Can nonlinear elasticity explain contact-line roughness at depinning?

We examine whether cubic nonlinearities, allowed by symmetry in the elastic energy of a contact line, may result in a different universality class at depinning. Standard linear elasticity predicts a roughness exponent zeta = 1/3 (one loop), zeta = 0.388 +/- 0.002 (numerics) while experiments give zeta approximately = 0.5. Within functional renormalization group methods we find that a nonlocal Kardar-Parisi-Zhang-type term is generated at depinning and grows under coarse graining. A fixed point with zeta approximately = 0.45 (one loop) is identified, showing that large enough cubic terms increase the roughness. This fixed point is unstable, revealing a rough strong-coupling phase. Experimental study of contact angles theta near pi/2, where cubic terms in the energy vanish, is suggested.     

Multipartite Composition of Contextuality Scenarios

Contextuality is a particular quantum phenomenon that has no analogue in classical probability theory. Given two independent systems, a natural question is how to represent such a situation as a single test space. In other words, how separate contextuality scenarios combine into a joint scenario. Under the premise that the the allowed probabilistic models satisfy the No Signalling principle, Foulis and Randall defined the unique possible way to compose two contextuality scenarios. When composing strictly-more than two test spaces, however, a variety of possible composition methods have been conceived. Nevertheless, all these formally-distinct composition methods appear to give rise to observationally equivalent scenarios, in the sense that the different compositions all allow precisely the same sets of classical and quantum probabilistic models. This raises the question of whether this property of invariance-under-composition-method is special to classical and quantum probabilistic models, or if it generalizes to other probabilistic models as well, our particular focus being \(\mathcal {Q}_1\) models. \(\mathcal {Q}_1\) models are physically important since, when applied to scenarios constructed by a particular composition rule, coincide with the well-defined “Almost Quantum Correlations”. In this work we see that some composition rules, however, give rise to scenarios with inequivalent allowed sets of \(\mathcal {Q}_1\) models. We find that the non-trivial dependence of \(\mathcal {Q}_1\) models on the choice of composition method is apparently an artifact of failure of those composition rules to capture the orthogonality relations given by the Local Orthogonality principle. We prove that \(\mathcal {Q}_1\) models satisfy invariance-under-composition-method for all the constructive compositions protocols which do capture this notion of Local Orthogonality.     

A non-conformal eXtended Finite Element approach: Integral matching Xfem

This work is dedicated to the mathematical and numerical analysis of a new Xfem approach: the integral maching Xfem. It is known that the quality of the approximation and the convergence rate of Xfem type methods is broadly influenced by the transition layer between the singular enrichment area and the rest of the domain. In the presented method, this transition layer is replaced by an interface associated with an integral matching condition of mortar type. We prove an optimal convergence result for such a non-conformal approximation method and we perform some numerical experiments showing the advantages of the integral matching Xfem with respect to former Xfem approaches.     

Phylogenetic and functional classification of ATP-binding cassette (ABC) systems

ATP binding cassette (ABC) systems constitute one of the most abundant superfamilies of proteins. They are involved in the transport of a wide variety of substances, but also in many cellular processes and in their regulation. In this paper, we made a comparative analysis of the properties of ABC systems and we provide a phylogenetic and functional classification. This analysis will be helpful to accurately annotate ABC systems discovered during the sequencing of the genome of living organisms and to identify the partners of the ABC ATPases.     

First enantioselective synthesis and absolute stereochemistry assignment of new monocyclic sesquiterpenes from Artemisia chamaemelifolia

We herein report the first enantioselective synthesis of two new monocyclic sesquiterpenes from Artemisia chamaemelifolia starting from an enantiopure building block. The key feature of the present approach is to allow complete control of all the stereogenic centers present in the natural products and to elucidate their absolute stereochemistry, which to date is unknown.     

Injection port silylation of γ-hydroxybutyrate and trans-hydroxycrotonic acid: conditions optimisation and characterisation of the di-tert-butyldimethylsilyl derivatives by GC-MS

Silylation is usually carried out on γ-hydroxybutyrate (GHB) for its analysis by Gas Chromatography/Mass Spectrometry (GCMS) and requires potentially long incubation times before injection during which the derivatisation reagent and derivatives (such as trimethyl-silyl compounds) can hydrolyse. Moreover, alternative internal standards (IS) are often useful depending on sample matrices, extraction/purification procedures, commercial availability and price. This study evaluated the possibility of silylating GHB with an injection port derivatisation procedure using N-methyl-N-[tert-butyldimethyl-silyl]trifluoroacetimide (MTBSTFA) with 1% tert-butyldimethylchlorosilane (TBCS) as the derivatisation reagent, producing di-tert-butyldimethyl-silyl derivatives as a novel means of analyzing GHB. In parallel, trans-hydroxycrotonic acid (t-HCA) was investigated as a potential IS for GHB quantification. Analyses were carried out with a temperature programmable injector and the GHB(t-BDMS)(2) and t-HCA(t-BDMS)(2) derivatives were successfully produced, characterised and derivatisation conditions optimised. t-HCA behaved very similarly to GHB through the derivatisation processes and was used as the IS for the determination of urinary endogenous GHB concentrations in human subjects where the method showed a limit of detection of 0.049 μg mL(-1), a limit of quantification of 0.162 μg mL(-1), and a limit of confirmation of 1.33 μg mL(-1), suitable for toxicological GHB concentration determination.     

