text:
\section{Introduction}

Among perovskite structured tantalates, sodium tantalate NaTaO$_3$ has received much attention for photocatalytic water splitting due to its outstanding quantum and photocatalytic efficiency \cite{Grabowska2016, Modak2016}. In this material the larger A-site cation (Na) is 12-fold coordinated by oxygen and located at the corners of a pseudocubic unit cell, while the center of this cell is occupied by the smaller B-site cation (Ta) that is octahedrally coordinated by oxygen (see Figure \ref{fig:bulk_surface_structure}a). For NaTaO$_3$, the formal charges of Na, Ta, and O are +1, +5, -2 respectively. Consequently, the (001) surface is formed by stacking of charged TaO$_2$ and NaO layers, with formal charges of +1 and -1 respectively (see Figure \ref{fig:bulk_surface_structure}b). The surface is hence of type III in Tasker's classification \cite{Tasker1979} and is polar and unstable due to its diverging electrostatic energy \cite{Noguera2000}. Such an instability can be compensated either by adsorption of charged species or electronic or ionic reconstruction \cite{Noguera2013, Deacon-Smith2014a}.

\begin{figure}
	\centering
	\includegraphics{figure1.png}
	\caption{NaTaO$_3$ a) bulk and b) non-reconstructed (001) surface.}
	\label{fig:bulk_surface_structure}
\end{figure}

While the atomic structure of NaTaO$_3$ surfaces has to the best of our knowledge not been investigated experimentally and only sparsely by theory \cite{Liu2015a, Zhao2018bc}, the closely related compound KTaO$_3$ has been investigated much more intensively. Secondary ion mass spectrometry revealed a gradual K enrichment of cleaved (001) surfaces that was interpreted as a bulk to surface migration of K atoms \cite{Szot2000}. A similar evolution of the surface was observed by helium atom diffraction, where an almost equal proportion of TaO$_2$ and KO terminations right after cleaving gradually converted to a pure KO termination \cite{Li2001}. Supported by density functional theory (DFT) calculations \cite{Fritsch1999}, the authors postulate a terraced surface structure and a migration of K atoms to KO step edges that leads to the disappearance of the TaO$_2$ termination \cite{Li2001, Li2003}. An ionic reconstruction with alternating KO and TaO$_2$ rows is also supported by more recent DFT calculations \cite{Deacon-Smith2014}, while other calculations reported a purely electronic reconstruction and a transition from a KO to a TaO$_2$ terminated surface when going from oxygen-poor to oxygen-rich conditions \cite{Wang2018}. The terraced surface structure of KTaO$_3$ is supported by a recent scanning tunnelling and atomic force microscopy study combined with DFT calculations \cite{Setvin2018}. While the cleaved surface exposes TaO$_2$ and KO terminated terraces that follow the domain pattern of the incipient ferroelectricity in this material, annealing ultimately converts it into a labyrinth-like structure of alternating TaO$_2$ and KO terminated terraces running along the [110] direction. The surface energy was determined to be minimal for terrace widths of 4-5 unit cells. After exposure to liquid water, the same authors found another structure type consisting of [001] oriented alternating single unit-cell rows of KO termination hat are stabilized by dissociative water adsorption \cite{Setvin2018}, which was confirmed by another theoretical study \cite{Zhao2018bc}.

Given the similarity in ionic and electronic structure of NaTaO$_3$ and KTaO$_3$, it seems sensible that NaTaO$_3$ will assume a surface reconstruction similar to KTaO$_3$ to compensate polarity. Significantly lower surface energies compared to the non-reconstructed terminations were reported for the terraced reconstructed surfaces of both NaTaO$_3$ and KTaO$_3$ with terrace widths of 3 cells \cite{Zhao2018bc}. However for both materials a so-called cation-exchange reconstruction was reported to be even lower in energy, the formation of which may however be kinetically hindered \cite{Zhao2018bc} leading to the experimentally reported prevalence of the terraced reconstruction for KTaO$_3$ \cite{Setvin2018}. Due to the larger driving force, the appearance of the cation-exchange reconstruction is more likely for NaTaO$_3$ than KTaO$_3$ \cite{Zhao2018bc} but due to a lack of experimental data is it yet unclear if the kinetic barriers retain the terraced reconstruction also for the former material. For this reason we work here under the assumption of a terraced reconstruction also for NaTaO$_3$.

Surface features such as the step edges appearing on this reconstruction are known to affect the surface chemistry of oxides. As such it was recently shown that stepped RuO$_2$ (110) surfaces are less active for the oxygen evolution reaction (OER) compared to flat oxygen-terminated surfaces \cite{Dickens2017}. For hematite Fe$_2$O$_3$ on the other hand, the surface orientation was shown to have a much stronger effect on the OER overpotential than reaction sites at different positions with respect to step edges \cite{Zhang2016b}. It is thus unclear what effect the terraced surface structure of NaTaO$_3$ will have on the photocatalytic OER activity. For this reason, we compare, by means of DFT calculations, the OER activity of the reconstructed terraced (001) surface with the one of the non-polar (113) surface already investigated in our previous work \cite{Ouhbi2018}. For the clean surface, stable at low potentials, we find Ta sites at the center of terrace on the reconstructed (001) surface to be the most active. At higher potentials relevant for photocatalytic applications, the surfaces are covered with O adsorbates and we find a lattice-oxygen mechanism at the center of the NaO terraces to be most active with a very low overpotential of 0.32 V. These results show that the reconstructed surface structure enables reaction pathways that are not favorable on alternative non-polar surface orientations nor on non-polar surfaces of chemically similar materials such as SrTaO$_2$N.

\section{Methods}

Density functional theory calculations were performed with the Quantum ESPRESSO package \cite{Giannozzi2009}, using the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional \cite{Perdew1996}. Ultrasoft pseudopotentials \cite{Vanderbilt1990} with Na(2s, 2p, 3s), Ta(5s, 5p, 5d, 6s) and O(2s, 2p) valence states were used to describe electron-nuclear interactions and wave functions were expanded in plane waves up to a kinetic energy cutoff of 40 Ry combined with 320 Ry for the augmented density.

Surface slabs were constructed based on the experimental orthorhombic NaTaO$_3$ \textit{Pbnm} perovskite structure \cite{Kennedy2006} that was fully relaxed at the PBE level of theory. The reconstructed (001) surface with terraces of width $w$=4 running along the [110] direction was modelled with an 8 atomic layer thick slab (4 NaO and 4 TaO$_2$) with lateral dimensions 5.49$\times$22.20 \AA, from which half of the topmost NaO layer has been moved to the bottom surface of the slab. Periodic images of the slab are separated by a vacuum of 15 \AA\ along the surface normal direction and the bottom two atomic layers as well as the moved NaO half layer were fixed at bulk positions. In addition, a dipole correction \cite{Bengtsson1999} was applied along the z-direction for all slab calculations. Reciprocal-space integration was performed with a 4$\times$1$\times$1 Monkhorst-Pack mesh \cite{Pack1977}. Structures were relaxed with a threshold of 10$^{-3}$ eV$\AA^{-1}$ and 10$^{-6}$ eV for forces and total energies respectively.

We characterise the stability of a surface by its surface energy, which for our stoichiometric slabs is given by
\begin{equation}
	\gamma = \frac{E_{slab} - N \times E_{bulk}}{2A},
\end{equation}
where $E_{slab}$ is the total energy of the slab, $N$ is the number NaTaO$_3$ bulk formula units in the slab, $E_{bulk}$ is the energy per formula unit in the bulk and $A$ is the surface area of the slab.

All reactions energies $\Delta G(U_b, \mathrm{pH})$ under given pH and potential ($U_b$) conditions were calculated within the computational standard hydrogen electrode approach \cite{Norskov2004}:
\begin{equation}
\Delta G(U_b, \mathrm{pH}) = \Delta E + (\Delta\mathrm{ZPE} - T\Delta S) - \mathrm{e}U_b - k_BT\cdot \ln(10)\cdot \mathrm{pH}
\label{eq:deltaG}
\end{equation}
where $\Delta E$ is the DFT-calculated reaction energy, -e$U_b$ and $-k_B T \cdot \ln(10) \cdot \mathrm{pH}$ account for the electron and proton reservoirs respectively and $\Delta$ZPE and $\Delta S$ are the changes in zero point energy and entropy respectively of the reaction step as given in our previous paper \cite{Ouhbi2018}. We characterize the OER activity of a given surface by its thermodynamic overpotential $\eta$, which is the potential for which all PCET steps have free-energy changes smaller than the equilibrium potential of 1.23 V:
\begin{equation}
	\eta = \frac{\max(\Delta G)}{e} - 1.23 \mathrm{V}
\label{eq:OP}
\end{equation}

\section{Results and discussion}

\subsection{Surface reconstruction}
For the reconstructed NaTaO$_3$ (001) surface with a terrace width $w$=4 shown in Figure \ref{fig:slab_models}a), we predict a surface energy of 1.20 Jm$^2$ (see Table \ref{table:surface_energies}), which is very similar to the previously reported 1.17 Jm$^2$ for $w$=3 \cite{Zhao2018bc}. Comparing this to the surface energies of the non-reconstructed (001) surfaces as well as the higher index non-polar (113) surface \cite{Ouhbi2018}, we find the NaO-terminated (001) surface to be the least stable followed by the reconstructed (001) and the TaO$_2$-terminated (001) surface, while the formally non-polar (113) surface (see Figure \ref{fig:slab_models}b) is the most stable (see Table \ref{table:surface_energies}). While the high energy of the NaO-terminated surface is not surprising, given the sequence of formally charged layers, the relatively low energy of the TaO$_2$-terminated surface is unexpected. We however believe it to be an artefact of our rather thin slabs as higher surface energies were reported for thicker slabs \cite{Zhao2018bc}. Taking this into considerations, the reconstructed (001) and the (113) surface both have low surface energies with a difference of only 0.08 J/m$^2$ and could both be exposed. As shown in Figure \ref{fig:slab_models}, these two surfaces differ in the coordination of their exposed Ta sites, which are square pyramidal (Ta$_{5c}$) coordinated on the reconstructed (001) surface but distorted tetrahedral coordinated (Ta$_{4c}$) on the (113) surface.

