New Reasons to Motivate Trope Theory: Endurantism and Perdurantism

In this paper, I argue that (non-presentist) endurantism is incompatible with the view that properties are universals. I do so by putting forward a very simple objection that forces the endurantist to embrace tropes, rather than universals. I do not claim that this is bad news for the endurantist—trope theory seems to me by all means more appealing than universals—rather, I would like to see this result as a further motivation to embrace tropes. I then also put forward a (more controversial) reason to believe that at least some versions of perdurantism also require tropes rather than universals.     

Modelling of Lévy walk kinetics of charged particles in edge electrostatic turbulence in tokamaks

We model and discuss the possible types of motion that charged particles may undergo in a stationary and spatially periodic electrostatic potential and a homogeneous magnetic field. The model is considered to be the simplest approximation of more complex phenomena of plasma edge turbulence in tokamaks. Therein, low frequency turbulence appears in the plasma edge, resulting in a fluctuation of the electron density, and also in the generation of a turbulent electrostatic field. Typical parameters of this turbulent electrostatic field are an electrical potential amplitude of 10–100 V and wave numbers k≈10³ m^-1. In our model, we consider these regimes, together with a homogeneous magnetic field with a magnitude of 1 T. We investigate the dynamics of singly-ionized carbon ions – a typical plasma impurity – with kinetic energies on the order of 10 eV. Besides the obvious Larmor and drift motions, a motion of random-walk and of Lévy walk character appear therein. All of these types of motion can play an important role in the modelling of the anomalous diffusion of particles from the plasma edge turbulence region. The dynamics mentioned will cause an inevitable escape of energetic particles and thus of power loss from the thermonuclear reactor. Moreover, Lévy walk kinetics represents a very interesting kind of kinetics, currently of great interest, which was previously not so often discussed.     

Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV₁₄O₄₀]^8? (in short V₁₄) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V₁₄ system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.     

Big,Strong, Neutral,Twisted, and Chiral π Acids

General synthetic access to expanded π‐acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion–π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron‐withdrawing substituents decreases and the high π acidity needed for strong anion–π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion–π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from ?3.96 to ?4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X‐ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation–π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches ?4.45 eV, whereas two sulfone moieties give a value of ?4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion–π interactions, these conceptually innovative π‐acidic surfaces are also of interest as electron transporters in conductive materials.     

Comparative metabolite profiling of carboxylic acids in rat urine by CE‐ESI MS/MS through positively pre‐charged and 2H‐coded derivatization

A new approach to the selective comparative metabolite profiling of carboxylic acids in rat urine was established using CE‐MS and a method for positively pre‐charged and ²H‐coded derivatization. Novel derivatizing reagents, N‐alkyl‐4‐aminomethyl‐pyridinum iodide (alkyl=butyl, butyl‐d9 or hexyl), containing quaternary amine and stable‐isotope atoms (deuterium), were introduced for the derivatization of carboxylic acids. CE separation in positive polarity showed high reproducibility (0.99–1.32% RSD of migration time) and eliminated problems with capillary coating known in CE‐MS anion analyses. Essentially complete ionization and increased hydrophobicity after the derivatization also enhanced MS detection sensitivity (e.g. formic acid was detected at 0.5 pg). Simultaneous derivatization of one sample using two structurally similar reagents, N‐butyl‐4‐aminomethyl‐pyridinum iodide (BAMP) and N‐hexyl‐4‐aminomethyl‐pyridinum iodide, provided additional information for recognizing a carboxylic acid in an unknown sample. Moreover, characteristic fragmentation acquired by online CE‐MS/MS allowed for identification and categorization of carboxylic acids. Applying this method on rat urine, we found 59 ions matching the characteristic patterns of carboxylic acids. From these 59, 32 ions were positively identified and confirmed with standards. For comparative analysis, 24 standard carboxylic acids were derivatized by chemically identical but isotopically distinct BAMP and N‐butyl‐d9‐4‐aminomethyl‐pyridinium iodide, and their derivatization limits and linearity ranges were determined. Comparative analysis was also performed on two individual urine samples derivatized with BAMP and N‐butyl‐d9‐4‐aminomethyl‐pyridinium iodide. The metabolite profiling variation between these two samples was clearly visualized.     

