packaging

Polyhydroxyalkanoates (PHAs) are gaining increasing attention in the biodegradable polymer market due to their promising properties such as high biodegradability in different environments, not just in composting plants, and processing versatility. Indeed among biopolymers, these biogenic polyesters represent a potential sustainable replacement for fossil fuel-based thermoplastics. Most commercially available PHAs are obtained with pure microbial cultures grown on renewable feedstocks (i.e. glucose) under sterile conditions but recent research studies focus on the use of wastes as growth media. PHA can be extracted from the bacteria cell and then formulated and processed by extrusion for production of rigid and flexible plastic suitable not just for the most assessed medical applications but also considered for applications including packaging, moulded goods, paper coatings, non-woven fabrics, adhesives, films and performance additives. The present paper reviews the different classes of PHAs, their main properties, processing aspects, commercially available ones, as well as limitations and related improvements being researched, with specific focus on potential applications of PHAs in packaging

First principles calculation of vibrational Raman spectra in large systems: signature of small rings in crystalline SiO2

We present an approach for the efficient calculation of vibrational Raman intensities in periodic systems within density functional theory. The Raman intensities are computed from the second order derivative of the electronic density matrix with respect to a uniform electric field. In contrast to previous approaches, the computational effort required by our method for the evaluation of the intensities is negligible compared to that required for the calculation of vibrational frequencies. As a first application, we study the signature of 3- and 4-membered rings in the the Raman spectra of several polymorphs of SiO2, including a zeolite having 102 atoms per unit cell.Comment: 4 pages, 2 figures, revtex4 Minor corrections; accepted in Phys. Rev. Let

Structure and stability of graphene nanoribbons in oxygen, carbon dioxide, water, and ammonia

We determine, by means of density functional theory, the stability and the structure of graphene nanoribbon (GNR) edges in presence of molecules such as oxygen, water, ammonia, and carbon dioxide. As in the case of hydrogen-terminated nanoribbons, we find that the most stable armchair and zigzag configurations are characterized by a non-metallic/non-magnetic nature, and are compatible with Clar's sextet rules, well known in organic chemistry. In particular, we predict that, at thermodynamic equilibrium, neutral GNRs in oxygen-rich atmosphere should preferentially be along the armchair direction, while water-saturated GNRs should present zigzag edges. Our results promise to be particularly useful to GNRs synthesis, since the most recent and advanced experimental routes are most effective in water and/or ammonia-containing solutions.Comment: accepted for publication in PR

Structure, Stability, Edge States and Aromaticity of Graphene Ribbons

We determine the stability, the geometry, the electronic and magnetic structure of hydrogen-terminated graphene-nanoribbons edges as a function of the hydrogen content of the environment by means of density functional theory. Antiferromagnetic zigzag ribbons are stable only at extremely-low ultra-vacuum pressures. Under more standard conditions, the most stable structures are the mono- and di-hydrogenated armchair edges and a zigzag edge reconstruction with one di- and two mono-hydrogenated sites. At high hydrogen-concentration ``bulk'' graphene is not stable and spontaneously breaks to form ribbons, in analogy to the spontaneous breaking of graphene into small-width nanoribbons observed experimentally in solution. The stability and the existence of exotic edge electronic-states and/or magnetism is rationalized in terms of simple concepts from organic chemistry (Clar's rule)Comment: 4 pages, 3 figures, accepted for publication by Physical Review Letter

PHB-rich biomass and BioH2 production by means of photosynthetic microorganisms

Polyhydroxyalkanoates (PHAs) are a family of biopolyesters produced by many bacteria as intracellular storage carbon and energy source. Poly-β-hydroxybutyrate (PHB) is probably the most common type of PHA. It is biodegradable and renewable, with relevant thermoplastic properties along with adjustable thermal and mechanical properties. The thermoplastic properties of PHB and its biodegradability make it a potential alternative to petroleum-based plastics. Several microorganisms growing in the dark and/or in the light produce PHB. The polymer is mainly accumulated in the cytoplasm of cells when microorganisms are growing under conditions of stress. If purple non-sulfur photosynthetic bacteria (PNSB) are grown under nitrogen starvation conditions, a photoevolution of molecular hydrogen occurs as well. The PHB amount increases when carbon and energy sources are in excess, but the growth is limited, for example, by the lack of a nitrogen, phosphorous or sulfur source. This work deals the possibility of producing PHAs by photosynthetic microorganisms belonging to cyanobacteria and PNSB. Different culture broths, with and without organic carbon sources, were investigated to maximize PHA production by photosynthetic microorganisms. An unbalanced agro-industrial wastewater has been also investigated in the present study. It concerns the olive mill wastewater (OMW) containing significant reusable carbon fractions suitable for an eco-efficient valorization by feeding photosynthetic processes. The maximum PHA concentration in a cyanobacterium drybiomass was 317 mg/L, when growing cells in a medium with a low content of acetic acid (LAC). In PNSB drybiomass the maximum PHB content was 215 mg/L, when growing PNSB in a synthetic medium. A simultaneous H2 co-production (1,295 mL/L of culture) was cumulated as well, at the end of the process

Thermoplastic Blends Based on Poly(Butylene Succinate-co-Adipate) and Different Collagen Hydrolysates from Tanning Industry: I—Processing and Thermo-mechanical Properties

In this study, blends of a biodegradable thermoplastic polyester, poly (butylene succinate-co-adipate) (PBSA) with two different raw hydrolyzed collagens (HCs), derived from the tannery industry, were investigated in terms of processability, rheological, thermal and mechanical properties. HCs, obtained by alkaline (HCa) and enzymatic (HCe) hydrolysis of the solid wastes generated during the shaving of the tanned leather, were used in PBSA/HC blends, up to 20 wt% of HC, produced by melting extrusion and processed by injection molding. All the blends up to 20 wt% HCs resulted suitable for the injection molding obtaining flexible molded specimens with good tensile properties. The different secondary structure of the two HCs influenced the rheology, morphology and mechanical properties of the produced blends. In particular, HCa, due its higher content of oligopeptides and free amino-acids, showed a good compatibility with the polymeric matrix acting as a plasticizer with consequent reduction of melt viscosity with increasing its loading. The molded dog-bones specimens containing 20 wt% HCa showed a value of elongation at break of 810%. While, HCe, due its higher presence of b-sheet structures, behaved as organic filler, showing a poor interfacial interaction with PBSA with consequent decrease of the tensile properties with increasing its loading. The good processability and satisfactory mechanical properties obtained encourage the use of both investigated collagen hydrolysates in the production of thermoplastic blends and relative molded products for applications in agriculture and plant nurseries, such as pots or small containers with fertilizing properties, due the presence of HCs