\begin{figure}
	\centering
	\includegraphics{figure2.png}
	\caption{Slab models of a) the reconstructed (001) and b) the (113) surface of NaTaO$_3$. The surface termination layers are highlighted by solid boxes and the $w=4$ unit-cell wide NaO half layer moved to the bottom surface is shown highlighted by the dashed box. The insets show the differently coordinates Ta sites on the (001) and (113) surface.}
	\label{fig:slab_models}
\end{figure}

\begin{table}
	\caption{Surface energies of the non-reconstructed (both NaO- and TaO$_2$-terminated), reconstructed (001) and (113) surfaces of NaTaO$_3$.}
	\begin{tabular}{l l}
	\hline
	Surface & Surface energy (J/m$^2$)\\
	\hline
	Reconstructed (001) & 1.20\\
	NaO-terminated (001) & 1.77\\
	TaO$_2$-terminated (001) & 1.17\\
	NaTaO-terminated (113) & 1.12 \\
	\hline
	\end{tabular}
	\label{table:surface_energies}
\end{table}

\subsection{OER on clean surfaces}

To study the effect of the surface reconstruction on the OER activity, we computed free energy differences for the reaction steps on the reconstructed (001) surface. Among the reaction mechanisms reported in the literature, we adopt the conventional one \cite{Rossmeisl2007}, which is a succession of four proton-coupled electron transfer reaction steps as shown schematically in Figure \ref{fig:coupling_schematic}a). In the first step a water molecule is deprotonated and forms an adsorbed hydroxyl *OH, which is then deprotonated to form an adsorbed oxygen *O. In contact with water a further deprotonation step leads to an adsorbed hydroperoxyl group *OOH, which is released as O$_2$ after a final deprotonation step as shown by equations \ref{eq:A}-\ref{eq:D}:
\begin{eqnarray}
	\ce{2H2O + {*} &->[A]& {*}OH + H2O + (H+ + e^-)}\label{eq:A}\\
	\ce{&->[B]& {*}O + H2O + 2(H+ + e^-)}\label{eq:B}\\
	\ce{&->[C]& {*}OOH + 3(H+ + e^-)}\label{eq:C}\\
	\ce{&->[D]& O2 + 4(H+ + e^-)}\label{eq:D},
\end{eqnarray}
Here * is the active site on the surface, *OH, *O, *OOH are intermediates adsorbed on the active site, and A, B, C, D, are labels for the water oxidation steps. We consider as active sites all inequivalent Na$_i$ or Ta$_i$ sites (see Figure \ref{fig:reconstructed_sites}), where the former are top sites, while the latter are bridge sites between two adjacent Na atoms.

\begin{figure}
	\centering
	\includegraphics{figure3.png}
	\caption{Schematic representation of a) the conventional and b) the coupling mechanism.}
	\label{fig:coupling_schematic}
\end{figure}

In Table \ref{table:binding_overpotentials} we report the adsorption energy of the OER adsorbates and the resulting overpotential for all inequivalent Ta and Na sites on the reconstructed (001) surface. The adsorption free energy with respect to water and hydrogen was computed as
\begin{equation}
	\Delta G_i = G_{\mathrm{slab}+i} - G_\mathrm{slab} - nG_\mathrm{H_2O} - mG_\mathrm{H_2},
\end{equation}
where the adsorbates are $i=\mathrm{OH, O, OOH}$, the free energies $G$ contain the DFT total energy as well as ZPE and entropy contributions and the coefficients $n$ and $m$ are chosen to provide the number of O and H atoms contained in the adsorbate. The differences between adsorption energies at different Ta sites are generally small. We see however a clear trend for less positive adsorption free energies (stronger binding) of all adsorbates at the step sites Ta$_1$ and Ta$_4$ compared to the terrace sites Ta$_2$ and Ta$_3$. Differences in binding geometry do not correlate with the binding strength (see supporting information Figure S1) and we hence associate the stronger binding at Ta$_1$ and Ta$_4$ with the interaction of the adsorbate with the Na ions at the step edge. For all Ta sites the overpotential-determining step (ODS) was found to be the formation of OOH (step C) and the lowest overpotential is about 0.70 V at the terrace sites Ta$_2$ and Ta$_3$. Since $\Delta G_\mathrm{O}$ - $\Delta G_\mathrm{OH}$ is larger for terrace than step sites, this is in good agreement with the universal scaling relations \cite{Man2011}.

\begin{figure}
	\centering
	\includegraphics{figure4.png}
	\caption{On-top Ta and bridging Na adsorption sites on the reconstructed (001) surface shown in a) top and b) side view. Only the surface layer is shown for clarity.}
	\label{fig:reconstructed_sites}
\end{figure}

\begin{table}
\caption{Binding energies ($\Delta G_i$) of the OER adsorbates ($i$ = OH, O, OOH) and the calculated overpotential ($\eta$) on Ta and Na sites of the reconstructed NaTaO$_3$ (001) surface.}
\begin{tabular}{c c c c c}
\hline
Site & $\Delta G_\mathrm{OH}$ (eV)& $\Delta G_\mathrm{O}$ (eV) & $\Delta G_\mathrm{OOH}$ (eV) & $\eta$ (V) \\
\hline
Ta$_1$& 0.11 & 1.45 & 3.54 & 0.80\\
Ta$_2$& 0.23 & 1.72 & 3.65 & 0.70\\
Ta$_3$& 0.23 & 1.72 & 3.66 & 0.71\\
Ta$_4$& 0.07 & 1.46 & 3.47 & 0.78\\
\hline
Na$_1$& 1.36 & 4.09 & 4.06 & 1.50\\
Na$_2$& 1.44 & 4.03 & 4.44 & 1.36\\
Na$_3$& 1.38 & 4.08 & 4.44 & 1.47\\
\hline
\end{tabular}
\label{table:binding_overpotentials}
\end{table}

Figure \ref{fig:free_energy_profile}a) shows the OER free energy profile at the Ta$_2$ site of the reconstructed (001) surface, comparing it with one for the Ta site on the (113) surface \cite{Ouhbi2018}. While step C is the ODS for both surfaces, the Ta$_2$ site of the reconstructed surface is more active for the OER ($\eta$ = 0.70 V) than its counterpart on the (113) surface ($\eta$ = 1.30 V). This is consistent with the adsorption strength of the O intermediate, which is less positive (stronger) on the (113) surface ($\Delta G_\mathrm{O}$= 0.86 eV) compared to the reconstructed (001) surface ($\Delta G_\mathrm{O}$ = 1.72 eV). The difference in activity is likely a result of the different coordination of the Ta site. For both surfaces we observe an upwards relaxation of the Ta site upon O adsorption, increasing the Ta--O bond length to an oxygen below the surface from 1.83 \AA\ to 2.52 \AA\ ($\Delta l$ = 0.69 \AA) for the reconstructed surface and from 1.90 \AA\ to 2.88 \AA\ ($\Delta l$ = 0.98 \AA) for the (113) surface. The 4-fold coordination on the (113) surface thus result in a higher structural flexibility and thus a stronger adsorption compared to the 5-fold coordinated Ta on the reconstructed (001) surface (see Figure \ref{fig:slab_models}).  Recently an overpotential of 1.43 V was reported for the non-reconstructed polar TaO$_2$ terminated (100) surface of NaTaO$_3$ with the ODS being step C \cite{Montoya2018}, which indicates that the reconstruction has a beneficial effect on the OER activity.

\begin{figure}
	\centering
	\includegraphics{figure5.png}
	\caption{Free energy diagram at pH = 0 and U$_b$ = 0 V of the OER reaction steps at the most active a) Ta site and b) Na site of the reconstructed (001) surface. The profiles on the (113) surface \cite{Ouhbi2018} are shown for comparison.}
	\label{fig:free_energy_profile}
\end{figure}

On the NaO terrace, we find bridge adsorption sites to be most favoured (see Figure \ref{fig:reconstructed_sites}). As shown in Table \ref{table:binding_overpotentials} the difference in adsorption energies of the intermediates are fairly small for the three Na sites and result in a difference in overpotential of about 0.1 V, the ODS being the deprotonation of OH (step B) in all cases. The Na$_2$ site at the center of the terrace has a lower overpotential (1.36 V) than Na$_1$ and Na$_3$ sites more towards the edge of the terrace. Comparing with the (113) surface, which has the same ODS (step B), we find that the most active Na sites on the reconstructed (001) surface have a significantly higher overpotential (1.36 V) compared to the (113) surface (0.88 V) \cite{Ouhbi2018}.

\subsection{OER under operating conditions}

Next, we determine the surface adsorbate coverage on the reconstructed (001) surface as a function of the potential by computing Pourbaix diagrams as shown in Figure \ref{fig:pourbaix}. We explored separately covering the TaO$_2$ and NaO terraces with O and OH adsorbates at coverages ranging from 1/4 to 1 monolayer (ML) as well as configurations where both terraces are covered simultaneously. The clean surface is only exposed at potentials below 0.76 V at pH 0, before it becomes OH covered on the TaO$_2$ terrace and ultimately O covered on both terraces for potentials greater than 1.32 V. For the (113) surface \cite{Ouhbi2018}, we found a similar sequence of transitions, however at slightly lower potentials (0.66 and 0.99 V) and with an intermediate 1 ML O coverage on just the Ta sites. Interestingly, we observe for both surfaces a recombination of adjacent O adsorbed on Na sites (see state S3 in Figure \ref{fig:pourbaix} and Figure \ref{fig:state3}a).

\begin{figure}
	\centering
	\includegraphics{figure6.png}
	\caption{Computed Pourbaix diagram of the reconstructed (001) surface. Atomic structures show the different surface states, where pink and white atoms represent the adsorbate oxygen and hydrogen atoms respectively.}
	\label{fig:pourbaix}
\end{figure}

Solar irradiation is expected to yield potentials above 1.32 V and we thus consider state S3 in Figure \ref{fig:pourbaix} as relevant under application conditions. Given that the O$_2$ formed on the NaO terrace is not bound to the surface, we remove it and consider a full O coverage only on the TaO$_2$ terrace as shown in side and top views in Figures \ref{fig:state3}b and \ref{fig:state3}c. We compute the OER on Ta sites, initially considering the conventional mechanism (Figure \ref{fig:coupling_schematic}a) starting with the formation of *OOH on a preexisting *O adsorbate (step C). We find an overpotential of 1.11 V at the step sites Ta$_1$ and Ta$_4$, while terrace sites Ta$_2$ and Ta$_3$ have an overpotential of 1.31 V. These overpotentials are higher than the ones reported above for the clean surface and the ODS changes from step C (OOH formation) on the clean surface to step B (O formation) on the S3 surface (see supporting information Figure S2 a). These results are in contrast to the usual effect of an increased adsorbate coverage leading to lower overpotentials \cite{Montoya2015a} that we also observed for the (113) surface (1.30 V $\rightarrow$ 0.92 V). A potential explanation for this effect is that the adsorbate coverage partially conceals the structural reconstruction, the O covered Ta terrace being intermediate between a TaO$_2$ and a NaO termination.

