Purification and characterization of a new Bacillus thuringiensis bacteriocin active against Listeria monocytogenes, Bacillus cereus and Agrobacterium tumefaciens

This study reports on the identification, characterization and purification of a new bacteriocin, named Bacthuricin F103, from a Bacillus thuringiensis strain BUPM103. Bacthuricin F103 production began in the early exponential phase and reached a maximum in the middle of the same phase. Two chromatographic methods based on high performance liquid chromatography and fast protein liquid chromatography systems were used to purify Bacthuricin F103. Sodium dodecyl sulphate-polyacrylamide gel electrophoresis revealed that this bacteriocin had a molecular weight of approximately 11 kDa. It also showed a wide range of thermostability of up to 80 °C for 60 min and a broad spectrum of antimicrobial activity over a pH range of 3.0–10.0. This bacteriocin was noted, and for the first time, to exhibit potent antimicrobial activity against Agrobacterium subsp. strains, the major causal agents of crown gall disease in tomato and vineyard crops, and against several challenging organisms in food, such as Listeria monocytogenes and Bacillus cereus. Complete killing with immediate impact on cells was observed within a short period of time. The sequence obtained for Bacthuricin F103 by direct N-terminal sequencing shared considerable homology with hemolysin. Bacthuricin F103 was noted to act through the depletion of intracellular ions, which suggest that the cell membrane was a possible target to Bacthuricin F103.     

Ferrocenyl-terminated redox stars: synthesis and electrostatic effects in mixed-valence stabilization

A family of rigid ferrocenyl-terminated redox stars has been synthesized-by Negishi coupling, including hexa(ferrocenethynyl)benzene complexes, a dodecaferrocenyl star, and stars with extended rigid tethers-and fully characterized. Cyclic voltammetry (CV) studies of the parent complex hexa(ferrocenylethynyl)benzene, 1, show a single wave for the six-electron oxidation of 1 using Nn-Bu(4)PF(6) as the supporting electrolyte on a Pt anode in CH(2)Cl(2), whereas three distinct two-electron reversible CV waves are observed using Nn-Bu(4)BAr(F)(4) (Ar(F) = 3,5-C(6)H(3)-(CF(3))(2,)). The CV of 1,3,5-tris(ferrocenylethynyl)benzene, 11, also shows only one wave for the three-electron transfer with Nn-Bu(4)PF(6) and three one-electron waves using Nn-Bu(4)BAr(F)(4). This confirms the lack of electronic communication between the ferrocenyl groups and a significant electrostatic effect among the oxidized ferrocenyl groups. This effect is not significant between para-ferrocenyl groups in 1,4-bis(ferrocenylethynyl)benzene for which only a single wave is observed even with Nn-Bu(4)BAr(F)(4) as the supporting electrolyte. The para-ferrocenyl substituents are quite independent, which explains that two para-ferrocenyl groups are oxidized at about the same potential in a single CV wave of 1. With the additional steric bulk introduced with a methyl substituent on the ferrocenyl group, however, even the para-methylferrocenyl groups are submitted to a small electrostatic effect splitting the six-electron transfer into six single-electron waves, probably because of the overall steroelectronic constraints. Contrary to 11, 1,3-bis(ferrocenylethynyl)benzene and related complexes with a third, different substituent in the remaining meta position different from a ferrocenylethynyl only show a single two-electron wave using Nn-Bu(4)BAr(F)(4), which is attributed to the transo?d conformation of the ferricinium groups minimizing the electrostatic effect. This shows that, in 11, it is the steric frustration that is responsible for the electrostatic effect, and the same occurs in 1. In several cases, ΔE(p) is much larger than the expected 60 mV value, characterizing a quasi-reversible (i.e., relatively slow) redox process. It is suggested that this slower electron transfer be attributed to conformational rearrangement of the ferrocenyl groups toward the transo?d position in the course of electron transfer. Thus both the thermodynamic and kinetic aspects of the electrostatic factor (isolated from the electronic factor), including the frustration effect, are characterized. The distinction between the electronic communication and through-space electrostatic effect was made possible in all of these complexes in which the absence of wave splitting using a strongly ion-pairing electrolyte shows the absence of significant electronic communication, and was confirmed by the new frustration phenomenon.     

