Film junction effect on foam drainage

Foam drainage is modelled by the flow of liquid through Plateau borders (PBs) that are the liquid channels resulting from the merging of three liquid films separating the gas bubbles. Available models generally neglect the influence of these films. Yet, within drainage conditions, experimental observations indicate a strong coupling of these films with the channels. We consider the influence of films on foam drainage through their effect on the cross-section geometry of the channels. More precisely, we assume that the Plateau border cross-section is enclosed by three circular arcs that are not always tangent but instead exhibit a non-zero contact angle θ as it has been observed experimentally. The liquid flow through the channels is studied using numerical simulations whose parameters are θ and the Boussinesq number, Bo, that reflects the surface shear viscosity of the interface. We show that, for values of Bo relevant for foam drainage conditions, a slight increase of θ results in a strong decrease of the average liquid velocity.     

Access to novel bicyclic fused γ-butyrolactone using [3,3]-sigmatropic rearrangement and acid-lactonization sequence as key transformation

In this Letter, we wish to disclose a new strategy for the construction of substituted γ-butyrolactones. The latter might not only be of potential interest in terms of biological activity and synthesis but also allow access to original heterocyclic scaffolds. According to previous study, efficient two-step sequence involving Eschenmoser-Claisen rearrangement and acid-lactonization reaction was successfully applied for the construction of original fused bicyclic γ-butyrolactones based on an 1,4-oxazine core.     

Well‐Defined Four‐Coordinate Iron(II) Complexes For Intramolecular Hydroamination of Primary Aliphatic Alkenylamines

Despite the growing interest in iron catalysis and hydroamination reactions, iron‐catalyzed hydroamination of unprotected primary aliphatic amines and unactivated alkenes has not been reported to date. Herein, a novel well‐defined four‐coordinate β‐diketiminatoiron(II) alkyl complex is shown to be an excellent precatalyst for the highly selective cyclohydroamination of primary aliphatic alkenylamines at mild temperatures (70–90 °C). Both empirical kinetic analyses and the reactivity of an isolated iron(II) amidoalkene dimer, [LFe(NHCH₂CPh₂CH₂CH?CH₂)]₂ favor a stepwise σ‐insertive mechanism that entails migratory insertion of the pendant alkene into an iron–amido bond associated with a rate‐determining aminolysis step.     

Synthesis of Oligonucleotides containing the cis-Interstrand Crosslink Produced by Mitomycins in their Reaction with DNA

Mitomycin C (MC) an antitumor drug and decarbamoylmitomycin C (DMC), a derivative of MC lacking the carbamoyl moiety, are DNA alkylating agents which can form DNA interstrand crosslinks (ICLs) between deoxyguanosine residues located on opposing DNA strands. MC forms primarily deoxyguanosine adducts with a 1“-R stereochemistry at the guanine-mitosene bond (1”-α, trans) whereas DMC forms mainly adducts with a 1“-S stereochemistry (1”-β, cis). The crosslinking reaction is diastereospecific: trans-crosslinks are formed exclusively at CpG sequences, while cis-crosslinks are formed only at GpC sequences. Until now, oligonucleotides containing 1“-β-deoxyguanosine adducts or ICL at a specific site could not be synthesized, thus limiting the investigation of the role played by the stereochemical configuration at C1′′ in the toxicity of these compounds. Here, a novel biomimetic synthesis to access these substrates is presented. Structural proof of the adducted oligonucleotides and ICL were provided by enzymatic digestion to nucleosides, high resolution mass spectral analysis, CD spectroscopy and UV melting temperature studies. Finally, a virtual model of the 25-mer 1”-β ICL synthesized was created to explore the conformational space and structural features of the crosslinked duplex.     

A multidimensional approach to the analysis of chemical shift titration experiments in the frame of a multiple reaction scheme

We present a method for fitting curves acquired by chemical shift titration experiments, in the frame of a three‐step complexation mechanism. To that end, we have implemented a fitting procedure, based on a nonlinear least squares fitting method, that determines the best fitting curve using a “coarse grid search” approach and provides distributions for the different parameters of the complexation model that are compatible with the experimental precision. The resulting analysis protocol is first described and validated on a theoretical data set. We show its ability to converge to the true parameter values of the simulated reaction scheme and to evaluate complexation constants together with multidimensional uncertainties. Then, we apply this protocol to the study of the supramolecular interactions, in aqueous solution, between a lanthanide complex and three different model molecules, using NMR titration experiments. We show that within the uncertainty that can be evaluated from the parameter distributions generated during our analysis, the affinities between the lanthanide derivative and each model molecule can be discriminated, and we propose values for the corresponding thermodynamic constants. Copyright © 2013 John Wiley & Sons, Ltd.     

Identification and Role of a 6‐Deoxy‐4‐Keto‐Hexosamine in the Lipopolysaccharide Outer Core of Yersinia enterocolitica Serotype O:3

The outer core (OC) region of Yersinia enterocolitica serotype O:3 lipopolysaccharide is a hexasaccharide essential for the integrity of the outer membrane. It is involved in resistance against cationic antimicrobial peptides and plays a role in virulence during early phases of infection. We show here that the proximal residue of the OC hexasaccharide is a rarely encountered 4‐keto‐hexosamine, 2‐acetamido‐2,6‐dideoxy‐D ‐xylo‐hex‐4‐ulopyranose (Sugp) and that WbcP is a UDP‐GlcNAc‐4,6‐dehydratase enzyme responsible for the biosynthesis of the nucleotide‐activated form of this rare sugar converting UDP‐2‐acetamido‐2‐deoxy‐D ‐glucopyranose (UDP‐D ‐GlcpNAc) to UDP‐2‐acetamido‐2,6‐dideoxy‐D ‐xylo‐hex‐4‐ulopyranose (UDP‐ Sugp). In an aqueous environment, the 4‐keto group of this sugar was present in the 4‐dihydroxy form, due to hydration. Furthermore, evidence is provided that the axial 4‐hydroxy group of this dihydroxy function was crucial for the biological role of the OC, that is, in the bacteriophage and enterocoliticin receptor structure and in the epitope of a monoclonal antibody.     

Investigation of RNA-Ligand Interactions by (19) F NMR Spectroscopy Using Fluorinated Probes

Spy swap: The interaction between an unlabeled RNA and unlabeled ligands (red hexagon) can be monitored by (19) F?NMR spectroscopy using small fluorinated diamines (green star) as spy reporters. This technique also enables the visualization of the conformational capture of a riboswitch by its ligand.     

Quadpack computation of Feynman loop integrals

The paper addresses a numerical computation of Feynman loop integrals, which are computed by an extrapolation to the limit as a parameter in the integrand tends to zero. An important objective is to achieve an automatic computation which is effective for a wide range of instances. Singular or near singular integrand behavior is handled via an adaptive partitioning of the domain, implemented in an iterated/repeated multivariate integration method. Integrand singularities possibly introduced via infrared (IR) divergence at the boundaries of the integration domain are addressed using a version of the Dqags algorithm from the integration package Quadpack, which uses an adaptive strategy combined with extrapolation. The latter is justified for a large class of problems by the underlying asymptotic expansions of the integration error. For IR divergent problems, an extrapolation scheme is presented based on dimensional regularization.