\begin{figure}
	\centering
	\includegraphics{figure7.png}
	\caption{S3 state of the reconstructed-NaTaO$_3$ (001) surface a) before and after O$_2$ desorption shown in b) side and c) top view. The LO$_1$ and LO$_2$ sites marked in c) are the oxygen atoms participating in the lattice mechanism and green arrows show Ta pairs considered for the coupling mechanism.}
	\label{fig:state3}
\end{figure}

In addition to the conventional mechanism at Ta sites, we also consider an alternative mechanisms that proceeds by direct coupling of O adsorbates at adjacent sites (see Figure \ref{fig:coupling_schematic} b) \cite{Lodi1978, Norskov2004}. While this mechanism was not possible on the (113) surface \cite{Ouhbi2018} due to the large distance of 5.47 \AA\ between Ta sites, the (001) surface has shorter Ta-Ta distances of $\sim$ 3.87 \AA. We consider the coupling between the sites marked with C$_1$ and C$_2$ arrows in Figure \ref{fig:state3}c and find overpotentials of 0.88 V and 0.95 V respectively, the deprotonation of the first OH (step C') being the ODS in both cases (see supporting information Figure S2 b).

On the NaO terrace, we consider both the conventional mechanism and coupling of neighboring O adsorbates and find both mechanisms to have the same overpotential of 1.11 V with the formation of *OH as the ODS. The (113) surface on the other hand had a significantly lower overpotential of 0.79 V for the coupling mechanism \cite{Ouhbi2018}. In addition, we notice a tendency for OH and O adsorbates on the NaO terrace to migrate away from the bridge site and to bind with lattice oxygen. We did observe this neither on the NaTaO$_3$ (113) nor the SrO-terminated SrTaO$_2$N (001) surface \cite{Ouhbi2018}, indicating a particular behaviour of the reconstructed NaTaO$_3$ (001) surface. For this reason we investigate a lattice oxygen evolution reaction (LOER) mechanism \cite{Fabbri2018} at sites LO$_1$ and LO$_2$ marked in Figure \ref{fig:state3}c. We find overpotentials of 0.32 V and 1.09 V respectively, step D (recovery of the lattice oxygen by deprotonation of OH at the LO site) being the ODS for both sites (see supporting information Figure S2 c) and the OOH intermediate being unstable, transferring its H to a neighboring oxygen.

\begin{figure}
	\centering
	\includegraphics{figure8.png}
	\caption{Surface reconstruction after exposure to water: a) side view at zero potential, b) and c) side view and top view under photocatalytic conditions respectively. Green arrows represent the various coupling pathways.}
	\label{fig:humid_structure}
\end{figure}

Above we discussed the OER on the reconstructed surface as it was observed under ultra-high vacuum (UHV) conditions \cite {Setvin2018}. However in the same study the authors report a second reconstruction with 2x1 periodicity that is based on hydroxylated steps running along the [100] direction and which forms after exposing the surface to water, which was confirmed in a later study \cite{Zhao2018bc}. We also consider the OER on this reconstruction (shown in Figure \ref{fig:humid_structure}a), which experimentally coexists with the one considered in the previous section \cite{Setvin2018}. We however assume that under photocatalytic conditions, the hydroxyls are deprotonated as shown in Figure \ref{fig:humid_structure}b) and c). Given the stepped structure of the surface, the conventional mechanism starting from an O at the step edge, can also be considered equivalent to the above LOER pathway on the NaO terrace. For this mechanism, we compute an overpotential of 0.64 V with step C (OOH formation) being the ODS. In analogy to what was shown above for the UHV reconstruction, the recombination of neighboring oxygen adsorbates represents an alternative pathway. We consider coupling of oxygen adsorbates from adjacent steps (pathway C$_3$), across a step (pathway C$_4$) and along the step edge (pathway C$_5$) as shown in Figure \ref{fig:humid_structure}c. We find the lowest overpotential of 0.52 V for pathway C$_3$, which does not involve interaction with Na atoms during coupling, while pathways C$_4$ and C$_5$ both have a larger overpotential of 0.63 V. We note however that these coupling pathways may be associated with additional kinetic barriers \cite{Rossmeisl2007}.

\section{Conclusions}

We have studied the OER activity on reconstructed (001) surfaces of NaTaO$_3$ by DFT calculations. On the clean UHV reconstructed surface we find the most active Ta and Na sites to have overpotentials of 0.70 and 1.36 V respectively. Compared to our previous results for NaTaO$_3$ (113) \cite{Ouhbi2018}, this implies that the Ta site is significantly more reactive on the reconstructed (001) surface, while the Na site is less reactive. Under photocatalytic conditions, the Ta sites are covered by O adsorbates, which leads to high overpotentials of $\sim$ 1.1 V. The adsorbate coverage however also results in a change in OER mechanism on the NaO terrace, where instead of the conventional mechanism, we now find a lattice oxygen evolution mechanism to be most active with a very small overpotential of 0.32 V. On an alternative surface reconstruction that was reported to be stable under exposure to water, we find a coupling mechanism between adjacent rows to be most active with an overpotential of 0.52 V. These results show a high sensitivity of the OER activity on the surface orientation and concomitant reconstructions of the same material. Moreover we show how different reconstructions of the same surface orientation can lead to dramatically different OER mechanisms and very different activities.

\begin{acknowledgement}

This work was funded by SNF Professorship Grant PP00P2\_157615. Calculations were performed on UBELIX (http://www.id.unibe.ch/hpc), the HPC cluster at the University of Bern.

\end{acknowledgement}


text:
Ideas & Books
Ideas and Speeches
Books and Other Reading
Craig Reed
Strategic Partner – Craig Reed, PhD. joined Battle Investment Group as a Strategic Partner in 2018. In this role, Craig supports strategic planning, business development, and value creation activities across our partner companies.
Craig has over 35-years of experience in government contracting for systems, solutions, and services with publicly-traded and privately-held companies; U.S. government policymaking/implementation; and management consulting, including the following senior leadership roles.
President & Chief Growth Officer at Altamira Technologies
Chief Growth Officer and Senior Vice President of Serco
President and COO of NT Concepts
SVP, Strategy & Corporate Development of Engility Corporation
SVP, Strategy & Corporate Development of DynCorp International VP, Business Development, Strategy & Planning, Mission Systems of Northrup Grumman
18-year career at Lockheed Martin in various leadership roles
Senior Policy Advisor and Executive Director of the Secretary of Energy Advisory Board, U.S. Department of Energy
Founder and managing member, Growth Strategy Leaders LLC
Craig holds a Bachelor of Arts degree in Political Science and Psychology from the State University of New York at Albany, a Master's degree in International Affairs from Columbia University's School of International and Public Affairs, and a PhD in Public Policy and National Security Studies from George Washington University.
Battle Investment Group, LLC is a private investment management firm focused on the North American defense/government, aerospace, industrial, and communications markets.
© 2020 Battle Investment Group, LLC all rights reserved.

redpajama_set_name: RedPajamaCommonCrawl


text:
Master of Public Health program offers full-tuition scholarships
The new Master of Public Health program (MPH) at the George Warren Brown School of Social Work is offering four new full-tuition, merit-based scholarships to support students interested in improving community health locally, nationally and internationally.
The scholarships are available to prospective MPH students who have professional interests or experience in a range of areas, including health communications, nursing and community or public service as well as to prospective students completing health and preprofessional health majors who seek career opportunities in public health. Additional tuition assistance also is available to students entering the program, which debuts with the fall 2009 class.
"Tackling today's public health challenges requires a new approach to graduate public health education," said Timothy McBride, Ph.D., professor and associate dean for public health. "Our innovative curriculum will provide students with a framework for understanding and addressing public health challenges that draws upon different disciplines, including architecture, community development, economics, environmental engineering, law, medicine and social work. We believe this approach will better prepare our graduates with the skills they need for a range of careers."
Recognizing that changing health behaviors is critical to improving individual and community health, the Brown School will award one full-tuition Health Communication Scholarship to a prospective student interested in melding an interest in communications, journalism, marketing, public policy, sociology or related fields with that of public health.
The school also is making a full-tuition scholarship available to a registered nurse who wants to pursue an MPH at WUSTL. The scholarship is available to prospective students who have at least a bachelor of science degree in nursing and who are seeking to advance their interests in public health.
The remaining full-tuition scholarships will be awarded to students with strong leadership potential and academic records and who are committed to improving the health of communities or specific populations.
The Brown School will give special consideration to those with extensive community service experience or who are alumni of service corps such as Peace Corps, Teach For America, AmeriCorps, City Year, Coro Fellows and others. Undergraduates majoring in health and preprofessional health disciplines will be given special consideration as well.
"I am pleased that we will be able to offer financial assistance to members of our inaugural MPH class," McBride said.
"The Brown School has a history of providing generous financial support to its graduate students, and we want to continue to provide the resources needed to attract the brightest minds looking to improve the quality of people's lives," he said.
Learn more about the MPH program at gwbweb.wustl.edu or start an application online at app.applyyourself.com/?id=wustl-sw.
For more information, contact the Brown School's Office of Admission and Recruitment at 935-6676.


