The infrared spectrum of DCCF in the 320–850 cm−1 region: bending states up to υ4+υ5 = 3

Infrared spectra of deuterated monofluoroacetylene, DCCF, have been recorded in the region between 320 and 850 cm^?1 at an effective resolution ranging from 0.0024 to 0.0031 cm^?1. In total, 6650 rotation vibration transitions were assigned to 37 bands involving the bending states with v₄ + v₅ and |l₄+l₅|, respectively, up to 3, allowing the characterisation of the ground state and of 18 vibrationally excited states. The vν₅ bending fundamental has been studied for the first time. In addition, the difference band v₃ ← v₄ has been detected and analysed. All the assigned transitions have been fitted simultaneously by adopting a model Hamiltonian that takes into account the vibration and rotation l?type resonances. Rotational transitions in the ground and in bending excited states reported in the literature have been included in the global analysis. The set of 57 derived spectroscopic parameters reproduces 6130 infrared and 90 microwave and millimetre?wave transitions satisfactorily with root mean square values of 5.3 × 10^?4 cm^?1 and 77 kHz, respectively.     

Solving survivable two-layer network design problems by metric inequalities

We address the problem of designing a multi-layer network with survivability requirements. We are given a two-layer network: the lower layer represents the potential physical connections that can be activated, the upper layer is made of logical connections that can be set up using physical links. We are given origin-destination demands (commodities) to be routed at the upper layer. We are also given a set of failure scenarios and, for every scenario, an associated subset of commodities. The goal is to install minimum cost integer capacities on the links of both layers in order to ensure that the commodities can be routed simultaneously on the network. In addition, in every failure scenario the routing of the associated commodities must be guaranteed. We consider two variants of the problem and develop a branch-and-cut scheme based on the capacity formulation. Computational results on instances derived from the SNDLib for single node failure scenarios are discussed.     

Secondary Amine‐Catalyzed Asymmetric γ‐Alkylation of α‐Branched Enals via Dienamine Activation

The direct and enantioselective γ‐alkylation of α‐substituted α,β‐unsaturated aldehydes proceeding under dienamine catalysis is described. We have found that the Seebach modification of the diphenyl‐prolinol silyl ether catalyst in combination with saccharin as an acidic additive promotes an S_N1 alkylation pathway, while ensuring complete γ‐site selectivity and a high stereocontrol. Theoretical and spectroscopic investigations have provided insights into the conformational behavior of the covalent dienamine intermediate derived from the condensation of 2‐methylpent‐2‐enal and the chiral amine. Implications for the mechanism of stereoinduction are discussed.     

Thickness, stability and contact angle of liquid films on and inside nanofibres, nanotubes and nanochannels

While the stability of liquid films on substrates is a classical topic of colloidal science, the availability of nanostructured materials, such as nanotubes, nanofibres and nanochannels, has raised the question of how the stability of liquid films and their wetting behaviour is affected by nanoscale confinement. This paper will present the conditions for the stability of liquid films on and inside cylindrical solid substrates with nanometre scale characteristic dimensions. It is shown that the stability is determined by an effective disjoining/conjoining pressure isotherm which differs from the corresponding disjoining/conjoining pressure isotherm of flat liquid films on flat solid substrates. From the former, the equilibrium contact angles of drops on an outer or inner surface of a cylindrical capillary have been calculated as a function of surface curvature, showing that the expressions for equilibrium contact angles vary for different geometries, in view of the difference in thickness of the film of uniform thickness with which the bulk liquid (drops or menisci) is at equilibrium. These calculations have been extended to the case of glass nanocapillaries and carbon nanotubes, finding good agreement with experimental results in the literature.     