Aminomethyl-bipyridine bearing two flexible nitronyl-nitroxide arms: a new podand for complexation of transition metals in a facial or meridional conformation

Transition metal complexes of 6-aminomethyl-bis[methyl-2-(4,5-dihydro-4,4,5,5- tetramethylimidazolinyl-3-oxide-l-oxy)]-2,2'-bipyridine, bpyN(NIT)(2), 1, have been synthesized and characterized by FAB-MS, UV-vis, FT-IR, and EPR spectroscopies, elemental analysis, and susceptibility measurements. Single-crystal X-ray diffraction studies have been performed on all compounds giving the following crystal data: bpyN(NIT)(2), 1, triclinic, P(-)1, Z = 2, a = 10.7224(4) A, b = 11.0995(4) A, c = 13.1134(3) A, alpha = 114.101(9) degrees, beta = 97.476(9) degrees, gamma = 99.667(9) degrees; ZnbpyN(NIT)(2), 2, hexagonal, P3(2), Z = 3, a = 15.4545(3) A, b = 15.4545(3) A, c = 13.5594(3) A; NibpyN(NIT)(2), 3, hexagonal, P3(2), Z = 3, a = 15.2867(1) A, b = 15.2867(1) A, c = 13.7160(1) A; CubpyN(NIT)(2), 4, triclinic, P(-)l, Z = 2, a = 11.8640(4) A, b = 13.2023(4) A, c = 13.2661(5) A, alpha = 90.539(9) degrees, beta = 104.983(9) degrees, gamma = 113.252(9) degrees. The two radicals of the free ligand 1 are almost perpendicular to one another in the solid state, favoring a weak ferromagnetic interaction (J/k(B) = 8.8 K). The complexes obtained by wrapping the ligand around a single metal center gave rise to two different coordination schemes where the two radicals of 1 adopt a ON(3)O meridional (with Ni and Zn) or a ON(3)O facial conformation (with Cu), which strongly affects the magnetic and electronic properties (O accounts for the coordinated oxygen atoms of the nitroxide radicals and N(3) accounts for the tertiary amine). For 2, a model of a dimer has been used giving rise to a weak antiferromagnetic interaction between the radicals (J/k(B) = -5.3 K). For 3, a very strong intramolecular antiferromagnetic coupling has been found and estimated at J/k(B) = -230 K and J'/k(B) = -110 K between the nickel and each radical using an asymmetric model of a trimer. For 4, an unusual magnetic behavior is observed, dominated by antiferromagnetic interactions with a residual plateau at chiT = 0.63 emu.K.mol(-)(1). Molecular modeling at the CASSCF level is in keeping with an antiferromagnetic coupling of the radical bound with the Cu(II) in the equatorial position. The combined structural, electronic, and magnetic characteristics suggest that the use of a flexible molecule provide an additional approach for fine-tuning magnetic interactions.     

Development of uncoated near-spherical gold nanoparticles for the label-free quantification of Lactobacillus rhamnosus GG by surface-enhanced Raman spectroscopy

The Surface-enhanced Raman spectroscopy (SERS) method based on gold nanoparticles as SERS substrate was investigated for the label-free detection and quantification of probiotic bacteria that are widely used in various pharmaceutical formulations. Indeed, the development of a simple and fast SERS method dedicated to the quantification of bacteria should be very useful for the characterization of such formulations in a more convenient way than the usually performed tedious and time-consuming conventional counting method. For this purpose, uncoated near-spherical gold nanoparticles were developed at room temperature by acidic treatment of star-like gold nanoparticle precursors. In this study, we first investigated the influence of acidic treatment conditions on both the nanoparticle physicochemical properties and SERS efficiency using Rhodamine 6G (R6G) as “model” analyte. Results highlighted that an effective R6G Raman signal enhancement was obtained by promoting chemical effect through R6G-anion interactions and by obtaining a suitable aggregation state of the nanoparticles. Depending on the nanoparticle synthesis conditions, R6G SERS signals were up to 10²–10³-fold greater than those obtained with star-like gold nanoparticles. The synthesized spherical gold nanoparticles were then successfully applied for the detection and quantification of Lactobacillus rhamnosus GG (LGG). In that case, the signal enhancement was especially due to the combination of anion-induced chemical enhancement and nanoparticle aggregation on LGG cell wall consecutive to non-specific interactions. Both the simplicity and speed of the procedure, achieved under 30 min, including nanoparticle synthesis, sample preparation, and acquisition of SERS spectra, appeared as very relevant for the characterization of pharmaceutical formulations incorporating probiotics.

Graphical abstract

     

Dibenzyl Structuresin a Macromolecular Chain. III. Dibenzyldiisocyanates Reactivity

The reactivity of the 2,2′-, 2,4′-, 4,4′-dibenzyldiisocyanate (2,2′-, 2,4′-, 4,4′-DBDI) with n-butanol in benzene has been studied. The concentrations of all species were monitored by using high performance liquid chromatography (HPLC). The reactivity of 4,4′-DBDI is similar to that of 4,4′-diphenylmethanediisocyanate (4,4′-MDI). Very strong intramolecular catalytic effects were noticed in the case of 2,2′-DBDI, probably due to the variable molecular geometry. These effects are responsible for the whole reaction pattern. The 2,4′-DBDI NCO ortho and para groups reactivities are different and comparable to that of 2,4-toluylenediisocyanate (2,4-TDI).