A March meeting of transportation officials and transportation-industry members in Crystal City, Va., began to lay the groundwork for a new movement in digital asset data collection.
This effort is designed at systematizing the process of network asset data collection and 3-D virtual design while possibly laying the foundation for a highway base map to assist in ushering in the first generation of autonomous vehicle technologies.
Imagine a 360º "cloud" traveling at highway speeds, digitally capturing and recording everything in its path—including road geometry, pavement cracking, signage, levels of retroreflectivity, location of guardrails, roadway markings, rumble strips and virtually any other safety device that is present on the roadway.
When finished, a high-resolution 3-D roadway profile is delivered to the state or local transportation agency where the data can be used to make better decisions in implementing more cost-effective and lifesaving roadway-safety improvements.
No need to imagine any further.
This futuristic, cutting-edge data collection technology exists today and is already providing roadway engineers with detailed inventories that give them a precise, clear picture of all of the assets that they are responsible for.
Nearly 100 of these like-minded data collectors recently gathered for the first annual meeting of the Geospatial Transportation Mapping Association (GTMA). Discussions focused on ways to improve agency decision-makers' ability to create a safer, environmentally sound and efficient transportation infrastructure through the use of sophisticated mapping and data-collection technologies.
It seems the days of manually counting signs in one's jurisdiction, visually measuring miles of guardrail or measuring the width of an edge line with a tape measure are soon to be over, replaced with something called lidar—or light detection and ranging.
Vehicles armed with lasers, cameras, software and sensors are traveling roadways today while their optical-sensing technology is simultaneously measuring the distance and specific properties of targets on the roadway. It does this by illuminating the objects with laser lights. The driver never has to get out of the vehicle, as data collection occurs automatically while traveling at regular speeds. The deliverable is a detailed and accurate inventory of everything on the roadway.
Such data collection and inventory is well under way in Utah, where that state's department of transportation—UDOT—contracted for the deployment of a mobile data-collection system that integrates lidar, photogrammetry, GPS, a 3-D pavement-imaging system and even some sign retroreflectivity technologies for a groundbreaking project that will set the stage for vastly improved asset management statewide. Utah's data sets will be used to improve and develop rigorous safety, planning, maintenance and preservation programs. By confidently knowing the full details of UDOT's multibillion-dollar infrastructure, the agency can make better decisions and ultimately save millions of dollars in maintenance costs.
UDOT chose the sophisticated system integration platform developed by Mandli Communications to gather no less than a dozen different roadway assets as their vehicles travel at posted speed limits. Assets include roadway distress data, surface areas, lane-miles, number of signs, right-of-way images, vertical clearances and more. Each of those categories is broken down even further into subcategories ranging from condition data to GPS data.
While the focus of the conference was asset collection, ways to improve maintenance operations also were on display. One example was provided by LimnTech Scientifics' vision system that combines GPS and sophisticated software to locate and record existing roadway pavement markings at posted speeds with precision and accuracy.
Mounted to any vehicle, this innovative roadway safety invention is completely automatic and virtually assigns the proper location for the installation of roadway markings.
Another use of the technology Limntech discovered was a benefit for snowplow operators.
"Recorded pavement markings give the snowplow operator a virtual image of where the pavement markings are—in an inch or in a foot of snow—keeping the driver safely on course in any condition," said Dolinar.
The benefits of these new technologies seem endless.
"Local agencies have smaller budgets and smaller staffs, but still have just as many roadway safety-improvement decisions to make every day. Collecting accurate data will help state and local officials pinpoint what needs a fix right now and what can wait until later," said Dingess.


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                Harassement Tracker 2.0

                        Form

                        Data Visualization

                        Contact

{STAT 1 GOES HERE}Freelancer is a free bootstrap theme created by Start Bootstrap. The download includes the complete source files including HTML, CSS, and JavaScript as well as optional LESS stylesheets for easy customization.

{STAT 2 GOES HERE}Whether you're a student looking to showcase your work, a professional looking to attract clients, or a graphic artist looking to share your projects, this template is the perfect starting point!

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                        We want to help alleviate harassment of any sort...

                                 Report Harrasment

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          <form action="something.php" method="post">

            Type of  Harassment (Check more than one box if applicable)

                <input type="checkbox" name="checkSexual" class="form-check-input">
                Sexual Harassment

                <input class="form-check-input" name="checkWork" type="checkbox" value="">
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              Relationship to Perpetrator

      <input id="radioStackedStranger" name="radioR" type="radio" value="radioStranger" class="custom-control-input">

      Stranger

      <input id="radioStackedColleague" name="radioR" type="radio" value="radioColleague" class="custom-control-input">

      Colleague

    <input id="radioStackedAcquaintance" name="radioR" type="radio" value="radioAcquaintance" class="custom-control-input">

    Acquaintance

  <input id="radioStackedPeer" name="radioR" type="radio" value="radioPeer" class="custom-control-input">

  School peer

  Please enter the enviornment in which the incident took place.
  <input type="Location" class="form-control" name="location" id="LocationInput" aria-describedby="Help" placeholder="Ex. Subway">
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  Please enter the city in which the incident took place.
  <input type="city" class="form-control" name="city" id="LocationCity" placeholder="Ex. Toronto">

    Description of Incident
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    What is victim's age?
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      What is victim's gender?

        <input id="radioStackedMale" name="radio" type="radio" value="radio male" class="custom-control-input">

        Male

        <input id="radioStackedFemale" name="radio" type="radio" value="radio female" class="custom-control-input">

        Female

        <input id="radioStackedTrans" name="radio" type="radio" value="radio trans" class="custom-control-input">

        Trans

        <input id="radioStackedNonBinary" name="radio" type="radio" value="radioNonBinary" class="custom-control-input">

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    <option selected>Sexual Orientation</option>
    <option value="1">heterosexuality</option>
    <option value="2">homosexuality</option>
    <option value="3">bisexuality</option>
    <option value="4">asexuality</option>
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      <input id="radioStackedCaucasian" name="radioE" type="radio"  value="radioCauasian" class="custom-control-input">

      Cauasian

      <input id="radioStackedAfrican" name="radioE" type="radio" value="radioAfrican" class="custom-control-input">

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      South Asian

      <input id="radioStackedHispanic" name="radioE" type="radio" value="radioHispanic" class="custom-control-input">

      Hispanic/Latino

      <input id="radioStackedFirstNations" name="radioE" type="radio" value="radioFirstNations" class="custom-control-input">

      First Nations

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data

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Contact Me

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Location

3481 Melrose Place

Beverly Hills, CA 90210

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Kansas Mesothelioma Lawyers
For a fast evaluation of your case, submit below
Welcome! Thank you for visiting our Kansas Mesothelioma lawyer web site. Here you will find experienced attorneys who represent the victims of Mesothelioma cancer. Our Kansas Mesothelioma attorneys are highly experienced in Mesothelioma law and provide the highest quality legal representation to all injured clients. Our Kansas Mesothelioma lawyers have successful track records, which are proven by superior case results and substantial monetary recoveries for their clients. If you are in need of an experienced Mesothelioma lawyer look no further. Our lawyers have recovered millions of dollars for their injured clients! So click here to start protecting your rights today, and to be connected with an experienced Kansas Mesothelioma lawyer.
For more than 100 years, asbestos has been used in building products, shipyards, and factories. It has been an airborne presence affecting millions of workers. Even those who do not work in an area where asbestos fibers are found can be affected by fibers brought home on clothing by other family members. With a latency period of 20 to 50 years, asbestos is the cause of diseases such as mesothelioma, asbestosis, and lung cancer many years after the initial exposure. It is estimated that as many as 21 million workers have been exposed to asbestos in the workplace in the last 50 years and nearly 3,000 new cases of disease attributable to asbestos exposure are diagnosed each year.
Claims of damage related to asbestos exposure were filed as early as 1929, when the dangers of such exposure were first noted. Since then, hundreds of suits have been filed against the manufacturers of asbestos products, charging negligence, design defect, and failure to warn, and millions of dollars have been awarded in damages.
People who have been involved in a Mesothelioma may suffer from both their sickness and emotional distress. Mesothelioma cancer treatments may require lengthy periods in the hospital, in addition to costly specialists, and medication. A qualified Mesothelioma attorney may be able to recover significant monetary compensation on your behalf, which can be used to assist in the payment of these expenses.
A knowledgeable Mesothelioma attorney is prepared with a variety of procedures that are necessary to a successful outcome in a Mesothelioma cancer case. Our attorneys investigate all of the facts associated with the case and collect evidence which is used to support your case. It is important that you hire a successful Mesothelioma lawyer as soon as possible, following your injury. They will be available to answer all of your Mesothelioma law questions, as well as provide you with practical and informative legal advice. All consultations are FREE and our lawyers work on a contingency basis. This means that you pay NOTHING until your case is WON!
If you or a loved one has had or has Mesothelioma or any other cancer that may have been cause from exposure to asbestos CLICK HERE to contact an experienced Mesothelioma Attorney today!
Find a Mesothelioma Lawyer or Law Firm near you:
Alabama Mesothelioma Lawyers • Alaska Mesothelioma Lawyers • Arkansas Mesothelioma Attorneys • Arizona Mesothelioma Attorneys • California Mesothelioma Lawyers • Colorado Mesothelioma Attorneys • Connecticut Mesothelioma Lawyers • Delaware Mesothelioma Attorneys • Florida Mesothelioma Attorneys • Georgia Mesothelioma Lawyers • Hawaii Mesothelioma Attorneys • Iowa Mesothelioma Lawyers • Illinois Mesothelioma Lawyers • Indiana Mesothelioma Attorneys • Idaho Mesothelioma Attorneys • Kansas Mesothelioma Lawyers • Kentucky Mesothelioma Lawyers • Louisiana Mesothelioma Attorneys • Maine Mesothelioma Attorneys • Maryland Mesothelioma Lawyers.com • Massachusetts Mesothelioma Lawyers • Michigan Mesothelioma Attorneys • Minnesota Mesothelioma Lawyers • Mississippi Mesothelioma Attorneys • Missouri Mesothelioma Lawyers • Montana Mesothelioma Lawyers • Nebraska Mesothelioma Attorneys • Nevada Mesothelioma Attorneys • New Hampshire Mesothelioma Lawyers • New Jersey Mesothelioma Lawyers • New Mexico Mesothelioma Attorneys • New York Mesothelioma Lawyers • North Carolina Mesothelioma Attorneys • North Dakota Mesothelioma Lawyers • Ohio Mesothelioma Attorneys • Oklahoma Mesothelioma Lawyers • Oregon Mesothelioma Lawyers • Pennsylvania Mesothelioma Attorneys • Rhode Island Mesothelioma Attorneys • South Carolina Mesothelioma Lawyers • South Dakota Mesothelioma Attorneys • Tennessee Mesothelioma Lawyers • Texas Mesothelioma Lawyers • Utah Mesothelioma Attorneys • Vermont Mesothelioma Attorneys • Virginia Mesothelioma Lawyers • Washington Mesothelioma Lawyers • Washington, D.C. Mesothelioma Attorneys • West Virginia Mesothelioma Attorneys • Wisconsin Mesothelioma Lawyers • Wyoming Mesothelioma Lawyers
Kansas Mesothelioma Lawyer Disclaimer: The Kansas Mesothelioma, asbestos cancer, asbestiosis, wrongful death, negligence or other legal information presented at this site should not be construed to be formal legal advice, nor the formation of a lawyer or attorney client relationship. Any results set forth here were dependent on the facts of that case and the results will differ from case to case. Please contact an Kansas Mesothelioma lawyer or Asbestos cancer attorney for advice on your rights.
Copyright © 2004-10 US Mesothelioma Lawyers - Kansas Mesothelioma Attorneys and Kansas Asbestos Lawyers serving the Kansas counties of: Allen County, Anderson County, Atchison County, Barber County, Barton County, Bourbon County, Brown County, Butler County, Chase County, Chautauqua County, Cherokee County, Cheyenne County, Clark County, Clay County, Cloud County, Coffey County, Comanche County, Cowley County, Crawford County, Decatur County, Dickinson County, Doniphan County, Douglas County, Edwards County, Elk County, Ellis County, Ellsworth County, Finney County, Ford County, Franklin County, Geary County, Gove County, Graham County, Grant County, Gray County, Greeley County, Greenwood County, Hamilton County, Harper County, Harvey County, Haskell County, Hodgeman County, Jackson County, Jefferson County, Jewell County, Johnson County, Kearny County, Kingman County, Kiowa County, Labette County, Lane County, Leavenworth County, Lincoln County, Linn County, Logan County, Lyon County Marion County, Marshall County, McPherson County, Meade County, Miami County, Mitchell County, Montgomery County, Morris County, Morton County, Nemaha County, Neosho County, Ness County, Norton County, Osage County, Osborne County, Ottawa County, Pawnee County, Phillips County, Pottawatomie County, Pratt County, Rawlins County, Reno County, Republic County, Rice County, Riley County, Rooks County, Rush County, Russell County, Saline County, Scott County, Sedgwick County, Seward County, Shawnee County, Sheridan County, Sherman County, Smith County, Stafford County, Stanton County, Stevens County, Sumner County, Thomas County, Trego County, Wabaunsee County, Wallace County, Washington County, Wichita County, Wilson County, Woodson County and Wyandotte County. Kansas Mesothelioma Lawyers serve all Kansas cities including: Kansas City, Overland Park, Topeka and Wichita. All Rights Reserved.
State Legal Resources - National Legal Resources