Oxidative C-H homodimerization of phenylacetamides

A range of secondary and tertiary phenylacetamides undergo oxidative homodimerization to afford biaryls. The reaction proceeds under palladium catalysis in the presence of a copper cocatalyst and oxygen and is most effective for electron-rich substrates.     

Poly(D,L-lactide)-block-poly(2-hydroxyethyl acrylate) block copolymers as potential biomaterials for peripheral nerve repair: in vitro and in vivo degradation studies

The properties of poly(D ,L ‐lactide)‐block‐poly(2‐hydroxyethyl acrylate) (PLA‐b‐PHEA) block copolymers by means of in vitro / in vivo (rat) degradation are investigated and compared to those of PLA homopolymer. Over 12 weeks, we observe mass loss and molecular weight decrease. In vitro and in vivo findings are very similar for each polymer tested. When a short PHEA block is used (PLA‐b‐PHEA 15 000–3 000 g · mol^?1, 85/15 wt%), the degradation process is found to be very similar to that of homo‐PLA, and to be typical of a bulk erosion mechanism, with no mass loss observed until week 7 and continuous decrease of molar mass within this timeframe. For a longer PHEA block length within the block copolymer (PLA‐b‐PHEA 15 000–7 500 g · mol^?1, 65/35 wt%), the degradation mechanism is modified, with a significant mass loss observed at early times and only a slight decrease in molar mass. The latter finding is related to the pronounced hydrophilicity and softness of the material induced by the PHEA block, which allow easy diffusion and rapid leakage of the degradation residues from the material towards the aqueous medium. Schwann cells are found to better adhere on spin‐coated films of PLA‐b‐PHEA (85/15 wt%) than on PLA ones. These results show the potential of such hydrophilized PLA‐based copolymers for use in peripheral nerve repair.

     

A centerless representation of the Virasoro algebra associated with the unitary circular ensemble

We consider the 2-dimensional Toda lattice tau functions τ_n(t,s;η,θ) deforming the probabilities τ_n(η,θ) that a randomly chosen matrix from the unitary group U(n), for the Haar measure, has no eigenvalues within an arc (η,θ) of the unit circle. We show that these tau functions satisfy a centerless Virasoro algebra of constraints, with a boundary part in the sense of Adler, Shiota and van Moerbeke. As an application, we obtain a new derivation of a differential equation due to Tracy and Widom, satisfied by these probabilities, linking it to the Painlevé VI equation.     

Redox strategy for reversible attachment of biomolecules using bifunctional linkers

Soft attachment of streptavidin to β-cyclodextrin-modified pegylated SAMs was efficiently performed in a reversible and repetitive way via orthogonal bifunctional linkers involving streptavidin-biotin recognition and redox-driven multivalent host-guest (β-cyclodextrin-ferrocene) interactions.     

Molecular clusters in aqueous solutions of pyridine and its methyl derivatives

Small-angle neutron scattering proved that molecules in aqueous solutions of pyridine, 2-methylpyridine and 2,6-dimethylpyridine form clusters. The clusters are dynamic aggregates consisting of hydrogen-bonded water-amine complexes. Strengthening of the hydrogen bonds between water and amine molecules due to the methyl groups in the ortho position in the pyridine ring makes the structures more stable, as was evidenced by relatively long times of the structural relaxation. The strong intermolecular forces affect the thermal expansion of the systems. No aggregates similar to those in aqueous systems are present in the methanolic ones. That points to the crucial role of water in the molecular clustering. A molecule of methanol, although capable of hydrogen bonding with the amines, cannot participate in larger structures because of the lack of protons that could form the enhanced network. Thus, even if the amine-methanol complexes occur, they are incapable of further association. It was shown that the co-operative nature of hydrogen bonds and the propensity of water to association are the main factors that determine the properties of aqueous systems.     

