Uncharged Water‐Soluble Metal‐Bis‐Porphyrins Like Molecular Tweezers for Amino Acids

Some new water‐soluble bis‐porphyrins, constituted of two porphyrin units spaced by means of aliphatic bridges of different lengths, were synthesized and characterized by MALDI‐TOF mass spectrometry, ¹H NMR and UV‐vis spectroscopy. The hydrosolubility of these uncharged compounds was guaranteed from the presence of six long PEG chains bound on the peripheral positions of the two porphyrins. Cobalt and zinc derivatives were also prepared. In the case of Co‐bis‐porphyrin, the appearance of induced circular dichroism (ICD) signals in water solution confirmed the formation of stable complexes with some amino acids, in which the bis‐porphyrin behaves like molecular tweezers.

     

Toric rings generated by special stable sets of monomials

In this paper we consider some subalgebras of the d-th Veronese subring of a polynomial ring, generated by stable subsets of monomials. We prove that these algebras are Koszul, showing that the presentation ideals have Gröbner bases of quadrics with respect to suitable term orders. Since the initial monomials of the elements of these Gröbner bases are square- free, it follows by a result of STURMFELS [S, 13.15], that the algebras under consideration are normal, and thus Cohen-Macaulay.     

Optimization of thin film solid phase microextraction and data deconvolution methods for accurate characterization of organic compounds in produced water

The continued rise in the extraction of unconventional oil and gas across the globe poses many questions about how to manage these relatively new waste‐streams. Produced water, the primary waste by‐product, contains a diverse number of anthropogenic additives together with the numerous hydrocarbons extracted from the well. Due to potential environmental hazards, it is critical to characterize the chemical composition of this type of waste before proper disposal or remediation/reuse. In this work, a thin film solid phase microextraction approach was developed and optimized to characterize produced water. The thin film device consisted of hydrophilic‐lipophilic balance particles embedded in polydimethylsiloxane and immobilized on a carbon mesh surface. These devices were chosen to provide broad extraction coverage and high reusability. Various parameters were evaluated to ensure reproducible results while minimizing analyte loss. This optimized protocol, consisting of a 15 min extraction followed by a short (3 s) rinsing step, enabled the reproducible analysis of produced water without any sample pretreatment. Extraction efficiency was suitable for both produced water additives and hydrocarbons. The developed approach was able to tentatively identify a total of 201 compounds from produced water samples, by using one‐dimensional gas chromatography hyphenated to mass spectrometry and data deconvolution.     

Deterministic particle approximation for nonlocal transport equations with nonlinear mobility

We construct a deterministic, Lagrangian many-particle approximation to a class of nonlocal transport PDEs with nonlinear mobility arising in many contexts in biology and social sciences. The approximating particle system is a nonlocal version of the follow-the-leader scheme. We rigorously prove that a suitable discrete piece-wise density reconstructed from the particle scheme converges strongly in $L_{loc}^1$ towards the unique entropy solution to the target PDE as the number of particles tends to infinity. The proof is based on uniform BV estimates on the approximating sequence and on the verification of an approximated version of the entropy condition for large number of particles. As part of the proof, we also prove uniqueness of entropy solutions. We further provide a specific example of non-uniqueness of weak solutions and discuss the interplay of the entropy condition with the steady states. Finally, we produce numerical simulations supporting the need of a concept of entropy solution in order to get a well-posed semigroup in the continuum limit, and showing the behaviour of solutions for large times.     

Real Spectra of PT-symmetric Operators and Perturbation Theory

A criterion is provided for the reality of the spectrum for a class of non self-adjoint operators in a Hilbert space invarariant under a particular discrete symmetry. Applications to the PT-symmetric Schrödinger operators are discussed.     

Small-angle X-ray scattering and light scattering on lysozyme and sodium glycocholate micelles

Small-angle X-ray scattering (SAXS) together with static (SLS) and dynamic light scattering (DLS) measurements were carried out on aqueous solutions of lysozyme (LY) and of the ionic biological detergent sodium glycocholate (NaGC). Apparent diffusion coefficients (D app), excess Rayleigh ratio, and SAXS spectra were measured for 0.1 M NaGC solutions at different ionic strengths (0.05-0.30 M NaCl). The same data were collected for LY in sodium acetate buffer 50 mM without and with 92 mM NaCl as a function of protein concentration (10-80 g L(-1)). A correlated analysis of SLS data and SAXS spectra was first tested on the LY samples and then extended to the interpretation of the NaGC data to infer information on particle structure and interaction potential. A hard-core (HC) interaction shell of uniform thickness, a screened Coulomb potential of the electric double layer (EDL) or the complete DLVO potential were alternatively used to represent the long-range tail of the interaction potential. Whenever an essentially repulsive tail is expected, all the representations give reasonable results, but the data analysis does not allow the discrimination between the oblate and the prolate symmetries of the NaGC aggregates. The DLVO model allows the interpretation of the data even when the attractive component determines the tail character. With this model an overall fit of the micelle data at all the NaCl concentrations was successfully performed by assuming a simple spherical symmetry of the micelles and invariant values of their ionization degree and Hamaker constant, thus considering just the screening effect of the added electrolyte. Whatever model is used, the results point out that the aggregates are quite hydrated (26-38 water molecules per monomer) and very slightly grow by increasing the NaCl concentration. When spherical symmetry is assumed the aggregate radii for all the samples fall in the range 15-16 A. From the SAXS and SLS, best fitting geometrical parameters, and interparticle structure factor, a D app value was calculated for each sample. An excellent consistence is achieved for LY results. On the contrary, calculated D app values systematically lower than the experimental values are always obtained for the NaGC micelles. Micelle polydispersity and internal dynamics seem to be the most probable reasons of the bad agreement.     

Determination of triazines and dinitroanilines in waters by high-performance liquid chromatography after solid-phase extraction

A rapid and selective method for the simultaneous determination of triazines and dinitroanilines in real water matrices is suggested based on a preliminary adsorption on an RP-18 cartridge, an elution step using acetonitrile and HPLC separation with a Lichrosorb RP- Select B column and UV detection. The washing step cartridge is critical for triazines: terbutryn is eluted with quantitative recovery only after washing with an NH₃ solution. The degree of enrichment of the compounds studied has been determined: triazine recoveries are quantitative, while dinitroaniline recoveries are between 66% and 78% at the lowest fortification level. The detection limits for the ten herbicides are in the range 0.03-0.1 μg/l. The analysis time is 2 h.     

The reaction of β-enaminoesters with organolithium reagents: a convenient method for the regioselective synthesis of enaminoketones

A simple and practical method for the regioselective preparation of β-enaminoketones is described. The method relies on the reaction of β-enaminoesters with organolithium reagents, and allows the preparation of a range of unusual β-enaminoketones.     

Rearrangement of N-Allyl-α,α-dichloroamides, β- or γ- Functionalized,to Substituted Analogues of the γ-Aminobutyric Acid (GABA)

The rearrangement of γ-chlm, β-hydroxy or β-vmyl N-allyl-N-benzyl-α,α-dichlorocarboxyamides to γ-aminobutynic acid analogues is efficiently promoted by CuCI\N,N,N′,N′-tetramethylethylendiamine. With the β-vinyl functionalization a tandem radical-radical reaction, yieldmg 3-aza-2-oxo-bicyclo[3,3,0]actatre adducts, is also observed.