winter highs are in the 70's, and winter nights come with lows in the 50's to Bear Lake Trail. The high level of precipitation makes Bear Lake Trail a relatively wet place. The month with most of the rain is June; December meanwhile is the driest month.
These outdoors activities are available near Bear Lake Trail.


text:
<?php

// /edit/index.php
// The /edit directory is solely for the use by local bars.
// They each have their own unique login, which allows them
// to edit their bar's information (events, open times, etc.)
session_start();

class Edit {

	function barlist() {
		require("/connect_db.php");
		$sql    = 'SELECT id,name FROM name';
		$result = mysql_query($sql, $link);
		print("<select name='bar_id'>");
		while ($row = mysql_fetch_assoc($result)) {
			print("<option name='barname[" . $row['id'] . "]' value='" . $row['id'] . "'>" . $row['name'] . "</option>");
		}
		print("</select");
	}

	function login_form() {

?>
		<form action='login.php?act=verify' method='post'>

Bar: <?php $this->barlist(); ?>

Password: <input name='barpassword' />

<input type="submit" value="Login" />

		</form>

<?php
	}

		function loggedin_header() {
			print("
You are logged in! (Logout)
");
			print("
From here, you can edit your bar entry within our system.
");
		}
	}

if (@$_SESSION['bar_id'] != NULL) {
$loggedin = TRUE;
$Edit = new Edit();
$Edit->loggedin_header();
} else {
$Edit = new Edit();
$Edit->login_form();
}


Did you know that pears can be an excellent source of dietary fibres? And using them in a salad makes them even more exotic! Pears can be perfect in a salad as their sweetness will balance out the salt and pepper and other ingredients. We will also be using hazelnut vinaigrette, made with authentic balsamic vinegar, so you can imagine the tangy flavour of the salad.
We will be complementing the pear with Belgian endives (chicory also works well if you can't find endives), lettuce, Gorgonzola cheese and several other delicious ingredients to make up the perfect salad for a summer evening accompanied by a glass of chilled Prosecco!
>> Ground black pepper and salt.
Place a bowl on top of a towel or cloth to help it grip the work surface.
Grind the toasted hazelnuts and incorporate with the honey and the vinegar in the bowl using a whisk. While whisking constantly, slowly keep adding the olive oil at regular intervals just as you would do to make mayonnaise.
Add all the oil and keep incorporating air by whisking until the mixture thickens.
Add salt and pepper to taste and place in the fridge.
If you wish you can prepare the vinaigrette up to a week in advance and refrigerate it.
Start off by heating the butter in a pan on a medium high heat.
Add the sugar and swirl around. Allow the sugar to caramelize just a little bit before adding in the pears.
Keep the pears moving around so that they become golden brown all over.
Cook for approximately four minutes and transfer on to a tray for cooling.
>> Seeds from 1 medium pomegranate.
Put the Pears, lettuce, endives and rocket in a salad bowl and toss to blend.
Lightly drizzle six tablespoons of vinaigrette on to the salad and evenly toss using hands. You may add more vinaigrette, salt and pepper to taste.
Once done, sprinkle Gorgonzola cheese and the pomegranate seeds on top immediately before serving.
Buon appetito! We hope that you enjoy this easy-to-prepare, nutrient-packed dish!


Condition: Semi furnished. Air-Conditioner, Water Heater, Bath-tub, Kitchen Table.
Facility: Swimming pool, parking lot, minimarket, bank, 24 hours security, acces-card.
Additional Info: Available several units in very good condition with different city-view, very cheap and flexible rent charge, cheap service charge at only Rp 10.500 per sqm per month, strategic location, close distance to PIK, Shopping malls, restaurants, hospitals, school, commercial areas. Easy access to toll-road to Soekarno-Hatta International airport, and Jakarta Outer ring road.
Additional Info: 10 menit ke PIK, 10 menit ke Toll Soetta, 10 ke Pantai Mutiara, 10 menit ke Green Bay Mall dan Pluit Village Mall.


The primary research focus of my laboratory is vision, how context affects our perception, and how our visual awareness might be related to the underlying neural processing.
2012 – 2014 National Health and Medical Research Council Project Grant, Functional anisotropies in the processing of orientation and direction-of-motion by human visual cortex, Clifford, C.W.G.
2012 – 2014 Australian Research Council Discovery Grant, Gaze perception and adaptation, Clifford, C.W.G.
2011 – 2015 Future Fellowship, Parallel and generative binding in human visual cortex, Clifford, C.W.G.


While InterCare Psychiatric Services has a well-established clinical staff, we are always interested in talented clinicians to enhance the capabilities of our group practice.
We provide treatment based on current medical evidence and proven psychotherapy techniques to help our patients understand their illnesses, mobilize their strengths, and realize their potential. If you are a licensed therapist, nurse practitioner, or psychiatrist interested in full or part time private practice in the South Hills of Pittsburgh, we would like to talk to you.
Please contact our practice administrator, Kristin Seitanakis at seitanakis@intercarehealth.com. Thank you for your interest.


