Probing local environments in paramagnetic europium-substituted Keggin solids by 31P magic angle spinning NMR spectroscopy

Paramagnetic Eu-substituted Keggin oxopolytungstates crystallize in different forms, determined by the nature of the counterions. The crystal packing is in turn responsible for the variations in the geometry of paramagnetic Eu sites with respect to the anion core. We probed the paramagnetic environments in a series of Eu-substituted Keggin solids, by 31P magic angle spinning NMR spectroscopy. 31P spinning sideband envelopes are dominated by the electron-nuclear dipolar interaction. For the compounds under investigation, both the magnitude and the asymmetry parameter of the electron-nuclear dipolar coupling tensor are sensitive to the mutual arrangements of paramagnetic Eu sites in the crystal lattice. and also report on the stoichiometry of the anion. The electron-nuclear dipolar coupling tensors were calculated from the crystallographic coordinates and the experimentally determined effective magnetic moments, assuming a point dipole approximation. The computed tensors are in very good agreement with the experimental spectra. Furthermore, the P-Eu distance estimates, accurate to within 0.06-0.12 A, can be obtained directly from the magnitude of the electron-nuclear dipolar coupling. This work demonstrates that 31P MAS NMR spectroscopy is a useful probe for investigating local environments in paramagnetic Keggin solids.     

Kinetics of J-aggregation of cyanine dyes in the presence of gelatin

The kinetics of formation of J-aggregates for 3,3'-bis[sulfopropyl]-R-4',5'-dibenzo-9-ethylthiacarbocyanines (R=5-methoxy; R=4,5-dibenzo) and 3,3'-bis[sulfopropyl]-5,5'-diphenyl-9-ethyloxacarbocyanine were studied in aqueous solution in the presence of gelatin at different pH values and at room and elevated temperatures. Addition of gelatin at concentrations of 0.0005-0.05 wt % to solutions of dyes results in the production of J-aggregates in the tens of seconds to tens of minutes range. The rate of J-aggregate formation increases with increasing concentrations of dye and gelatin, correlates with the rate of decay of dimers, and is also dependent on the dye structure, temperature, and pH. The rate of J-aggregation is increased for and decreased for with an increase in temperature. For and, the rate increases with increasing [H+] and reaches the maximum value at pH 3.3-4.3 for 3. The interaction of with gelatin is considered to be a cooperative binding process, and J-aggregation is characterized by the time-dependent rate constant. Sigmoidal- and nonsigmoidal-type kinetic curves of both formation of J-aggregates and decay of the dimers are best fitted with a stretched exponential function.     

The dirichlet problem in lipschitz domains for higher order elliptic systems with rough coefficients

We study the Dirichlet problem, in Lipschitz domains and with boundary data in Besov spaces, for divergence form strongly elliptic systems of arbitrary order with bounded, complex-valued coefficients. A sharp corollary of our main solvability result is that the operator of this problem performs an isomorphism between weighted Sobolev spaces when its coefficients and the unit normal of the boundary belong to the space VMO.     

Superinsulator–superconductor duality in two dimensions

For nearly a half century the dominant orthodoxy has been that the only effect of the Cooper pairing is the state with zero resistivity at finite temperatures, superconductivity. In this work we demonstrate that by the symmetry of the Heisenberg uncertainty principle relating the amplitude and phase of the superconducting order parameter, Cooper pairing can generate the dual state with zero conductivity in the finite temperature range, superinsulation. We show that this duality realizes in the planar Josephson junction arrays (JJA) via the duality between the Berezinskii–Kosterlitz–Thouless (BKT) transition in the vortex–antivortex plasma, resulting in phase-coherent superconductivity below the transition temperature, and the charge-BKT transition occurring in the insulating state of JJA and marking formation of the low-temperature charge-BKT state, superinsulation. We find that in disordered superconducting films that are on the brink of superconductor–insulator transition the Coulomb forces between the charges acquire two-dimensional character, i.e. the corresponding interaction energy depends logarithmically upon charge separation, bringing the same vortex-charge-BKT transition duality, and realization of superinsulation in disordered films as the low-temperature charge-BKT state. Finally, we discuss possible applications and utilizations of superconductivity–superinsulation duality.     