A novel ruthenium(II) complex for two-photon absorption-based optical power limiting in the near-IR range

In this article, the synthesis of a novel high-conjugated ligand and its corresponding Ru(II) complex PTFTF:Ru is reported, along with the linear and nonlinear optical characterizations. Two-photon absorption based optical power limiting properties (OPL), especially in the near infrared, are described and compared to those of the analogous complexes previously published. Combined with a preliminary theoretical approach, this allows us to highlight several key parameters for OPL optimization in such molecular systems and more particularly the spectral overlap between TPA and excited-state absorption.     

A Multi-Fluid Compressible System as the Limit of Weak Solutions of the Isentropic Compressible Navier–Stokes Equations

This paper mainly concerns the mathematical justification of a viscous compressible multi-fluid model linked to the Baer-Nunziato model used by engineers, see for instance Ishii (Thermo-fluid dynamic theory of two-phase flow, Eyrolles, Paris, 1975), under a “stratification” assumption. More precisely, we show that some approximate finite-energy weak solutions of the isentropic compressible Navier–Stokes equations converge, on a short time interval, to the strong solution of this viscous compressible multi-fluid model, provided the initial density sequence is uniformly bounded with corresponding Young measures which are linear convex combinations of m Dirac measures. To the authors’ knowledge, this provides, in the multidimensional in space case, a first positive answer to an open question, see Hillairet (J Math Fluid Mech 9:343–376, 2007), with a stratification assumption. The proof is based on the weak solutions constructed by Desjardins (Commun Partial Differ Equ 22(5–6):977–1008, 1997) and on the existence and uniqueness of a local strong solution for the multi-fluid model established by Hillairet assuming initial density to be far from vacuum. In a first step, adapting the ideas from Hoff and Santos (Arch Ration Mech Anal 188:509–543, 2008), we prove that the sequence of weak solutions built by Desjardins has extra regularity linked to the divergence of the velocity without any relation assumption between λ and μ. Coupled with the uniform bound of the density property, this allows us to use appropriate defect measures and their nice properties introduced and proved by Hillairet (Aspects interactifs de la m’ecanique des fluides, PhD Thesis, ENS Lyon, 2005) in order to prove that the Young measure associated to the weak limit is the convex combination of m Dirac measures. Finally, under a non-degeneracy assumption of this combination (“stratification” assumption), this provides a multi-fluid system. Using a weak–strong uniqueness argument, we prove that this convex combination is the one corresponding to the strong solution of the multi-fluid model built by Hillairet, if initial data are equal. We will briefly discuss this assumption. To complete the paper, we also present a blow-up criterion for this multi-fluid system following (Huang et al. in Serrin type criterion for the three-dimensional viscous compressible flows, arXiv, 2010).     

On mean-field limits and quantitative estimates with a large class of singular kernels: Application to the Patlak–Keller–Segel model

In this note, we propose a modulated free energy combination of the methods developed by P.-E. Jabin and Z. Wang [Inventiones (2018)] and by S. Serfaty [Proc. Int. Cong. Math. (2018) and references therein] to treat more general kernels in mean-field limit theory. This modulated free energy may be understood as introducing appropriate weights in the relative entropy developed by P.-E. Jabin and Z. Wang (in the spirit of what has been recently developed by D. Bresch and P.-E. Jabin [Ann. of Math. (2) (2018)]) to cancel the most singular terms involving the divergence of the flow. Our modulated free energy allows us to treat singular potentials that combine large smooth part, small attractive singular part, and large repulsive singular part. As an example, a full rigorous derivation (with quantitative estimates) of some chemotaxis models, such as the Patlak–Keller–Segel system in subcritical regimes, is obtained.