Malignant pleural mesothelioma (MPM) often develops decades following exposure to asbestos. Current best therapy produces a response in only half of patients, and the median survival with this therapy remains under a year. A search for novel targets and therapeutics is underway, and recently identified targets include VEGF, Notch, and EphB4-Ephrin-B2. Each of these targets has dual activity, promoting tumor cell growth as well as tumor angiogenesis.
We investigated EphB4 expression in 39 human mesothelioma tissues by immunohistochemistry. Xenograft tumors established with human mesothelioma cells were treated with an EphB4 inhibitor (monomeric soluble EphB4 fused to human serum albumin, or sEphB4-HSA). The combinatorial effect of sEphB4-HSA and biologic agent was also studied.
EphB4 was overexpressed in 72% of mesothelioma tissues evaluated, with 85% of epithelioid and 38% of sarcomatoid subtypes demonstrating overexpression. The EphB4 inhibitor sEphB4-HSA was highly active as a single agent to inhibit tumor growth, accompanied by tumor cell apoptosis and inhibition of PI3K and Src signaling. Combination of sEphB4-HSA and the anti-VEGF antibody (Bevacizumab) was superior to each agent alone and led to complete tumor regression.
EphB4 is a potential therapeutic target in mesothelioma. Clinical investigation of sEphB4-HSA as a single agent and in combination with VEGF inhibitors is warranted.
Malignant pleural mesothelioma (MPM) is a uniformly fatal disease. It originates from normal mesothelial cells lining the pleural or peritoneal cavity long after exposure to asbestos [1, 2]. There are three main histological types of malignant mesothelioma (epitheloid, sarcomatoid, and mixed or biphasic), with longer survival in epitheloid and shorter survival in sarcomatoid types . Nearly 3,000 new cases are diagnosed each year in the United States . The median overall survival of MPM patients ranges from 12 to 24 months .
The most effective treatment regimen (cisplatin and pemetrexed) induces partial response in half of patients and improves survival from 9 to 12 months . Novel targeted therapies have been investigated in MPM with limited success, including vascular endothelial growth factor (VEGF) inhibitors [5, 6]. Discovery of additional targets and rational combinations of targeted therapies may lead to effective novel therapies. The type 1 receptor tyrosine kinase EphB4 and its cognate ligand Ephrin-B2 are a pair of potential novel targets.
EphB4 and Ephrin-B2 are normally expressed on endothelial cells of venous and arterial lineage, respectively, and their interaction is critically required for new vessel formation, fusion between vessel compartments, and blood flow [7, 8]. In addition, Ephrin-B2 is also expressed on pericytes and vascular smooth muscle cells, where it plays critical role in vessel maturation [9, 10]. In tumor angiogenesis, loss of Ephrin-B2 leads both to significantly reduced tumor vessel density and to tumor growth [11–14]. EphB4, on the other hand, is overexpressed in a variety of epithelial cancers, including breast, prostate, ovarian, esophageal, colon, and head and neck cancers [15–23]. Importantly, we have also shown that EphB4 is expressed in mesothelioma and provides a survival advantage to tumor cells .
Both EphB4 and Ephrin-B2 are transmembrane proteins and direct cell-cell contact leads to bidirectional signaling. EphB4 activation leads to downstream activation of the phosphoinositide kinase-3 (PI3K) pathway in tumor cells , while Ephrin-B2 activation leads to activation of Src [25, 26]. Inhibition of EphB4-Ephrin-B2 signaling blocks tumor angiogenesis, which in turn leads to hypoxia and induces VEGF expression . Targeting VEGF and EphB4-Ephrin-B2 simultaneously is thus a potentially effective therapy.
In this study, we investigated the aberrant expression of EphB4 in a cohort of primary MPM tissues. We show that a significant proportion of MPM tumors expressed EphB4, which provides survival advantage to tumor cells. We also investigated the efficacy of sEphB4-HSA as an inhibitor of EphB4-Ephrin-B2 in MPM xenograft models. sEphB4-HSA induces cell death in MPM tumor xenografts in vivo and down-regulates major signaling pathways including PI3K and Src. In addition, we demonstrate that the combination of sEphB4-HSA and VEGF antibody has superior efficacy than either single agent alone, leading to complete tumor regression. Based on these promising preclinical results, future clinical investigation of the efficacy of sEphB4-HSA combined with VEGF inhibitors in MPM is warranted.
Soluble EphB4 cDNA fused in-frame with human serum albumin cDNA  was expressed as a seamless fusion protein in CHO cells and purified to homogeneity. EphB4-specific antibody (MAb131) was produced by VasGene Therapeutics Inc. Bevacizumab (Genentech Inc) was purchased. Phosphorylated AKT (Ser473), S6 (Ser235/Ser236) and Src (Tyr416) antibodies were from Cell Signaling, Ki67 antibody was from Abcam, CD31 and NG2 antibodies were from BD Biosciences, and terminal deoxynucleotidyl transferase–mediated dUTP nick end labeling (TUNEL) fluorescent kit was from Promega.
NCI-H2373 and MSTO-211H mesothelioma cell lines were obtained from American Type Culture Collection (Manassas, VA). Cells were maintained in RPMI 1640 supplemented with 10% heat-inactivated fetal bovine serum (FBS; Life Technologies, Gaithersburg, MD) and penicillin/streptomycin (Invitrogen, Carlsbad, CA).
Formalin-fixed paraffin-embedded malignant mesothelioma tumors were analyzed. Tissue analysis was approved by the institutional review board. 4-μm sections were deparaffinized, rehydrated, and washed with TBS/Tween-20. Antigens were retrieved with exposure to 1 mM EDTA (pH 8.0; DakoCytomation) for 20 minutes. Endogenous peroxidase activity in samples was blocked by exposure to 3% hydrogen peroxide/PBS (Fisher Scientific, Fair Lawn, NJ) and serum-free protein block (DakoCytomation). Tissue sections were incubated with primary antibodies overnight at 4°C. Standard avidin/biotin immunoperoxidase methods with diaminobenzidines as the chromogen were used for detection (DakoCytomation). The intensity of staining was quantified with ImageJ (NIH). EphB4-specific monoclonal mouse anti-human antibody MAb131 was used for MPM tissues. Positive controls included the 293T cell line stably expressing full-length EphB4. Negative controls included co-incubation of tissues with primary antibody and immunizing peptide.
Male BALB/c nu/nu mice (9 weeks old) were injected with 5 × 106 tumor cells in the flank. When tumor sizes reached 150 mm3, mice were grouped (8 tumors per group) and treated with intraperitoneal (i.p.) injection of PBS (control, 3 times per week), sEphB4-HSA (20 mg/kg, 3 times a week), Bevacizumab (20 mg/kg, 3 times a week), or a combination of sEphB4-HSA and Bevacizumab. Tumor volume was measured three times a week and calculated using the following formula: tumor volume = 0.52 × length × width2, where length and width are the longest and shortest dimensions of a palpable tumor. All procedures were approved by Institutional Animal Care and Use Committee and performed in accordance with the Animal Welfare Act regulations.
Xenograft tumors were harvested and immediately snap frozen. 5-μm fresh frozen tissue sections were fixed in phosphate-buffered 4% paraformaldehyde, blocked with goat serum, and incubated with primary antibody overnight at 4°C. Antibody binding was localized with appropriate AlexaFluor-conjugated secondary antibodies (Invitrogen, Carlsbad, CA). Nuclei were counterstained with 6-diamidino-2-phenylindole dihydrochloride hydrate (DAPI). Images were obtained with a Nikon Eclipse 80i fluorescence microscope and Meta Morph imaging series system. The intensity of staining and the positive signal coverage area were quantified with ImageJ (NIH).
A student's t-test (two-tailed, unpaired) was used to calculate P values between groups where indicated.
39 human MPM tumor samples consisting of 27 epithelioid, 8 sarcomatoid, 2 papillary epithelioid, 1 mixed, and 1 desmoplastic subtypes were studied for EphB4 expression by immunohistochemistry. 85% of epithelioid, 38% of sarcomatoid, and 100% of mixed cell type were positive for EphB4 overexpression (moderate or strong staining, Figure 1A). The representative IHC pictures of EphB4 expression in epithelioid and sarcomatoid MPM subtypes are shown in Figure 1B. In light of personalized therapeutics, this observation that EphB4 overexpression is more frequent in epithelioid tissues is important for clinical study design with therapeutic compounds targeting EphB4 and consideration to select appropriate cases.
EphB4 overoverexpression in MPM. (A) A panel of MPM tissues was stained with EphB4-specific antibody MAb131, and EphB4 expression level was scored and summarized. Moderate and strong expression was considered overexpression. (B) Representative images demonstrating EphB4 expression patterns in epithelioid and sarcomatoid subtypes. (C) 293T cells grown on 8-well chamber slide were transfected with human EphB4 overexpresion vector or empty vector pCDNA3.1. 2 days after transfection, cells were fixed with 4% paraformaldehyde and stained with MAb131 that was also used for staining in (A). Nuclei were counter-stained with DAPI.
The EphB4 antibody (MAb131) used for mesothelioma tissue staining has been shown to have no cross-reactivity to other EphB receptors . To further confirm its specificity in staining, we used it to stain 293T cells ectopically expressing EphB4 and 293T cells transfected with empty vector. Only EphB4 overexpressing 293T cells showed signal (Figure 1C), confirming the specificity of MAb131.
sEphB4 is a soluble decoy of EphB4 that blocks EphB4-Ephrin-B2 bi-directional signaling . sEphB4-HSA has full-length human serum albumin fused to the C-terminus of sEphB4 to improve half life and delivery [14, 29]. We have previously shown that both variants of the protein the sEphB4 alone and sEphB4-HSA have anti-tumor activities in multiple tumor models [14, 28, 30].
Utilizing anti-sense oligonucleotides against EphB4, we had previously reported decreased survival of mesothelioma cell lines . Here, we studied the antitumor activity of sEphB4-HSA in mesothelioma xenograft models using the human sarcomatoid mesothelioma cell line H2373 that has robust overexpression of EphB4. Sarcomatoid is also a category of mesothelioma that is the most difficult to treat. After 25 days of treatment, mice receiving sEphB4-HSA had a 66% reduction in tumor volume (Figure 2A, P < 0.02) compared to control group, and a 20% regression from the starting tumor volume (P < 0.05). Tissues harvested at the conclusion of the study showed reduced vessel density (18% of control; Figure 2B), cell proliferative index (36% of control; Figure 2B), and increased apoptosis (19-fold increase over control; Figure 2C). Thus, blockade of EphB4 activation inhibited tumor angiogenesis and mesothelioma cell proliferation and also induced mesothelioma cell apoptosis in vivo.
sEphB4-HSA inhibited proliferation and induced apoptosis of MPM cell in vivo . (A) sEphB4-HSA (20 mg/kg, 3 times a week) profoundly inhibited H2373 tumor growth in vivo. (B) Representative images of CD31 and Ki67 staining of harvested H2373 tumors showing reduced vessel density and tumor cell proliferation by sEphB4-HSA treatment. CD31 and Ki67 coverage were normalized to DAPI coverage. (C) Representative images of TUNEL staining of harvested H2373 tumors showing induced tumor cell apoptosis by sEphB4-HSA treatment. TUNEL coverage was normalized to DAPI coverage. (D) Representative images of phosphorylated Akt, S6, and Src staining of harvested H2373 tumors showing inhibited PI3K and Src signaling by sEphB4-HSA treatment. At least 4 images from each analysis were used for quantification and statistical analysis. *, P<0.01; **, P<0.002. Error bars indicate standard error of mean.
The PI3K pathway is a major pathway downstream of EphB4 and a critical pathway in mesothelioma [20, 31]. It is also known that activation of the PI3K pathway increases EphB4 levels , thus establishing a positive feedback loop. Here, sEphB4-HSA-treated MPM tumors showed marked decreases in PI3K signaling measured by the downstream levels of phophorylated Akt (Ser473) and phosphorylated ribosomal protein S6 (Ser235/Ser236; Figure 2D). sEphB4-HSA also reduced phosphorylation of Src, which signals downstream of Ephrin-B2 activation [25, 26]. Activated Src induces Bcl-xL and Mcl-1 ; thus, inhibition of Src activation may contribute to the sEphB4-HSA-induced apoptosis seen here. In addition, inhibition of phosphorylation of Akt, S6, and Src was observed at the end of the 25-day treatment, suggesting that the treatment did not trigger a rebound effect.
We have shown previously that VEGF and VEGFRs are expressed in MPM, which is one of the few tumors that utilizes VEGF as an autocrine growth factor . sEphB4-HSA has been shown to markedly inhibit tumor angiogenesis leading to elevated tumor VEGF levels , suggesting that the combination of sEphB4-HSA with VEGF inhibition may lead to enhanced anti-angiogenesis and antitumor activity. We thus combined sEphB4-HSA and the VEGF-neutralizing antibody Bevacizumab in a xenograft study. In light of the H2373 data, we tested another mesothelioma cell line, 211H. This cell line also overexpresses EphB4 and was derived from a patient with biphasic histology, a hard to treat category of mesothelioma . Both agents were highly active alone (71% and 77% reduction in tumor volume at day 21 compared to control group for Bevacizumab and sEphB4-HSA, respectively), while combination therapy led to complete regression of the established tumor after 38 days of treatment (Figure 3), suggesting that this combination warrants further clinical investigation as a therapeutic regimen.
In vivo efficacy of sEphB4-HSA combined with Bevacizumab. 211H tumors were treated with sEphB4-HSA alone (20 mg/kg, 3 times a week), Bevacizumab alone (20 mg/kg, 3 times a week), or sEphB4-HSA combined with Bevacizumab. PBS was used as control. Treatment in single-agent groups and control group was continued for 21 days, whereas treatment in the combination group was continued for 42 days until complete tumor regression. *, P<0.05; **, P<0.02; ***, P<0.01. Error bars indicate standard error of mean.
Since tumors went to complete remission after combinatorial treatment of sEphB4-HSA and Bevacizumab, we had no tumor tissues for analysis. Therefore, we performed a one-week treatment of 211H tumors to analyze the mechanism of the combinatorial effects of sEphB4-HSA and Bevacizumab (Figure 4). After one week treatment, sEphB4-HSA and Bevacizumab each alone reduced vessel density (P < 0.01 and P < 0.05, respectively). sEphB4-HSA had much greater inhibition of tumor vessel density than Bevacizumab, which is consistent with our previous study in Kaposi's Sarcoma . However, tumor growth inhibitions after 3 weeks of treatment with sEphB4-HSA and Bevacizumab were similar (Figure 3). This is very likely due to Bevacizumab's effects on tumor cells directly - mesothelioma is one of only few tumor types that express VEGFR2, produce VEGF and thus have an autocrine loop .
Combinatorial effects of sEphB4-HSA and Bevacizumab on tumor vasculature and tumor cells. 211H tumors were treated as in Figure 3 for one week. Tumors were then harvested for immunofluorescence analysis. Tumor vessel density was evaluated by CD31 staining. Pericyte recruitment to tumor vessel was evaluated by colocalization of NG2-positive pericytes and CD31-positive endothelial cells. Cell proliferative index was evaluated by Ki67 staining and apoptosis was assessed with TUNEL staining. At least 4 images from each analysis were used for quantification and statistical analysis. *, P<0.05; **, P<0.01; ***, P<0.002. Error bars indicate standard error of mean.
We also observed that vessels in Bevacizumab-treated tumors appeared normal in caliber while sEphB4-HSA led to not only significantly reduced vessel density, but also markedly reduced vessel length, vessel caliber, and pericyte recruitment (measured by co-localization of NG2-positive pericytes and CD31-positive endothelial cell; P < 0.002) compared to Bevacizumab treatment.
Ephrin-B2 is strongly expressed on tumor vessels and is necessary for maintaining tumor vasculature. The EphB4-Ephrin-B2 inhibitor sEphB4-HSA prevents EphB4-induced Ephrin-B2 activation in MPM tumor cells. This blockade has two outcomes on tumor vasculature. First, since Ephrin-B2 binds directly to VEGFRs and its activation is required for VEGFR activation [11, 13], EphB4-Ephrin-B2 blockade will inhibit VEGF-induced signaling. Second, pericyte recruitment and vessel maturation will be impaired because Ephrin-B2 is also expressed on pericytes and is necessary for these processes. sEphB4-HSA treatment thus leads to not only fewer but also less mature tumor vessels. When sEphB4-HSA and Bevacizumab were combined, vessel density is further decreased (P < 0.01 compared to Bevacizumab alone), along with diminished pericyte recruitment (P < 0.05 compared to Bevacizumab alone). This enhanced anti-angiogenesis activity combined with direct antitumor activity led to more significantly reduced proliferation (Ki67 staining, P < 0.002 compared to Bevacizumab alone) and increased apoptosis (TUNEL staining, P < 0.05 compared to Bevacizumab alone) than either single agent alone (Figure 4). This may explain the complete regression seen in the long-term combinatorial treatment.
In this study, we found that EphB4 is highly expressed in MPM, especially in epithelioid subtype, and represents a potential therapeutic target. We also found that the EphB4-Ephrin-B2 inhibitor sEphB4-HSA, alone or combined with the anti-VEGF antibody Bevacizumab was highly active in inhibiting mesothelioma growth in xenograft models. sEphB4-HSA is currently in a clinical Phase 1 trial (ClinicalTrials.gov Identifier: NCT01642342). The data presented here suggest that mesothelioma should be a target disease in clinical investigation of this novel therapy, and the combination of sEphB4-HSA and Bevacizumab should undergo further clinical investigation.
Ren Liu, Benjamin D Ferguson contributed equally to this work.
This work was in part supported by SBIR grants (1R43 CA 171538-01 and 1R43 CA 168158-01) to VK, mesothelioma Foundation of America to PSG and DOD to RS.
Kranthi Naga and Valery Krasnoperov are employees of VasGene Therapeutics Inc.
RL and YZ carried out the xenograft studies and immunoanalysis of tumor tissues. BF performed immunoanalysis of human MPM tissues. KN and VK produced EphB4 antibody and sEphB4-HSA for this study. RS, PSG, and VK participated in the design of the study. RL, BF, RS, PSG, and VK drafted the manuscript. All authors read and approved the final manuscript.


