W^+W^-, WZ and ZZ production in the POWHEG-BOX-V2

We present an implementation of the vector boson pair production processes $ZZ$ , $W^+W^-$ and $WZ$ within the POWHEG-BOX-V2. This implementation, derived from the POWHEG BOX version, has several improvements over the old one, among which the inclusion of all decay modes of the vector bosons, the possibility to generate different decay modes in the same run, speed optimization and phase space improvements in the handling of interference and singly resonant contributions.     

Photoacclimation Responses of the Brown Macroalga Sargassum Cymosum to the Combined Influence of UV Radiation and Salinity: Cytochemical and Ultrastructural Organization and Photosynthetic Performance

The photoacclimation responses of the brown macroalga Sargassum cymosum were studied to determine its cytochemical and ultrastructural organization, as well as photosynthetic pigments and performance. S. cymosum was cultivated in three salinities (30, 35 and 40 psu) under four irradiation treatments: PAR‐only, PAR + UVA, PAR + UVB and PAR + UVA + UVB. Plants were exposed to PAR at 70 μmol photons m^?2 s^?1, PAR + UVB at 0.35 W m^?2 and PAR +UVA at 0.70 W m^?2 for 3 h per day during 7 days in vitro. Growth rate was not significantly affected by any type of radiation or salinity. The amount of pigments in S. cymosum was significantly influenced by the interaction of salinity and radiation treatments. Compared with PAR‐only, UVR treatments modified the kinetics patterns of the photosynthesis/irradiance curve. After exposure to UVR, S. cymosum increased cell wall thickness and the presence of phenolic compounds. The number of mitochondria increased, whereas the number of chloroplasts showed few changes. Although S. cymosum showed insensitivity to changes in salinity, it can be concluded that samples treated under four irradiation regimes showed structural changes, which were more evident, but not severe, under PAR + UVB treatment.     

Metal‐Free Photochemical Aromatic Perfluoroalkylation of α‐Cyano Arylacetates

We report here an operationally simple protocol for the direct aromatic perfluoroalkylation and trifluoromethylation of α‐cyano arylacetates. This metal‐free approach, which occurs at ambient temperature and under visible‐light irradiation, is driven by the photochemical activity of electron donor–acceptor (EDA) complexes, formed in situ by the interaction of transiently generated enolates and perfluoroalkyl iodides. Preliminary mechanistic studies are reported.     

Manganese(II) pyrimidine-4,6-dicarboxylates: synthetic, structural, magnetic, and adsorption insights

A series of manganese(II) coordination polymers containing the bridging ligand pyrimidine-4,6-dicarboxylate (pmdc) have been prepared. The stoichiometries and structural features of these materials, which range from the one-dimensional (1D) chains in ([Mn(mu-pmdc)(H2O)3].2H2O)n (1) and ([Mn2(mu-pmdc)2(H2O)5].2H2O)n (2) to the two-dimensional layers in ([Mn(mu3-pmdc)(H2O)].H2O)n (3) or the three-dimensional porous network in ([Mn(pmdc)].2H2O)n (4), are extremely dependent on the synthetic conditions (i.e., temperature and solvent). In spite of the structural diversity of these systems, crystallographic studies revealed that the pmdc ligand typically displays a tetradentate mu-(kappaO,kappaN:kappaO',kappaN') coordination mode with the carboxylate groups almost coplanar with the pyrimidine ring [as in compounds 1 and 2 and compound 5 described below)]. In compound 3, the pmdc moiety adopts a pentadentate mu3-(kappaO,kappaN:kappaO',kappaN':kappaO) coordination mode. The thermal, magnetic, and adsorption properties of these systems were also studied. The results showed that these compounds behave as antiferromagnets as a consequence of efficient magnetic exchange through the pmdc bridges. Compound 4 possesses permanent porosity, as proved by gas sorption data (N2 at 77 K and CO2 at 293 K). Finally, the heteronuclear iron(II)/manganese(II) compound ([FeMn(mu-pmdc)2(H2O)5].2H2O)n (5), which is isomorphous to 2, was also prepared and fully characterized.     

