Front Cover: Can Nanoplastics Alter Cell Membranes? (ChemPhysChem 1/2020)

Whilst the formation of plastic nanoparticles (nanoplastics) from plastic wastes has been unequivocally evidenced, little is known about the effects of these materials on living organisms at the subcellular or molecular levels. In the present contribution we show through molecular dynamics simulations that polyethylene nanoparticles dissolve in the hydrophobic core of lipid bilayers into a network of disentangled, single polymeric chains. The thereby induced structural and dynamic changes in the bilayer alter vital functions of the cell membrane, which if lacking a mechanism to decompose the polymer chains may result in the death of the cell.     

The initial transient of natural convection during copper electrolysis in the presence of an opposing Lorentz force: Current dependence

Magnetic fields are well-established in electrochemistry as an attractive tool to improve both the quality of the deposit as well as the deposition rate. The key mechanism is a mass transfer enhancement by Lorentz-force-driven convection. However, during electrolysis this convection interacts with buoyancy-driven convection, which arises from concentration differences, in a sometimes intriguing way. In the case of a Lorentz force opposing buoyancy, this is due to the growth of a bubble-like zone of less-concentrated cupric ion solution at the lower part of the vertical cathode when copper electrolysis is performed. If buoyancy is strong enough to compete with the Lorentz force, this zone rises along the cathode and causes surprisingly unsteady initial transient behaviour. We explore this initial transient under galvanostatic conditions by analyzing the development of the concentration and velocity boundary layers obtained by Mach-Zehnder interferometry and particle image velocimetry. Particular attention is also paid to higher current densities above the limiting current, obtained from potentiodynamic measurements, at which a chaotic advection takes place. The results are compared by scaling analysis.     

Bioavailability and biotransformation of sulforaphane and erucin metabolites in different biological matrices determined by LC–MS–MS

The food-related isothiocyanate sulforaphane (SFN), a hydrolysis product of the secondary plant metabolite glucoraphanin, has been revealed to have cancer-preventive activity in experimental animals. However, these studies have often provided inconsistent results with regard to bioavailability, bioaccessibility, and outcome. This might be because the endogenous biotransformation of SFN metabolites to the structurally related erucin (ERN) metabolites has often not been taken into account. In this work, a fully validated liquid chromatography tandem mass spectrometry (LC–MS–MS) method was developed for the simultaneous determination of SFN and ERN metabolites in a variety of biological matrices. To reveal the importance of the biotransformation pathway, matrices including plasma, urine, liver, and kidney samples from mice and cell lysates derived from colon-cancer cell lines were included in this study. The LC–MS–MS method provides limits of detection from 1 nmol L^?1 to 25 nmol L^?1 and a mean recovery of 99 %. The intra and interday imprecision values are in the range 1–10 % and 2–13 %, respectively. Using LC–MS–MS, SFN and ERN metabolites were quantified in different matrices. The assay was successfully used to determine the biotransformation in all biological samples mentioned above. For a comprehensive analysis and evaluation of the potential health effects of SFN, it is necessary to consider all metabolites, including those formed by biotransformation of SFN to ERN and vice versa. Therefore, a sensitive and robust LC–MS–MS method was validated for the simultaneous quantification of mercapturic-acid-pathway metabolites of SFN and ERN.

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Graphical Abstract Biotransformation of sulforaphane and erucin metabolites in mice and cell culture

     

On integro‐differential inclusions with operator‐valued kernels

We study integro‐differential inclusions in Hilbert spaces with operator‐valued kernels and give sufficient conditions for the well‐posedness. We show that several types of integro‐differential equations and inclusions are covered by the class of evolutionary inclusions, and we therefore give criteria for the well‐posedness within this framework. As an example, we apply our results to the equations of visco‐elasticity and to a class of nonlinear integro‐differential inclusions describing phase transition phenomena in materials with memory. Copyright © 2014 John Wiley & Sons, Ltd.     

C2-symmetric chiral disulfoxide ligands in rhodium-catalyzed 1,4-addition: from ligand synthesis to the enantioselection pathway

A family of chiral C(2)-symmetric disulfoxide ligands possessing biaryl atropisomeric backbones has been synthesized by using the Andersen methodology. Complete characterization includes X-ray crystallographic studies of all ligands and some of their rhodium complexes. Their synthesis, optical purity, electronic properties, and catalytic behavior in the prototypical rhodium-catalyzed 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one are presented through an in depth study of this ligand class. Density functional theory calculations on the step of the catalytic cycle that determines the enantioselectivity are presented and reinforce the first hypothetical explanations for the high levels of asymmetric induction observed.     