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Brazil election: Lula makes stunning comeback
Brazil has taken a turn to the left as former president Luiz Inácio Lula da Silva beat far-right incumbent Jair Bolsonaro in the presidential election.
Sri Lanka: President Rajapaksa to resign after palace stormed
Sri Lankan President Gotabaya Rajapaksa has announced he will step down after protesters stormed his official residence and set the prime minister's house on fire.
Sri Lanka president flees as protesters storm palace
Sri Lanka's President Gotabaya Rajapaksa fled his official residence on Saturday shortly before protesters, angered by an unprecedented economic crisis, stormed and overran the compound.
Kagame to seek fourth term as Rwandan president
The Rwandan leader, Paul Kagame, says he will stand for president again at the next election in 2024.
Zimbabwe court charges man for saying he buys human toes
Claims that hard-pressed Zimbabweans had resorted to selling their toes for survival went viral on social media a fortnight ago and a top government official slammed the jokes as an attempt to harm the country's image.
The authorities in Malawi have stopped South African celebrity Zodwa Wabantu from coming into the country to perform because her revealing dance moves are thought to be out of tune with the nation's moral standards.
US condemns sacking of Tunisia judges
The US has accused Tunisian President Kais Saied of an "alarming pattern" of actions "undermining" Tunisia's independent institutions after he fired dozens of judges.
Malawi slashes the value of its currency
The authorities in Malawi have announced a 25% devaluation of the local currency, the kwacha, starting on Friday.
kidnapping crisis: Why Nigeria wants to jail those who pay ransoms
Having paid a ransom three times to secure the freedom of his loved ones, Nigerian businessman Lawal Ado is not impressed by moves to outlaw payments to kidnappers.
Man gets back his dowry from in-laws after court order
It was a big win for a 52-year-old man seeking dowry refund from in-laws after the Kitale Court granted his wish.


Nailed It: My Latest Creation Is Soo Hot!
Hey my loves! Check out my latest creation… temperature changing nail polish with a chrome overlay. Everyone's been raving about this nail polish, so I finally decided on this pretty pink shade, and I love it so much. It changes color when the temperature reaches 91°F, so even when you get just a little bit warmer – your normal temperature is 98.6 °F – you get this really cool ombré effect on your nails. How much cuter is it with this shimmering chrome overlay? I'm obsessed!
Get my look: I painted my acrylic nails with two coats of temperature changing polish, applied a clear chrome powder, and then sealed it with a gel top coat.
My Nail Polish Collaboration with Formula X!
Hey My Loves! You may have already seen my post and video announcing my new collaboration with Formula X! I've always loved the finish of Formula X polishes — they go on so beautifully and are really long-lasting so when they asked me to collab with them on a few colors, it was a no-brainer for me! I really hope you love these colors as much as I do. There was so much going on my mood board when I was trying to decide what I had to have in this collection, but I boiled it down to these must-have colors for the Fall!
Jetsetter (a gunmetal black with a platinum shimmer) – I thought this color was very futuristic. It made me think of the universe, and the galaxy. It's a twist and a notch more festive than a classic black. And of course, the name is very much reflective of my life these days!
Date Night (deep plum with red undertones) – I really love getting a burgundy color like this — it's my go to for date night (hence the name!). I also thought it was a gorgeous, deep color perfect for fall.
Baroque Babe (a metallic rose gold) – This is my go-to color of the moment. It's really been the color of MY YEAR, and I couldn't do this collection without it.
I really wanted to make statement-making shades that were super versatile to wear on any occasion. The shades are sophisticated and rich– the gold and silver accents were added as a play on the finer things in life, and the decadent burgundy is marked with an elegance I really wanted in this collection.
Tried & Tested | Bio Sculpture Gel Nails!
Would You Wear it?!! 24K Nail Polish!


