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The Sky, Order and Chaos
admin - August 8, 2014 September 5, 2014
The following is an extract from a book called The Sky, Order and Chaos by Jean-Pierre Verdet and Anthony Zielonka which surmises and describes many aspects of wonder that our early ancestors would have pondered upon, the consequences of which leads to the kinds of questions Quantum Gaze interest and intrigue seeks to explore.
"For more than a million years, one hears nothing of mankind. Human beings left very little evidence of their technical achievements, and even though those artifacts that have been found – sharpened pebbles, tools made of stone fragments, scrapers – presuppose a degree of intelligence, there is no material evidence testifying to their mental activity. It was only in the last part of the Stone Age, approximately 50,000 years ago, that evidence of human expression appeared: bones decorated with red pigment, small balls of limestone adorned with bits of stone and fragments of bone, the first engraved stones, the first attempts at sculpture, the first tombs. On the earliest engraved stones one can make out groups of stars, or constellations, indicating that even prehistoric people fixed their gaze upon the sky.
From the dawn of time people have observed unchanging regularities in the cosmos days, seasons and phases of the moon.
From the moment they first connected the alternation of night and day with the motion of the heavens, human beings have been fascinated by astronomy, or the science of celestial bodies – their origins, their composition, their movements. Long before they knew how to write, people knew the phases of the moon, which formed the basis of the first calendars. They noticed the periodic return of the seasons. They watched the daily movement of the stars, which they saw as circular and uniform, and observed every night that the stars reappeared in the sky in what seemed to be permanent arrangements; they found it useful to group the stars into constellations and sometimes to label them according to the images they saw in them. Scholars believe that even from prehistoric times the study of the sky has stimulated a dual development in human thought: the search for natural and unchanging laws by which events, such as those that occur in or derive from the sky, could be understood ands so planned for, and the temptation to place in the sky, which then appeared inaccessible, omnipotent beings to explain many of those mysterious and sometimes frightening events.
Links between certain celestial and earthly phenomena were recognised from an early period. For example, the phases of the moon could be correlated with the schedule of the tides, and the succession of the seasons with the sun's progress through the stars. Evidence of specific, labelled constellations of stars – the Bull, the Scorpion and the Lion – can be traced to the Euphrates valley around 4000 BC. It was much later, probably sometime in the 5th century BC, that the ecliptic – the apparent path of the sun through the heavens during the course of a calendar year – was identified in Babylon, and perhaps in Greece also. The Babylonians took all the stars that fell across the ecliptic and divided them into the twelve constellations known today as the signs of the zodiac. They studied the positions of these stars in relation to other celestial bodies in order to determine the wishes of their gods and assure the well-being of their kings, and they developed stories, or myths, that connected occurrences in the sky with the activities of the gods. The study of the influence of the stars and planets on human affairs became known as astrology.
Order and disorder, those fundamental opposites, appear in both scientific and popular studies of the night sky.
Early people must have been fascinated also by the movement of the planets against the great network of the stars. Along with the major periodical astronomical phenomena there occurred exceptional, often spectacular events, such as solar or lunar eclipses or the appearance of comets or shooting stars. The sky overhead could also grow angry, producing thunder and lighting, flooding rains and violent windstorms such as hurricanes or tornadoes. Thus, along with the order that controlled so many constant and apparently eternal events, there existed an unpredictable and often terrifying disorder. The duality is reflected in many creation myths that show the universe emerging out of chaos, returning to disorder and bursting forth again, regenerated and reordered.
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\section{Introduction}

The ubiquitous presence of helical architectures in nature, as well as their
diverse potential applications in materials science, for
optoelectronics \cite{PercecETAL02}, sensors \cite{YashimaMIFN09}, responsive
materials \cite{PijperF08}, and asymmetric catalysis \cite{GierBFS98}, has
motivated interest in design and synthesis.
Molecular self-assembly, in particular,
is a promising route to helicity \cite{Lehn02,YashimaMIFN09}. Self- or
directed-assembly of nanoparticles and colloidal building blocks has enormous
potential as a means of fabrication because of the scope for tuning
the interactions \cite{GlotzerS07,SacannaICP10}. A delicate balance between a
variety of weak forces often governs the assembled
structure \cite{MinAKGI08}. A thorough understanding of these forces holds the
key to rational design.

