On the next-to-next-to-leading order QCD corrections to heavy-quark production in deep-inelastic scattering

The contribution of quarks with masses m >> Lambda_QCD is the only part of the structure functions in deep-inelastic scattering (DIS) which is not yet known at the next-to-next-to-leading order (NNLO) of perturbative QCD. We present improved partial NNLO results for the most important structure function F_2(x,Q^2) near the partonic threshold, in the high-energy (small-x) limit and at high scales Q^2 >> m^2; and employ these results to construct approximations for the gluon and quark coefficient functions which cover the full kinematic plane. The approximation uncertainties are carefully investigated, and found to be large only at very small values, x smaller about 10^-3, of the Bjorken variable.Comment: 62 pages, LaTeX, 13 figures. Erratum for eq.(B.7

A crystallographic route to understand drug solubility: the case of 4- aminoquinoline antimalarials

Most Active Pharmaceutical Ingredients (API) can be prepared in various crystalline forms [1] displaying largely different physical/chemical properties and bioavailability. Salt formation represents the most common and simplest chemical way to modify the overall features but also the toxicity and biopharmaceutical availability of a drug substance. However, it is often unclear how and why the chemical and crystallographic characters can cooperate in determining these changes. We here face the problem from the perspective of the antiplasmodial drug piperaquine (PQ, C29H32Cl2N6) [2]. Being highly lipophilic, both neutral PQ and its commercial hydrogen phosphate tetrahydrate salt are poorly soluble in water, resulting in a reduced oral bioavailability. We synthesized five novel PQ salts and characterized them by both single crystal X\u2013ray diffraction methods and T-dependent (20 \u2013 50 \ubaC) UV\u2013Vis spectroscopy. Our aim was to explore possible relationships among non-covalent interaction networks in the crystals and measured solubilities. We also estimated changes in thermodynamic state functions related to the solvation process by DFT simulations, both in vacuo and in the solid state. We found that solubilities of PQ salts conform in most cases to the Hard and Soft Acid and Bases (HSAB) rules, i.e. less soluble compounds bear ions of comparable hardness. Crystal packing plays a far less important role, even though disorder-related entropic effects can influence the response of solubility to temperature. A possible take-home message is that intensive thermodynamic properties stem from a non-trivial cooperation several physicochemical effects. A first-principle understanding of the drug solubility cannot rely just on the description of the crystal packing, but must take into account the explicit evaluation of interaction energetics and pertinent electronic factors. [1] R. Hilfiker and M. von Raumer, Polymorphism in the Pharmaceutical Industry: Solid Form and Drug Development. 2019, Wiley-VCH, Weinheim (Germany). ISBN: 978-3-527-34040-8. [2] P. Sacchi, L. Loconte, G. Macetti, S. Rizzato and L. Lo Presti Crystal Growth Des. 2019. 19, 139

Joint Alignment and Modeling of Correlated Behavior Streams

The Variable Time-Shift Hidden Markov Model (VTS- HMM) is proposed for learning and modeling pairs of cor- related streams. Unlike previous coupled models for time series, the VTS-HMM accounts for varying time shifts be- tween correlated events in pairs of streams having different properties. The VTS-HMM is learned on a set of pairs of unaligned streams and, thus, learning entails simultaneous estimation of the varying time shifts and of the parameters of the model. The formulation is demonstrated in the analysis of videos of dyadic social interactions between children and adults in the Multimodal Dyadic Behavior Dataset (MMDB). In dyadic social interactions, an agent starts an interaction with one or more \u201cinitiating behaviors\u201d that elicit one or more \u201cresponding behaviors\u201d from the partner within a temporal window. The proposed VTS-HMM explicitly accounts for varying time shifts between initiating and responding behaviors in these behavior streams. The experiments confirm that modeling of these varying time shifts in the VTS-HMM can yield improved estimation of the level of engagement of the child and adult and more accurate dis- crimination among complex activities

The TACO Puzzle: A Phase-Transition Mystery Revisited

The organic salt (5-methyl-1-thia-5-azacyclo-octane-1-oxide) perchlorate (TACO) is known to undergo a single-crystal-to-single-crystal phase transition in the 276-298 K T range without a change in the external shape of the sample. Despite extensive computational and experimental investigations, no safe conclusions about the transition mechanism could be drawn till now. The two packing patterns are very similar, and symmetry is conserved, apart from an interchange of cell axes from P21/c (\u3b1-TACO, low-T) to P21/a (\u3b2-TACO, high-T). Yet, the phase transition implies a significant conformational rearrangement, coupled with 3c180\ub0-wide rotations, of 1/2 of the cations, in conjunction with reorientation of the anions. Here, we analyze the crystal packing of the two phases in terms of pairwise molecule-molecule interaction energies, as derived from the PIXEL approach. Rigid-body molecular reorientations are simulated by solid-state Monte Carlo calculations, while the likelihood of conformational rearrangements is estimated through gas-phase density functional theory M06/6-311G(p,d) simulations. We demonstrate that rotational motion of the cations is not hampered by substantial energetic barriers, while the ring flip can be described as a two-step process with a main kinetic barrier of 3c45 kJ\ub7mol-1, which might explain the metastable behavior of the \u3b2 phase at low T. A possible mechanism of the phase transition is proposed, accounting for the present computational evidences in the context of the former experimental findings