Phase behavior and some calorimetric and physical properties of diurethanes from perfluoropolyether macromonomers

Density and calorimetric measurements have been carried out on copolymeric perfluoropolyethers of molecular weight ranging between 500 and 4700, terminated at both chain ends either with  CH₂OH or ethylurethane groups. Samples of the second series are models for perfluoropolyethers based polyurethanes. Density measurements point out that the terminal alcoholic group brings about a negative excess volume, which increases with decreasing the molecular weight; a lower excess volume is found for urethane‐terminated molecules. Calorimetric traces, T_g, and Δc_p at T_g show that alcoholic‐terminated molecules are amorphous and one phase systems, while urethane‐terminated compounds are crystalline; phase separation is observed for this last series when the molecular weight of the fluorinated segment is larger than 1000. The trend of T_g with molecular weight is discussed for one‐ and two‐phase systems in the light of current theories for the glass transition. The decrease of the melting point with increasing the molecular weight for the urethane series can be described by the Flory equation for random copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1609–1622, 1999     

High-Energy Proton-Beam-Induced Polymerization/Oxygenation of Hydroxynaphthalenes on Meteorites and Nitrogen Transfer from Urea: Modeling Insoluble Organic Matter?

Formation and structural modification of oxygenated polycyclic aromatic hydrocarbons (oxyPAHs) by UV irradiation on minerals have recently been proposed as a possible channel of PAH transformation in astrochemical and prebiotic scenarios of possible relevance for the origin of life. Herein, it is demonstrated that high-energy proton-beam irradiation in the presence of various meteorites, including stony iron, achondrite, and chondrite types, promotes the conversion of two representative oxyPAH compounds, 1-naphthol and 1,8-dihydroxynaphthalene, to complex mixtures of oxygenated and oligomeric derivatives. The main identified products include polyhydroxy derivatives, isomeric dimers encompassing benzofuran and benzopyran scaffolds, and, notably, a range of quinones and perylene derivatives. Addition of urea, a prebiotically relevant chemical precursor, expanded the range of identified species to include, among others, quinone diimines. Proton-beam irradiation of oxyPAH modulated by nitrogen-containing compounds such as urea is proposed as a possible contributory mechanism for the formation and processing of insoluble organic matter in meteorites and in prebiotic processes.     

A Molecular Tool Targeting the Base-Flipping Activity of Human UHRF1

During DNA replication, ubiquitin-like, containing PHD and RING fingers domains 1 (UHRF1) plays key roles in the inheritance of methylation patterns to daughter strands by recognizing through its SET and RING-associated domain (SRA) the methylated CpGs and recruiting DNA methyltransferase 1 (DNMT1). Herein, our goal is to identify UHRF1 inhibitors targeting the 5′-methylcytosine (5mC) binding pocket of the SRA domain to prevent the recognition and flipping of 5mC and determine the molecular and cellular consequences of this inhibition. For this, we used a multidisciplinary strategy combining virtual screening and molecular modeling with biophysical assays in solution and cells. We identified an anthraquinone compound able to bind to the 5mC binding pocket and inhibit the base-flipping process in the low micromolar range. We also showed in cells that this hit impaired the UHRF1/DNMT1 interaction and decreased the overall methylation of DNA, highlighting the critical role of base flipping for DNMT1 recruitment and providing the first proof of concept of the druggability of the 5mC binding pocket. The selected anthraquinone appears thus as a key tool to investigate the role of UHRF1 in the inheritance of methylation patterns, as well as a starting point for hit-to-lead optimizations.     

Inhibitory Effect of Lithospermic Acid on the HIV-1 Nucleocapsid Protein

The HIV-1 nucleocapsid protein (NC) is a desirable target in antiretroviral therapy due to its high conservation among HIV-1 strains, and to its multiple and crucial roles in the HIV-1 replication cycle. Natural products represent a valuable source of NC inhibitors, with the catechol group being a privileged scaffold in NC inhibition. By coupling molecular modeling with NMR spectroscopy and fluorescence-based assays, we disclosed lithospermic acid, a catechol derivative extracted from Salvia miltiorrhizza, as a potent and chemically stable non-covalent inhibitor of the NC. Being different from other catechol derivative reported so far, lithospermic acid does not undergo spontaneous oxidation in physiological conditions, thus becoming a profitable starting point for the development of efficient NC inhibitors.