Parametrical studies of electroosmotic transport characteristics in submicrometer channels

Spatially two-dimensional nonequilibrium mathematical model describing electroosmotic flow through a submicrometer channel with an electric charge fixed on the channel walls is presented. This system is governed by the hydrodynamic, electrostatic, and mass transport phenomena. The model is based on the coupled mass balances, Poisson, Navier-Stokes, and Nernst-Planck equations. Nonslip boundary conditions are employed. The effect of an imposed electric field on the system behavior is studied by means of a numerical analysis of the model equations. We have obtained the following findings. If the channel width is comparable to the thickness of the electric double layer, the system behaves as an ion-exchange membrane and the dependence of the electric current passing through the channel on the applied voltage is strongly nonlinear. In the case of negatively (positively) charged walls, a narrow region of very low conductivity (so-called ionic gate) is formed in the free electrolyte near the channel entry facing the anode (cathode) side. For a wide channel, the electric current is proportional to the applied voltage and the velocity of electrokinetic flow is linearly proportional to the electric field strength. Complex hydrodynamics (eddy formation and existence of ionic gates) is the most interesting characteristics of the studied system. Hence, current-voltage and velocity-voltage curves and the corresponding spatial distributions of the model variables at selected points are studied and described in detail.     

Two-dimensional lanthanide coordination polymers with bis(diphenylphosphino)hexane dioxide. The determination of the polymeric structure from twinned crystals

Lanthanide nitrates and bis(diphenylphosphino)hexane dioxide (dpphO₂) formed under solvothermal conditions a series of coordination polymers [Ln(dpphO₂)₂(NO₃)₂](NO₃) (Ln = Pr (1), Nd (2), Sm (3), Dy (4), Lu (5)), featuring two-dimensional network structure of the (4, 4) topology. The compounds [Ln(dpphO₂)₂Cl₂]Cl (Ln = Pr (6), Nd (7), Gd (8)) were obtained from corresponding chlorides. Coordination polymer 7 formed regular single crystals of the orthorhombic Pna₂₁$\mathit{Pna}{2}_1$ space group. The nitrate complexes crystallized in the orthorhombic Aea2 space group, however, the crystals were pseudo-merohedral twins simulating a tetragonal diffraction pattern. Unlike our previously characterized neutral polymers with bis(diphenylphosphino)ethane dioxide, all present coordination networks are cationic, with anions located between or within the two-dimensional layers.     

UVA-induced photo recovery during early zebrafish embryogenesis

DNA photorepair has been widely studied in simple aquatic organisms that live in the marine environment, but is less understood in more complex species that live in freshwater. In the present study, we evaluated UVA-induced DNA photo recovery in embryonic stages of zebrafish, Danio rerio, a freshwater model species. Evaluation of UVB exposure and UVA photo recovery of zebrafish embryos revealed different UVB tolerances and capacities for UVA photo recovery at different stages of development. Effective UVA photo recovery was observed at 3h post-fertilization (hpf), 6-7 hpf, and 12 hpf, but not in the early cleavage stage (2-32 cells). UVA photo recovery was most effective during the gastrula stage (6-7 hpf) of development, and less effective at earlier stages (e.g., 3 hpf) or later stages (e.g., 12 hpf). Embryos at the cleavage stage of development were found to be tolerant to extreme levels of UVB exposure, and possible mechanisms were discussed. For embryos at 6-7 hpf, examination of time window (or delay of UVA exposure) that would still permit recovery from UVB exposure suggested a short time period of 2h. The transgenic fli-1 zebrafish with fluorescent vascular structure was used to show that embryos with normal morphological appearance could exhibit a disrupted vascular patterning, suggesting that this endpoint could provide a sensitive tool for detection of UV damage.     

Screening of pi-basic naphthalene and anthracene amplifiers for pi-acidic synthetic pore sensors

Synthetic ion channels and pores attract current attention as multicomponent sensors in complex matrixes. This application requires the availability of reactive signal amplifiers that covalently capture analytes and drag them into the pore. pi-Basic 1,5-dialkoxynaphthalenes (1,5-DAN) are attractive amplifiers because aromatic electron donor-acceptor (AEDA) interactions account for their recognition within pi-acidic naphthalenediimide (NDI) rich synthetic pores. Focusing on amplifier design, we report here the synthesis of a complete collection of DAN and dialkoxyanthracene amplifiers, determine their oxidation potentials by cyclic voltammetry, and calculate their quadrupole moments. Blockage experiments reveal that subtle structural changes in regioisomeric DAN amplifiers can be registered within NDI pores. Frontier orbital overlap in AEDA complexes, oxidation potentials, and, to a lesser extent, quadrupole moments are shown to contribute to isomer recognition by synthetic pores. Particularly important with regard to practical applications of synthetic pores as multianalyte sensors, we further demonstrate that application of the lessons learned with DAN regioisomers to the expansion to dialkoxyanthracenes provides access to privileged amplifiers with submicromolar activity.