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Alberta Ferretti Limited Edition
Latest in Fall 2018 Couture
Couture Is All About the Details—Glorious Details. Here, Our 45 Best Close-Ups From the 2018 Collections
By Laird Borrelli-Persson
Violet Chachki Takes on Paris Couture Week—And It's Fabulous
By Rachel Hahn
From Ana Khouri to Tasaki, a Survey of Couture Week's Coolest Jewels
By Tina Isaac-Goizé
The Fall 2018 Couture Collections, as Seen by Illustrator Piet Paris
When Beige Isn't Boring: The Story Behind Dior's Toile de Jouy Couture Gown
By Emily Farra
7 Couture Beauty Looks That Blew Up on the Paris Runways
By Lauren Valenti
Naomi Campbell, Ashley Graham, and More of the Best Dressed at the Paris Couture Shows
Phil Oh's Best Street Style Photos From the Fall '18 Paris Haute Couture Shows
[Paris couture week](https://www.vogue.com/fashion-shows) is technically only four days long, but there are enough shows, Resort appointments, jewelry presentations, and parties to keep the fashion crowd busy for a full week—and then some. This season, things kicked off with a celebrity-studded [Miu Miu show](https://www.vogue.com/fashion-shows/designer/miu-miu) (Uma Thurman, Chloë Sevigny, and Sadie Sink were just a few of the actresses on the runway). On Sunday, [Vetements](https://www.vogue.com/fashion-shows/designer/vetements) showed its men's and women's Spring 2019 ready-to-wear collection under a bridge. Talk about an interesting street style opportunity. There's plenty more to look forward to this week, and Phil Oh will be there to shoot the best looks every step of the way. See all of his photos so far in the slideshow here, and check back every day for more updates.
By Phil Oh
If You Want a Made-to-Measure Minidress, Giovanni Bedin Is Your Man
By Tiziana Cardini


text:
Q: OpenShift brmsworkshop not serving content I am a new user on Openshift and trying to follow the steps to get the bmrsworkshop up and running.
Created an Openshift account ok.
Clicked the "Click to install into Openshift".
Does not respond when i try to open the app url.
Connecting to the back end of the app tells me it is trying to serve the directory.
"[Wed May 11 04:03:47 2016] [error] [client 127.3.121.129] Attempt to serve directory: /var/lib/openshift/5732e5037
628e1867c00005f/app-root/runtime/repo/public/"
There is nothing in this directory.
I also tried installing this from the rhc command line as
** NOW USING **

rhc app create brmsworkshop -t ruby-2.0 --from-code git://github.com/eschabell/openshift-brms-workshop.git

Now i get
[Wed May 11 14:05:17 2016] [error] [client 127.2.236.129] Attempt to serve  directory: /var/lib/openshift/573373e52d52713baf000053/app-root/runtime/
repo/public/
[11/May/2016:14:05:17 -0400] "HEAD / HTTP/1.1" 404 - "-" "-"
[Wed May 11 14:05:17 2016] [error] [client 127.2.236.129] Attempt to serve  directory: /var/lib/openshift/573373e52d52713baf000053/app-root/runtime/
repo/public/
- - - [11/May/2016:14:05:17 -0400] "HEAD / HTTP/1.1" 404 - "-" "-"
(98)Address already in use: make_sock: could not bind to address   127.2.236.129:8080
no listening sockets available, shutting down
Unable to open logs
[Wed May 11 14:07:01 2016] [error] [client 127.2.236.129] Attempt to serve directory: /var/lib/openshift/573373e52d52713baf000053/app-root/runtime /repo/public/
86.142.3.138 - - [11/May/2016:14:07:01 -0400] "GET / HTTP/1.1" 404 295 "-"  "Mozilla/5.0 (Macintosh; Intel Mac OS X 10.11; rv:45.0) Gecko/20100101     Firefox/45.0"

redpajama_set_name: RedPajamaStackExchange


We've all been under the weather here. We're finally getting back to normal and so this morning the kids and I decided we needed a quick little project – make play-doh!
Until recently, I've never made my own play-doh. I've got to say though, I'm hooked now. It is super easy, the colors are endless, and it's a pretty fun activity to do with the kids.
Mix together 1 cup of flour, 2 tsp. cream of tartar and 1/2 cup of salt. This can be mixed right into your cooking pot by the kiddos (off the stove).
In a separate bowl, mix 1 cup of water, 1/2 tbsp. cooking oil, and add some food coloring for color. Pour this into your pot.
Mix the wet and dry ingredients well.
Cook the mixture over med-low heat, stirring occasionally, until it hardens up. This only takes about 5 minutes and it should look like this.
Turn out your dough onto a work surface and carefully knead in a bit of flour. I say carefully just because the dough is hot.
Once cooled, let your helpers play with the new play-doh they helped make!
I adore playdoh and made it so often when my kids were young. Only difference – instead of food colouring use a packet of koolaid and you get colour PLUS the wonderful smell!
All original images and text on this website are copyright and the property of Vanessa Lynch of Punkin Patterns and PunkinPatterns.com. All rights reserved. Note: All projects, patterns and tutorials featured on this website are for personal use only. Feel free to link to my website, but please ask permission to use any photographs.


My narwhal fun print is a perfect gift for those unicorn of the sea lovers. The narwhals are hand drawn with water colour adornments on their backs and tail.
Un-editioned, unframed stamped and signed on the back.
Digitally printed onto recycled card pulp and posted flat with card mailer.


Parachute Media is thrilled to announce the opening of their second location in Charlotte, North Carolina.
As the agency continues to grow with proven success on national clients such as Kirkland's, Merrell and Universal Music Group, we started to look at other cities in the region that could use our help for our second location. With Charlotte being one of the fastest growing cities in the southeast, we knew it would be a great place to expand. Long-time Paratrooper, Elise Kelly, recently packed her bags and embarked on the journey to get the Charlotte office up and running! She will be our first local employee, working out of Hygge coworking space in the heart of Uptown.
Check out our new Charlotte page.


Baldwin School Building Project: Neighborhood Community Forum on Monday, November 26, 2018 6:30 PM to 8:00 PM, Baker School Auditorium. Community members will receive an update on the overall timeline of the project and the Design Feasibility Phase. Time will also be given for the public to provide input and ask questions about the possible expansion of the Baldwin School.
Driscoll School Building Project Community Forum November 26, 2018 6:30 PM to 8:00 PM Driscoll School Library Update on the overall timeline of the project and the Design Feasibility Phase and time for community members to provide input and ask questions about the upcoming renovation and expansion of Driscoll School.


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The 60th anniversary of Eurovision to be produced by the BBC
ImageNewsUnited Kingdom
By Ervin Juhász On Oct 22, 2014
According to the news portal tuner.be, there will be a special 60th Anniversary show of the Eurovision Song Contest, and this show will be produced by the BBC!
Just over nine years ago, the EBU has organized the 50th Anniversary of the Eurovision Song Contest in Copenhagen, a show called "Congratulations!". Now as the Contest hits its 60th edition, another special show will be produced, this time by the BBC.
Tuner.be also informs that this show will be hosted by Petra Mede, who hosted the Eurovision Song Contest last year in Malmo, and she will be joined by Graham Norton, BBC's commentator of the Eurovision Song Contest since 2009, but also co-hosted both editions of Eurovision Dance Contest in 2007 and in 2008.
More information about this show is yet to be announced.
BBCCongratulationseurovision song contestGraham NortonPetra Mede
Ervin Juhász 2125 posts 8 comments
I watched Eurovision in 1998 for the first time (by accident), and wondered what this show was where this girl with a cape sang in Croatian on Hungarian television. It's needless to say that I watch this show ever since. 2008 in Belgrade was the first Eurovision I've ever been to, and the one in Tel Aviv was my 11th.
My favourite Eurovision winner is "Everyway That I Can", and one of my all time favorite Eurovision songs is "Igranka".
Franklin talks to us about "Still Here", his song in Malta Eurovision!
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text:
Brandt Martinez
Brandt Martinez is originally from Peoria, Arizona where he trained at a very young age at Spisak Dance Academy in Ballet, Tap, Jazz, and Hip-Hop. He later furthered his dance education at Tempe Dance Academy where he learned many different styles that make him the versatile dancer he is today. Brandt has been a featured dancer in the International Dance Alliance. He also was an inaugural dancer in the show Ballroom Blitz!, through Stiletto Entertainment wher...read more
Brandt Martinez is originally from Peoria, Arizona where he trained at a very young age at Spisak Dance Academy in Ballet, Tap, Jazz, and Hip-Hop. He later furthered his dance education at Tempe Dance Academy where he learned many different styles that make him the versatile dancer he is today. Brandt has been a featured dancer in the International Dance Alliance. He also was an inaugural dancer in the show Ballroom Blitz!, through Stiletto Entertainment where he got to travel the Caribbean and Mediterranean on a vista class Holland America ship. Brandt has worked with many choreographers such as Tabitha and Napoleon, Tyce Diorio, Joe Lanteri, Joey Downing, Jason Parsons, and Adrienne Canterna.
In early 2010 he was a featured dancer behind Sir Elton John at Carnegie Hall, for Sting's Rainforest Fund Benefit show. He is also known as an international teacher, dancer, and choreographer who has danced all over the nation and has performed in over fifteen different countries from 2009 to now. Brandt is now working with City Ballet of San Diego for the upcoming performance of Romeo and Juliet.
He recently finished touring all over Europe with Rasta Thomas' Bad Boys of Dance in the show Rock the Ballet. He has also gotten the opportunity to dance along side Rasta Thomas at the II International Ballet Awards Ceremony for Dance Open in St. Petersburg, Russia. Although Brandt has accomplished a lot at a young age, he prides himself on remaining teachable for all the years to come.


According to Thursday's results, RIM netted a $934-million profit on total revenue of $5.6 billion during the last quarter of 2010.
During this period, the BlackBerry maker shipped 14.9 million smart phones, taking its total shipment to 52.3 million units in fiscal 2010 - a jump of 43 percent over 2009.
But the rather surprising gloomy forecast for the current quarter came amid mounting excitement about the company's PlayBook tablet due for release April 19.
Analysts ascribed the gloomy outlook to the transition period at RIM which is switching to a new operating system for its phones and tablets.
However, RIM co-CEIO Jim Balsillie said that by discarding its old BlackBerry operating system in favour of the QNX software, Balsillie said RIM would now offer a new class of "super phone'' to its clients.
The PlayBook tablet will be the first RIM device to run on the new operating system developed by QNX Software Systems.
RIM acquired this Ottawa-based software company for $200 million in April last year to have exclusive access to its software technology for its tablet.
RIM had announced to run its tablet on the powerful QNX operating system rather than the BlackBerry 6 operating system which was unveiled along with the BlackBerry Torch 9800 in July.
"We are pleased to report record shipments and financial performance in fiscal 2011,'' RIM co-CEIO Jim Balsillie said, after the fourth quarter results.
"As we enter fiscal 2012, RIM is in an excellent position to benefit from the continuing convergence of the mobile communications and mobile computing markets. We are laying a strong foundation for RIM's expanding market opportunity through focused investments and we are extremely excited about our smartphone, tablet and platform roadmaps,'' the co-CEO said.
Interestingly, the Canadian wireless giant also announced that its PlayBook tablet will also run Android applications, currently available only on tablets and smart phones that are run by Google's Android operating system.
Since RIM is way behind Apple in offering apps, its decision to run Android applications will give PlayBook users access to 200,000 more apps.
"We feel very good about the PlayBook,'' said Balsillie.