A successful chemical strategy to induce oligothiophene self-assembly into fibers with tunable shape and function

Functional supramolecular architectures for bottom-up organic nano- and microtechnology are a high priority research topic. We discovered a new recognition algorithm, resulting from the combination of thioalkyl substituents and head-to-head regiochemistry of substitution, to induce the spontaneous self-assembly of sulfur overrich octathiophenes into supramolecular crystalline fibers combining high charge mobility and intense fluorescence. The fibers were grown on various types of surfaces either as superhelices or straight rods depending on molecular structure. Helical fibers directly grown on a field effect transistor displayed efficient charge mobility and intrinsic 'memory effect'. Despite the fact that the oligomers did not have chirality centers, one type of hand-helicity was always predominant in helical fibers, due to the interplay of molecular atropisomerism and supramolecular helicity induced by terminal substituents. Finally, we found that the new sulfur overrich oligothiophenes can easily be prepared in high yields through ultrasound and microwave assistance in green conditions.     

Photogenerated defects in shape-controlled TiO2 anatase nanocrystals: a probe to evaluate the role of crystal facets in photocatalytic processes

The promising properties of anatase TiO(2) nanocrystals exposing specific surfaces have been investigated in depth both theoretically and experimentally. However, a clear assessment of the role of the crystal faces in photocatalytic processes is still under debate. In order to clarify this issue, we have comprehensively explored the properties of the photogenerated defects and in particular their dependence on the exposed crystal faces in shape-controlled anatase. Nanocrystals were synthesized by solvothermal reaction of titanium butoxide in the presence of oleic acid and oleylamine as morphology-directing agents, and their photocatalytic performances were evaluated in the phenol mineralization in aqueous media, using O(2) as the oxidizing agent. The charge-trapping centers, Ti(3+), O(-), and O(2)(-), formed by UV irradiation of the catalyst were detected by electron spin resonance, and their abundance and reactivity were related to the exposed crystal faces and to the photoefficiency of the nanocrystals. In vacuum conditions, the concentration of trapped holes (O(-) centers) increases with increasing {001} surface area and photoactivity, while the amount of Ti(3+) centers increases with the specific surface area of {101} facets, and the highest value occurs for the sample with the worst photooxidative efficacy. These results suggest that {001} surfaces can be considered essentially as oxidation sites with a key role in the photoxidation, while {101} surfaces provide reductive sites which do not directly assist the oxidative processes. Photoexcitation experiments in O(2) atmosphere led to the formation of Ti(4+)-O(2)(-) oxidant species mainly located on {101} faces, confirming the indirect contribution of these surfaces to the photooxidative processes. Although this work focuses on the properties of TiO(2), we expect that the presented quantitative investigation may provide a new methodological tool for a more effective evaluation of the role of metal oxide crystal faces in photocatalytic processes.     

Water evaporation from gel beads

Hydrogels are characterized by properties which make them ideal candidates for applications in several fields, such as drug delivery, biomedicine, and functional foods. Molecular diffusion out of a hydrogel matrix depends on their hydrodynamic radii and the mesh sizes within the matrix of the gel. A quantitative experimental and mathematical understanding of interactions, kinetics, and transport phenomena within complex hydrogel systems assists network design by identifying the key parameters and mechanisms that govern the rate and extent of solute release. In this article a calorimetric differential scanning calorimetry (DSC) study reports on the approach to parallel water effusion from a hydrogel matrix to the release of a model protein. The measurement of the water evaporation is taken as the simplest routine determination of a phenomenon that is basically due to a diffusive process through the porous structure of the gel and thermodynamically governed by the difference in the water chemical potential inside and outside of the bead. The analysis of the experimental calorimetric curves is made with the purpose of extracting several numerical parameters characteristic of each curve. The rationale is to develop a simple methodology to understand the release properties of the porous structure of the complex gel matrix by means of DSC.     