The present contribution reports on two complementary routes to helical
nanostructures, starting from anisotropic building blocks.
The first strategy employs directed assembly of achiral
colloidal building blocks \cite{ChakrabartiFW09,ZerroukiBPCB08}, where an
interplay between two length scales for the anisotropic interactions determines
the emergent chirality of the nanostructure. Such competing length scales are
present in DNA \cite{WatsonC53}, one characterising the distance between
consecutive nucleotides in the sugar-phosphate backbone, and the other
governing the stacking of the base pairs. Here the
competing length scales arise due to electrostatic and
magnetic dipolar interactions. While much progress has been made in obtaining emergent
chirality from achiral building blocks, biasing the superstructure to a
particular handedness \cite{HowsonETAL12}, or controlling the
pitch \cite{SrivastavaETAL10}, has proved more difficult. We address the latter
challenge using theory and simulation, and demonstrate that significant control
(around $30\%$) over the pitch length can be achieved by modulating the Debye screening
length of the electrostatic interactions over an experimentally accessible
range. The resulting tunable pitch length for helical superstructures
holds significant promise for
the design of a novel class of responsive materials.

The second design principle considered here involves clusters
of Janus particles. Several models have been used recently to study
the dynamics and aggregation properties of systems composed of Janus-type building
blocks \cite{janus_langmuir_2008,janus_softmatter_2012,janus_langmuir_2012,janus_langmuir_2013},
and the resulting phase diagrams exhibit a wide variety of potential target morphologies
for self-assembly, depending on the anisotropic
properties (shape and interactions). Interestingly, none of the models employed
so far was able to reproduce assembly into Bernal spirals (BC spirals or
tetrahelices) from anisotropic building blocks, although such systems have been designed and observed
experimentally \cite{janus_2011}. Here we report the design of a Janus building
block that prefers assembly into Bernal spirals, suitably guided by
experimentally relevant, anisotropic interaction potentials \cite{janus_langmuir_2008,janus_2011}.

Assembly into one-dimensional polytetrahedral clusters, locally organized as Bernal spirals, has also been achieved
for isotropic particles \cite{Campbell2005}, and reproduced computationally, by tuning the balance
between a long-range screened isotropic repulsion
and a short-range attraction term in the potential \cite{Mossa2004,Sciortino2005}.

\section{Methods}

We have used basin-hopping global optimisation \cite{Scheraga87,WalesD97,waless99} as implemented in the {\tt GMIN} program \cite{GMIN}
to predict global minima. Basin-hopping global optimisation involves perturbations of geometry
followed by energy minimisation.
The perturbations are designed to avoid any overlapping
particles. For the dipolar dumbbells, we run 50000 basin-hopping steps for each set of parameters presented in this paper.
Global minima for Janus clusters have been identified by running 10000 basin-hopping steps for at least 10 random starting
structures.

The energy landscapes for 20 and 24 Janus particles described in \S \ref{sec:Janus} were explored
using double-ended pathway searches between local minima with the discrete path sampling \cite{Wales02,Wales04,Wales06} approach,
as implemented in our {\tt OPTIM} \cite{optim} and {\tt PATHSAMPLE} \cite{pathsample} programs.
We have employed the doubly-nudged \cite{trygubenkow04} elastic band \cite{henkelmanj99,HenkelmanUJ00,HenkelmanJ00}
(DNEB) method \cite{trygubenko04} to locate transition state
candidates. The method has been adapted to avoid overlapping geometries for
Janus building blocks, by diagnosing overlap between the ellipsoids in each interpolated structure
and moving the overlapping ellipsoids by small random amounts until there is no overlap in the cluster.
Transition states were refined using gradient-only hybrid eigenvector-following \cite{MunroW99} from TS candidates
identified with the DNEB algorithm.
The most likely rearrangement mechanisms (pathways with the largest contribution to
the steady-state rate constant ignoring recrossings \cite{Wales06}) were obtained using Dijkstra analysis \cite{Dijkstra59}
of the resulting kinetic transition network.

