What is the form of muscimol from fly agaric mushroom (Amanita muscaria) in water? An insight from NMR experiment supported by molecular modeling

The biologically active alkaloid muscimol is present in fly agaric mushroom (Amanita muscaria), and its structure and action is related to human neurotransmitter _γ-aminobutyric acid (GABA). The current study reports on determination of muscimol form present in water solution using multinuclear ¹H and ¹³C nuclear magnetic resonance (NMR) experiments supported by density functional theory molecular modeling. The structures of three forms of free muscimol molecule both in the gas phase and in the presence of water solvent, modeled by polarized continuous model, and nuclear magnetic isotropic shieldings, the corresponding chemical shifts, and indirect spin–spin coupling constants were calculated. Several J-couplings observed in proton and carbon NMR spectra, not available before, are reported. The obtained experimental spectra, supported by theoretical calculations, favor the zwitterion form of muscimol in water. This structure differs from NH isomer, previously determined in dimethyl sulfoxide (DMSO) solution. In addition, positions of signals C3 and C5 are reversed in both solvents.     

Approximating Clarke’s subgradients of semismooth functions by divided differences

We show that the algorithm presented in an earlier paper by Studniarski (Numer. Math., 55:685–693, 1989) can be applied, after only a small modification, to approximate numerically Clarke’s subgradients of semismooth functions of two variables. Results of computational testing of this modified algorithm are also reported.      

Synthesis and crystal and molecular structure of newN-substituted γ-hydroxybutyramides

TheN-(2-phenylethyl)amide of-(1, 1-ethylenedioxy)-ethyl--hydroxybutyric acid (II) and theN-(p-methoxybenzyl)amide of-(1, 1-ethylenedioxy)-ethyl--hydroxybutyric acid (III) have been synthesized and the crystal structure ofIII has been solved. CompoundIII, C₁₆H₂₃O₅N, crystallizes in the monoclinic space groupP2₁/c witha=12.572(2),b=11.149(2),c=12.317(2) Å and=106.53(1)°. The structure was solved by direct methods, and refined by full-matrix least squares to giveR=0.040 (R _w =0.047) for 2004 intensities. The dioxolane ring has a deformed half-chair conformation.     

Extraction of glyphosate by a supported liquid membrane technique

The possible application of the supported liquid membrane (SLM) technique for the extraction of glyphosate is presented. For the extraction of this compound the SLM system has been applied with utilisation of Aliquat 336 as a cationic carrier incorporated into the membrane phase. The extraction efficiency of glyphosate [N-(phosphonomethyl)glycine] is dependent on the donor phase pH, carrier concentration in the organic phase and NaCl concentration in the acceptor phase. The optimal extraction conditions are: donor phase pH>11, acceptor phase of 2 M NaCl solution and the organic phase composed of 20% (w/w) Aliquot 336 solution in di-hexyl ether. Counter-coupled transport of chloride anions from the acceptor phase to the donor phase is a driving force of the mass transfer in this system.     

Do intramolecular halogen bonds exist? Ab initio calculations and crystal structures’ evidences

Cl···O intramolecular contacts are analysed here. Hence the Cambridge Structural Database (CSD) search was performed to find five-membered Cl–C=C–C=O pseudo-rings closed through Cl···O intramolecular contacts. Such rings were analysed and it was found that some of Cl···O distances are smaller than the corresponding sum of van der Waals radii. Additionally ab initio MP2/6-311++G(d,p) calculations and AIM analyses were carried out here on 3-chloropropenal and its fluoro derivatives to deepen the nature of intramolecular Cl···O interactions, some of findings may indicate that they are attractive and stabilizing ones. This paper is dedicated to Prof. T. M. Krygowski on the occasion of his 70th birthday     

Thiol-ene chemistry as an effective tool for hydrophobization of cotton fabrics

In this paper, several methods of hydrophobization of cotton fabrics using the thio-ene click reaction were compared. Durable, superhydrophobic textiles were obtained in an easy way. Various variants of functionalized silsesquioxanes were used for the hydrophobization of fabrics. The synthesis of bifunctional silsesquioxanes (RSiMe₂O)₄(ViSiMe₂O)₄Si₈O₁₂ and (RSiMe₂O)₄(R’SiMe₂O)₄Si₈O₁₂ were performed via hydrothiolation of silsesquioxane derivative (ViSiMe₂O)₈Si₈O₁₂. Alkoxysilyl, alkyl and fluoroalkyl moieties were introduced as functional groups. Samples were prepared using four methods, differing in the modification method and the number of stages. During the research, fabrics were modified via (a) the dip-coating process, (b) carrying out thiol-ene click reactions directly on the surface of the fabric and (c) using both of these methods. The hydrophobicity of the fabric was evaluated by measuring the Water contact angle (WCA). The obtained samples were also examined using infrared analysis (FT-IR), Scanning electron microscope (SEM), and Elemental analysis (SEM–EDS). All analyses were performed before and after the washing process in order to verify the stability of the performed modifications.

Graphical abstract

     

Structural assignment of organotin hydrides containing the oxazoline ligand

A series of triorganotin hydrides and diorganotin dihydrides containing the optically active 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand have been characterized by means of the multinuclear low-temperature NMR investigations, the results of which are discussed. In the corresponding organotin hydrides values of the ¹J(¹H-^117/119Sn) couplings appeared to be temperature dependent, supporting an axial/equatorial position of the hydrogen attached to the tin.