A priori estimates for rough PDEs with application to rough conservation laws

We introduce a general weak formulation for PDEs driven by rough paths, as well as a new strategy to prove well-posedness. Our procedure is based on a combination of fundamental a priori estimates with (rough) Gronwall-type arguments. In particular this approach does not rely on any sort of transformation formula (flow transformation, Feynman–Kac representation formula etc.) and is therefore rather flexible. As an application, we study conservation laws driven by rough paths establishing well–posedness for the corresponding kinetic formulation.     

Embedding a novel objective function in a two-phased local search for robust vertex coloring

In this paper, we propose a two-phased local search for vertex coloring. The algorithm alternately executes two closely interacting functionalities, i.e., a stochastic and a deterministic local search. The stochastic phase is basically based on biased random sampling that, according to a probability matrix storing the probability a vertex can be assigned to a color, iteratively constructs feasible colorings. The deterministic phase, instead, consists in assigning sequentially, according to a given ordering, each vertex to the color which causes the lowest increase of the solution penalty, and then, when the schedule is constructed, swap operations are executed to improve the performance. The interaction between the two phases is implemented by tunnelling information of what happened during a phase to the successive ones. Beyond the algorithm scheme, the novelty of the approach stems from the fact that the objective function is not minimizing the number of colors but a new penalty function. The proposed approach is tested on known benchmarks for the studied problem available on the public domain. From a comparison to the state of the art it appears that the proposed approach is robust and is able to achieve best known results.     

Synthesis of novel rigid-rod and tripodal azulene chromophores

Two novel azulene chromophores 1 and 2 were synthesized to study dynamics of ultrafast electron injection at the interface of TiO₂ semiconductor nanoparticles. Fluorescence quenching was observed upon binding.     

Dynamical Aspects of TEM-1 β-Lactamase Probed by Molecular Dynamics

The dynamical aspects of the fully hydrated TEM-1 β-lactamase have been determined by a 5 ns Molecular Dynamics simulation. Starting from the crystallographic coordinates, the protein shows a relaxation in water with an overall root mean square deviation from the crystal structure increasing up to 0.17 nm, within the first nanosecond. Then a plateau is reached and the molecule fluctuates around an equilibrium conformation. The results obtained in the first nanosecond are in agreement with those of a previous simulation (Diaz et al., J. Am. Chem. Soc., (2003) 125, 672–684). The successive equilibrium conformation in solution shows an increased mobility characterized by the following aspects. A flap-like translational motion anchores the Ω-loop to the body of the enzyme. A relevant part of the backbone dynamics implies a rotational motion of one domain relative to the other. The water molecules in the active site can exchange with different residence times. The H-bonding networks formed by the catalytic residues are frequently interrupted by water molecules that could favour proton transfer reactions. An additional simulation, where the aspartyl dyad D214–D233 was considered fully deprotonated, shows that the active site is destabilized.     

On the effect of a point mutation on the reactivity of CuZn superoxide dismutase: a theoretical study

In this paper, we investigate the effects of a point mutation on the enzymatic activity of copper-zinc superoxide dismutase, which we recently studied in detail by means of a theoretical-computational procedure. Comparison of the reactivity of the initial catalytic steps in this mutant (G93A mutation far from the active site) with our previous data, reveals the beautiful mechanical-dynamical architecture of the enzyme, altered by such an apparently irrelevant mutation. Finally, our results suggest a possible atomic-molecular-based explanation for the mutant-pathology correlation, in line with the most recent experimental data.     

Ordered patterning of nanometric rings of single molecule magnets on polymers by lithographic control of demixing

We report a new patterning process which takes place as a result of demixing of a binary polymer/solute mixture. An efficient, sustainable approach for ordering nanosized rings of so-called single molecule magnets (SMMs) is thus provided. It exploits the self-organization process in which SMM patterned film evolves to a spatially correlated pattern of nanosized rings. At long time, the anisotropic patterning of the film drives the ring to coalesce, into parallel lines of nanometric width.