Combining Solid-State NMR with Structural and Biophysical Techniques to Design Challenging Protein-Drug Conjugates

Several protein-drug conjugates are currently being used in cancer therapy. These conjugates rely on cytotoxic organic compounds that are covalently attached to the carrier proteins or that interact with them via non-covalent interactions. Human transthyretin (TTR), a physiological protein, has already been identified as a possible carrier protein for the delivery of cytotoxic drugs. Here we show the structure-guided development of a new stable cytotoxic molecule based on a known strong binder of TTR and a well-established anticancer drug. This example is used to demonstrate the importance of the integration of multiple biophysical and structural techniques, encompassing microscale thermophoresis, X-ray crystallography and NMR. In particular, we show that solid-state NMR has the ability to reveal effects caused by ligand binding which are more easily relatable to structural and dynamical alterations that impact the stability of macromolecular complexes.     

Synthesis of Bioctacene-Incorporated Nanographene with Near-Infrared Chiroptical Properties

We report the synthesis of a hexabenzoperihexacene (HBPH) with two incorporated octacene substructures, which was unambiguously characterized by single-crystal X-ray analysis. The theoretical isomerization barrier of the (P,P)-/(P,M)-forms was estimated to be 38.4 kcal mol⁻¹, and resolution was achieved by chiral HPLC. Notably, the enantiomers exhibited opposite circular dichroism responses up to the near-infrared (NIR) region (830 nm) with a high g_abs value of 0.017 at 616 nm. Moreover, HBPH demonstrated NIR emission with a maximum at 798 nm and an absolute PLQY of 41 %. The excited-state photophysical properties of HBPH were investigated by ultrafast transient absorption spectroscopy, revealing an intriguing feature that was attributed to the rotational and/or conformational dynamics of HBPH after excitation. These results provide new insight into the design of chiral nanographene with NIR optical properties for potential chiroptical applications.     

Separation of intact proteins on γ‐ray‐induced polymethacrylate monolithic columns: A highly permeable stationary phase with high peak capacity for capillary high‐performance liquid chromatography with high‐resolution mass spectrometry

Polymethacrylate‐based monolithic capillary columns, prepared by γ‐radiation‐induced polymerization, were used to optimize the experimental conditions (nature of the organic modifiers, the content of trifluoroacetic acid and the column temperature) in the separation of nine standard proteins with different hydrophobicities and a wide range of molecular weights. Because of the excellent permeability of the monolithic columns, an ion‐pair reversed‐phase capillary liquid chromatography with high‐resolution mass spectrometry method has been developed by coupling the column directly to the mass spectrometer without a flow‐split and using a standard electrospray interface. Additionally, the high working flow and concomitant high efficiency of these columns allowed us to employ a longer column (up to 50 cm) and achieve a peak capacity value superior to 1000. This work is motivated by the need to develop new materials for high‐resolution chromatographic separation that combine chemical stability at elevated temperatures (up to 75°C) and a broad pH range, with a high peak capacity value. The advantage of the γ‐ray‐induced monolithic column lies in the batch‐to‐batch reproducibility and long‐term high‐temperature stability. Their proven high loading capacity, recovery, good selectivity and high permeability, moreover, compared well with that of a commercially available poly(styrene‐divinylbenzene) monolithic column, which confirms that such monolithic supports might facilitate analysis in proteomics.     

Molecular dynamics simulations of proteins and peptides: from folding to drug design

Computer simulations of proteins, lipids and nucleic acids at equilibrium have become essentially routine. However, the fact remains that complete sampling of conformational space continues to be a bottle-neck in the field. The challenge for the future is to overcome such problems and use computational approaches to understand recognition and spontaneous self-organization in biomolecular systems (folding, aggregation and assembly of complexes), processes that cannot be directly observed experimentally. In this review, examples illustrating the extent to which simulations can be used to understand these phenomena in biomolecular systems will be presented along with examples of methodological developments to increase our physical understanding of the processes. The study cases will cover the problems of peptide-receptor recognition and the use of the information obtained for the design of new non-peptidic ligands; the study of the folding mechanism of small proteins and finally the study of the initial stages of peptide self-aggregation.