Investigation of the interaction of Mercurochrome® constituents with proteins using liquid chromatography/mass spectrometry

The interaction of Mercurochrome®, a medical preparation based on the mercuryorganic compound merbromin, with free thiols in low molecular weight peptides and in proteins has been investigated by means of liquid chromatography (LC) and electrospray mass spectrometry (ESI-MS). β-Lactoglobulin A (β-LGA) from bovine milk (18.4 kDa) has been used as the model protein. It was found that, in contrast to assumptions in literature, the commercial product itself is a heterogeneous mixture of moderate chemical stability, which may contain precipitated Hg salts depending on storage time and conditions. Further variability results from different degrees of bromination of the fluorescein backbone of the compound. The formation of mercury compound–protein adducts was detected. The peptide sequence T13 containing a free thiol residue was identified as the binding site for mercury species after tryptic digestion of β-lactoglobulin A. While fresh Mercurochrome® tends to the formation of a Hg(II)-β-LGA adducts due to excess Hg²⁺ in solution, investigations after precipitation of Hg salts yield Hg(merbromin)(β-LGA) as the major product.     

Investigation of the pathways of excess electron transfer in DNA with flavin-donor and oxetane-acceptor modified DNA hairpins

Oxetane is a potential intermediate that is enzymatically formed during the repair of (6-4) DNA lesions by special repair enzymes (6-4 DNA photolyases). These enzymes use a reduced and deprotonated flavin to cleave the oxetane by single electron donation. Herein we report synthesis of DNA hairpin model compounds containing a flavin as the hairpin head and two different oxetanes in the stem structure of the hairpin. The data show that the electron moves through the duplex even over distances of 17 A. Attempts to trap the moving electron with N2O showed no reduction of the cleavage efficiency showing that the electron moves through the duplex and not through solution. The electron transfer is sequence dependent. The efficiency is reduced by a factor of 2 in GC rich DNA hairpins.     

Dissociative electron attachment to furan, tetrahydrofuran, and fructose

We study dissociative electron attachment to furan (FN) (C(4)H(4)O), tetrahydrofuran (THF) (C(4)H(8)O), and fructose (FRU) (C(6)H(12)O(6)) using crossed electron/molecular beams experiments with mass spectrometric detection of the anions. We find that FN and THF are weak electron scavengers and subjected to dissociative electron attachment essentially in the energy range above 5.5 eV via core excited resonances. In striking contrast to that, FRU is very sensitive towards low energy electrons generating a variety of fragment ions via a pronounced low energy feature close to 0 eV. These reactions are associated with the degradation of the ring structure and demonstrate that THF cannot be used as surrogate to model deoxyribose in DNA with respect to the attack of electrons at subexcitation energies (<3 eV). The results support the picture that in DNA the sugar moiety itself is an active part in the initial molecular processes leading to single strand breaks.     

X-ray diffraction and STM study of reactive surfaces under electrochemical control: Cl and I on Cu(100)

The surface structure of Cu(100) modified by chloride and iodide has been studied in an electrochemical environment by means of in-situ scanning tunneling microscopy in combination with in-situ surface X-ray diffraction with a particular focus on adsorbate and potential dependent surface relaxation phenomena. For positive potentials close to the on-set of the copper dissolution reaction, the X-ray data disclose an extraordinarily large Cu-Cl bond length of 2.61 A for the c(2 x 2)-Cl phase. This finding points to a largely ionic character of the Cu-Cl interaction at the Cu(100) surface, with chloride particles likely to retain their full charge upon adsorption. Together with the positive surface charging at these high potentials, this ionic Cu-Cl bond drives the observed 2.2% outward relaxation between the first two copper layers. These results indicate that the bond between the first and the second copper layer is significantly weakened which appears as the crucial prerequisite for the high surface mobility of copper-chloride species under electrochemical annealing conditions at these high potentials. With 2.51 A the Cu-I bond is 4% shorter than the Cu-Cl bond implying that the nature of the Cu-I bond is mainly covalent. Accordingly, we observe a significant inward relaxation of the top Cu layers upon substituting chloride by iodide at the same electrode potential, which suggests that the iodide adsorption involves charge transfer from the halide to the copper substrate.