A numerical study of the superadiabatic flame temperature phenomenon in HN3 flames

The phenomenon of superadiabatic flame temperature (SAFT) was discovered and investigated in a low-pressure HN₃/N₂ flame using numerical modelling. A previously developed mechanism of chemical reactions in the HN₃/N₂ flame at the pressure 50 Torr and the initial temperature T₀ = 296 K was revised. Rate constants of several important reactions involving HN₃ (HN₃ (+N₂) = N₂ + NH (+N₂), R1; HN₃ (+HN₃) = N₂ + NH (+HN₃), R2; HN₃ + H = N₂ + NH₂, R4; HN₃ + N = N₂ + NNH, R5; and HN₃ + NH₂ = NH₃ + N₃, R7) were calculated using quantum chemistry and reaction rate theories. Modified Arrhenius expressions for these reactions are provided for the 300–3500 K temperature range. Modelling of the flame structure and flame propagation velocity of the HN₃/N₂ flame at p = 50 Torr and T₀ = 296 K was performed using the revised mechanism. The results demonstrate the presence of the SAFT phenomenon in the HN₃/N₂ flame. Analysis of the flame structure and the kinetic mechanism indicates that the cause of SAFT is in the kinetic mechanism: exothermic reactions of radicals with hydrogen atoms occur in the post flame zone, which results in the formation of super equilibrium H₂ concentrations. The flame propagation velocity is largely determined by the second-order HN₃ decomposition reaction and not by the reaction of HN₃ with H, as was previously assumed. Calculation of the flame propagation velocity according to the Zeldovich-Frank-Kamenetsky theory with the decomposition reaction as a limiting stage yielded a value that agrees with that obtained in numerical modelling using the complete reaction mechanism.     

Conformational Dynamics Underlies Different Functions of Human KDM7 Histone Demethylases

The human KDM7 subfamily histone H3 Nϵ-methyl lysine demethylases PHF8 (KDM7B) and KIAA1718 (KDM7A) have different substrate selectivities and are linked to genetic diseases and cancer. We describe experimentally based computational studies revealing that flexibility of the region linking the PHD finger and JmjC domains in PHF8 and KIAA1718 regulates interdomain interactions, the nature of correlated motions, and ultimately H3 binding and demethylation site selectivity. F279S an X-linked mental retardation mutation in PHF8 is involved in correlated motions with the iron ligands and second sphere residues. The calculations reveal key roles of a flexible protein environment in productive formation of enzyme-substrate complexes and suggest targeting the flexible KDM7 linker region is of interest from a medicinal chemistry perspective.     

Exploring the Interplay between Drug Release and Targeting of Lipid-Like Polymer Nanoparticles Loaded with Doxorubicin

Targeted delivery of doxorubicin still poses a challenge with regards to the quantities reaching the target site as well as the specificity of the uptake. In the present approach, two colloidal nanocarrier systems, NanoCore-6.4 and NanoCore-7.4, loaded with doxorubicin and characterized by different drug release behaviors were evaluated in vitro and in vivo. The nanoparticles utilize a specific surface design to modulate the lipid corona by attracting blood-borne apolipoproteins involved in the endogenous transport of chylomicrons across the blood–brain barrier. When applying this strategy, the fine balance between drug release and carrier accumulation is responsible for targeted delivery. Drug release experiments in an aqueous medium resulted in a difference in drug release of approximately 20%, while a 10% difference was found in human serum. This difference affected the partitioning of doxorubicin in human blood and was reflected by the outcome of the pharmacokinetic study in rats. For the fast-releasing formulation NanoCore-6.4, the AUC_0→1h was significantly lower (2999.1 ng × h/mL) than the one of NanoCore-7.4 (3589.5 ng × h/mL). A compartmental analysis using the physiologically-based nanocarrier biopharmaceutics model indicated a significant difference in the release behavior and targeting capability. A fraction of approximately 7.310–7.615% of NanoCore-7.4 was available for drug targeting, while for NanoCore-6.4 only 5.740–6.057% of the injected doxorubicin was accumulated. Although the targeting capabilities indicate bioequivalent behavior, they provide evidence for the quality-by-design approach followed in formulation development.     

Conforming and nonconforming harmonic finite elements

ABSTRACT

Instead of using the full polynomial space, a conforming and a nonconforming finite element methods are designed where only harmonic polynomials (a much smaller space) are employed in the computation. The conforming quadratic harmonic polynomial finite element is defined only on a special triangular grid. The nonconforming quadratic harmonic finite element is defined on general triangular grids. The optimal order of convergence is proved for both finite element methods, and confirmed by numerical computations. In addition, numerical comparisons with the standard conforming and nonconforming finite elements are presented.