SUP&R DSS: A sustainability-based decision support system for road pavements

Road pavement community members are increasingly becoming aware of the need to incorporating the principles of sustainable development into the sector. Policies are also going in this direction and as a consequence in the recent years researchers and practitioners are coming up with new materials, technologies and practices designed to reduce the negative impacts of their activities in the surroundings. Within this framework the road pavements sector is witnessing a paradigm shift towards the development of pavement technologies incorporating high-content of recycled materials, as well as best practices to decrease the overall carbon footprint. These are all promising solutions that to the most can sound as sustainable practices. However the whole road pavement community is still investigating methodologies and tools to define what actually sustainable means and thereby performing a sustainable decision-making. It is within this context that the need of a sustainability-based decision support system (DSS) that could help road pavement engineers at the design stage was identified and is here presented. The Sustainable Pavements & Railways DSS (SUP&R DSS) relies on a multi-criteria decision analysis (MCDA) method to rank the sustainability of alternatives. It applies life cycle-based approaches to quantify the values of a set of indicators purposely and methodologically selected to capture the cause- effect link between the general concepts of the three wellbeing dimensions of sustainability, i.e., environmental, economic and social, and the infrastructure construction and maintenance practice. Furthermore, the system allows selecting different weighting for the indicators but offers also a default set of values derived from a survey conducted with over 50 stakeholders in Europe and beyond. Together with the development, structure and features of the SUP&R DSS, this paper present its applicability by means of a case study aiming at identifying the most sustainable asphalt mixture for wearing courses. Several promising options for flexible road pavements were selected, ranging from low to hot temperature asphalt. The results show that a foamed warm mix asphalt mixture with a reclaimed asphalt pavement content of 50% is the most sustainable among the competing alternatives. Furthermore, a sensitivity analysis conducted to investigate the influence of the indicators weights, the parameters of the MCDA method and the long-term performance of the alternative asphalt mixtures on the stability of the ranking showed that its first position in the ranking remained unaffected

Gesture Modeling by Hanklet-based Hidden Markov Model

In this paper we propose a novel approach for gesture modeling. We aim at decomposing a gesture into sub-trajectories that are the output of a sequence of atomic linear time invariant (LTI) systems, and we use a Hidden Markov Model to model the transitions from the LTI system to another. For this purpose, we represent the human body motion in a temporal window as a set of body joint trajectories that we assume are the output of an LTI system. We describe the set of trajectories in a temporal window by the corresponding Hankel matrix (Hanklet), which embeds the observability matrix of the LTI system that produced it. We train a set of HMMs (one for each gesture class) with a discriminative approach. To account for the sharing of body motion templates we allow the HMMs to share the same state space. We demonstrate by means of experiments on two publicly available datasets that, even with just considering the trajectories of the 3D joints, our method achieves state-of-the-art accuracy while competing well with methods that employ more complex models and feature representations

Correlations of Crystal Structure and Solubility in Organic Salts: The Case of the Antiplasmodial Drug Piperaquine

Five organic salts of the antiplasmodial drug piperaquine (PQ, C29H32Cl2N6) were synthesized and characterized by X-ray diffraction methods. The corresponding solubilities in water and acetic acid solutions were evaluated in the 20-50 \ub0C (293-323 K) T range by UV-vis spectroscopy, with the aim of elucidating how they depend on chemical, structural, and thermodynamic factors. Experiments were complemented by DFT calculations, both in vacuo and in the solid state, to estimate changes in thermodynamic state functions related to the solvation process. It is demonstrated that solubility is mainly governed by the electronic and chemical properties of the anion, while lattice energies and packing effects, including in-crystal conformational changes of the drug, play a less important role. PQ salts generally conform to the predictions of hard and soft acid and bases (HSAB) theory, as less soluble compounds bear ions of comparable hardness, and vice versa. A remarkable exception is the PQ hydrogen sulfate salt, whose poor solubility can be ascribed to an exceptionally stable crystal lattice. Other factors, such as entropic effects related to solid-state disorder, can influence the response of solubility to temperature

Unravelling the Chemistry of the [Cu(4,7-Dichloroquinoline)2Br2]2 Dimeric Complex through Structural Analysis: A Borderline Ligand Field Case

Large dark prismatic crystals (P 1\uaf ) consisting of closely packed centrosymmetric [Cu(4,7-dichloroquinoline)2]2Br4 binuclear units are formed when 4,7-dichloroquinoline (DCQ, C9H5NCl2) binds copper(II). Cu2+ adopts a strongly distorted square pyramidal coordination geometry, perturbed by electrostatic interactions with two axial \u3bc\u2013Br ligands acting as highly asymmetric bridges. It is shown that, as electronic states of ligands are higher in energy than the metal ones, antibonding orbitals bear significant ligand-like character and electronic charge is partially transferred from inner-sphere coordinated halogen atoms to copper. Overall, the title compound sits on the Hoffman\u2019s border between main group and transition chemistry, with non-negligible contributions of the ligands to the frontier orbitals. The relative energy placement of metal and ligand states determines an internal redox process, where the metal is slightly reduced at the expense of partial oxidation of the bromide ligands. In fact, the crystal structure is partially disordered due to the substitution of some penta-coordinated Cu(II) centers with tetra-coordinated Cu(I) ions. The geometry of the complex is rationalized in terms of electrostatic-driven distortions from an ideal octahedral prototype. Implications on the reactivity of Cu(II)\u2013quinoline complexes are discusse