Insights into the mechanism of energy transfer with poly(heptazine imide)s in deoximation reaction

Following our previous studies on potassium poly(heptazine imide) (K-PHI) – catalyzed photooxidative [3+2] aldoxime-to-nitrile addition to form 1,2,4-oxadiazoles, we discovered that electron-rich oximes yield the parent aldehydes instead of target products. In this work, the mechanism of this singlet oxygen-mediated deoximation process was established using a series of control reactions and spectroscopic measurements such as steady-state and time-resolved fluorescence quenching experiments. Additionally, singlet-triplet energy gap value was obtained for K-PHI in suspension, and the reaction scope was broadened to include ketoximes

Multisite PCET with photocharged carbon nitride in dark

A combination of photochemistry and proton coupled electron transfer (PCET) is a primary strategy employed by biochemical systems and synthetic chemistry to enable uphill reactions under mild conditions. Degenerate nanometer-sized n-type semiconductor nanoparticles (SCNPs) with the Fermi level above the bottom of the conduction band are strongly reducing and act more like metals than semiconductors. Application of the degenerate SCNPs is limited to few examples. Herein, we load microporous potassium poly(heptazine imide) (K-PHI) nanoparticles with electrons (e–) and charge balancing protons (H+) in an illumination phase using sacrificial agents. e–/H+ in the K-PHI nanoparticles are weakly bound and therefore could be used in a range of PCET reactions in dark, such as generation of aryl radicals from aryl halides, ketyl radicals from ketones, and 6e–/6H+ reduction of nitrobenzene to aniline. The integration of several features that until now were intrinsic for plants and natural photosynthesis into a transition metal free nanomaterial composed of abundant elements (C, N, and K) offers a powerful tool for synthetic organic chemistry

Continuum theory of vacancy-mediated diffusion

We present and solve a continuum theory of vacancy-mediated diffusion (as evidenced, for example, in the vacancy driven motion of tracers in crystals). Results are obtained for all spatial dimensions, and reveal the strongly non-gaussian nature of the tracer fluctuations. In integer dimensions, our results are in complete agreement with those from previous exact lattice calculations. We also extend our model to describe the vacancy-driven fluctuations of a slaved flux line.Comment: 25 Latex pages, subm. to Physical Review

The Atomic Slide Puzzle: Self-Diffusion of an Impure Atom

In a series of recent papers van Gastel et al have presented first experimental evidence that impure, Indium atoms, embedded into the first layer of a Cu(001) surface, are not localized within the close-packed surface layers but make concerted, long excursions visualized in a series of STM images. Such excursions occur due to continuous reshuffling of the surface following the position exchanges of both impure and host atoms with the naturally occuring surface vacancies. Van Gastel et al have also formulated an original lattice-gas type model with asymmetric exchange probabilities, whose numerical solution is in a good agreement with the experimental data. In this paper we propose an exact lattice solution of several versions of this model.Comment: Latex, 4 pages, 2 figures, to appear in Phys. Rev. E (RC

Productiemetingen aan mosselzaad-invang-installaties (MZI's) 2009, 2010, 2011: technisch rapport project meerjarige effect- en productiemetingen aan MZI's in de westelijke Waddenzee, Oosterschelde en Voordelta

Ter onderbouwing van de beschrijving van de effecten van de MZI’s op de ecosystemen van de Oosterschelde en Waddenzee zijn gegevens nodig van aanwas, groei, sterfte en totale biomassa van MZI-mosselen gedurende het seizoen. Deze gegevens zijn tevens nodig als input voor modelberekeningen. Met toestemming van de MZI-ondernemers zijn metingen verricht aan bestaande MZI’s, met als doel: het bepalen van individuele groei (in lengte en gewicht) van zaadmosselen; het bepalen van de toename in aantallen en biomassa van zaadmosselen per vierkante meter net of per meter touwlengte; het bepalen van de biomassa aan MZI-systemen gedurende het seizoen. Deze metingen zijn verricht in de Oosterschelde en Waddenzee

Ultra-Slow Vacancy-Mediated Tracer Diffusion in Two Dimensions: The Einstein Relation Verified

We study the dynamics of a charged tracer particle (TP) on a two-dimensional lattice all sites of which except one (a vacancy) are filled with identical neutral, hard-core particles. The particles move randomly by exchanging their positions with the vacancy, subject to the hard-core exclusion. In case when the charged TP experiences a bias due to external electric field ${\bf E}$, (which favors its jumps in the preferential direction), we determine exactly the limiting probability distribution of the TP position in terms of appropriate scaling variables and the leading large-N ($n$ being the discrete time) behavior of the TP mean displacement $\bar{{\bf X}}_n$; the latter is shown to obey an anomalous, logarithmic law $|\bar{{\bf X}}_n| = \alpha_0(|{\bf E}|) \ln(n)$. On comparing our results with earlier predictions by Brummelhuis and Hilhorst (J. Stat. Phys. {\bf 53}, 249 (1988)) for the TP diffusivity $D_n$ in the unbiased case, we infer that the Einstein relation $\mu_n = \beta D_n$ between the TP diffusivity and the mobility $\mu_n = \lim_{|{\bf E}| \to 0}(|\bar{{\bf X}}_n|/| {\bf E} |n)$ holds in the leading in $n$ order, despite the fact that both $D_n$ and $\mu_n$ are not constant but vanish as $n \to \infty$. We also generalize our approach to the situation with very small but finite vacancy concentration $\rho$, in which case we find a ballistic-type law $|\bar{{\bf X}}_n| = \pi \alpha_0(|{\bf E}|) \rho n$. We demonstrate that here, again, both $D_n$ and $\mu_n$, calculated in the linear in $\rho$ approximation, do obey the Einstein relation.Comment: 25 pages, one figure, TeX, submitted to J. Stat. Phy

A One-Dimensional Model for Many-Electron Atoms in Extremely Strong Magnetic Fields: Maximum Negative Ionization

We consider a one-dimensional model for many-electron atoms in strong magnetic fields in which the Coulomb potential and interactions are replaced by one-dimensional regularizations associated with the lowest Landau level. For this model we show that the maximum number of electrons is bounded above by 2Z+1 + c sqrt{B}. We follow Lieb's strategy in which convexity plays a critical role. For the case of two electrons and fractional nuclear charge, we also discuss the critical value at which the nuclear charge becomes too weak to bind two electrons.Comment: 23 pages, 5 figures. J. Phys. A: Math and General (in press) 199

Nothing moves a surface: vacancy mediated surface diffusion

We report scanning tunneling microscopy observations, which imply that all atoms in a close-packed copper surface move frequently, even at room temperature. Using a low density of embedded indium `tracer' atoms, we visualize the diffusive motion of surface atoms. Surprisingly, the indium atoms seem to make concerted, long jumps. Responsible for this motion is an ultra-low density of surface vacancies, diffusing rapidly within the surface. This interpretation is supported by a detailed analysis of the displacement distribution of the indium atoms, which reveals a shape characteristic for the vacancy mediated diffusion mechanism that we propose.Comment: 4 pages; for associated movie, see http://www-lion.leidenuniv.nl/sections/cm/groups/interface/projects/therm

Inventarisatie van Japanse oesterbanken in de ooesterschelde en Waddenzee in 2011

Het areaal aan oesterbanken is voor de Waddenzee geschat op 909 hectare. Hiervan is 743 hectare in het veld ingemeten en 166 hectare gereconstrueerd in GIS