To visualise the corresponding
multidimensional potential energy surfaces we
construct disconnectivity
graphs \cite{BeckerK97,WalesMW98} from the databases of minima and transition states explored during discrete path sampling.
Further details of all the geometry optimisation and visualisation techniques exploited
in this potential energy landscapes framework can be found in previous
reports and reviews \cite{Wales03,Wales06,Wales10a,Wales12}.

\section{Controllable Helix Pitch}

\subsection{A Decorated Rigid Body Model}
The colloidal building blocks considered here are charged dipolar asymmetric dumbbells, which
involve screened electrostatic as well as dipolar interactions. We modelled these particles
using multiple interaction sites that decorate a rigid framework. Each dumbbell involves two
lobes, each modelled by a spherically symmetric effective Yukawa pair potential \cite{RobbinsKG92,LowenK93},
where the inverse screening length $\kappa$ controls the range as well as the softness of the
screened electrostatic interactions, which can be tuned in experiment by modulating the salt
concentration of the medium \cite{LowenK93,YethirajB03}. Additionally, there is a magnetic point
dipole between the lobes, directed perpendicular to the axis.
The total energy of a system of $N$ such dumbbells in an external magnetic field $\boldsymbol{B}$ is given by
\begin{eqnarray}
U &=& \displaystyle \sum_{I=1}^{N-1} \displaystyle \sum_{J=I+1}^{N}
\displaystyle \sum_{i\in I}^{1,2} \displaystyle \sum_{j \in J}^{1,2}
\epsilon_{ij} \frac{ \exp [ - \kappa(r_{ij} - \sigma_{ij})]}{r_{ij}/\sigma_{ij}} \nonumber \\
&+& \sum_{I=1}^{N-1} \sum_{J=I+1}^{N} \frac{\mu_{D}^{2}}{r_{IJ}^{3}}
\Biggl[(\boldsymbol{\hat \mu}_{I} \cdot \boldsymbol{\hat \mu}_{J}) - 3 (\boldsymbol{\hat \mu}_{I} \cdot
{\bf \hat r}_{IJ}) (\boldsymbol{\hat \mu}_{J} \cdot \boldsymbol{\hat r}_{IJ}) \Biggr]
- \mu_{D}\displaystyle \sum_{I=1}^{N} \boldsymbol{\hat \mu}_{I} \cdot \boldsymbol{B}.
\label{eq:dmbl}
\end{eqnarray}
Here, ${\bf r}_{I}$ is the position vector for the magnetic point dipole on dumbbell
$I$, $\boldsymbol{\hat \mu}_{I}$ is the unit vector defining the direction of
the dipole moment, whose magnitude is $\mu_{D}$, ${\bf r}_{IJ} = {\bf r}_{I} -
{\bf r}_{J}$ is the separation vector between dipoles on dumbbells $I$ and $J$
with magnitude $r_{IJ}$, ${\bf \hat r}_{IJ} = {\bf r}_{IJ} / r_{IJ} $, and
$r_{ij}$ is the separation between the Yukawa sites $i$ and $j$. The units of
energy and length are chosen as the Yukawa parameters $\epsilon_{Y}$ and
$\sigma_{11}$, respectively. For the Yukawa interactions we set $\epsilon_{11}
= \epsilon_{22} = \epsilon_{12} = 0.1 \epsilon_{\rm Y}$ and $\sigma_{11} = 1$.
$\sigma_{22} < 1$ defines the asymmetry parameter $\alpha = \sigma_{11}/\sigma_{22}$;
$\sigma_{12}$ is chosen to be the arithmetic average $\sigma_{12} =
(\sigma_{11} + \sigma_{22})/2$. The direction of the external field
$\boldsymbol{B} = (0, 0, B)$ was held fixed along the $z$-axis of the
space-fixed frame as its strength, $B$, was varied. The magnetic dipole
$\mu_{D}$ is then in reduced units of $(4\pi\epsilon_{Y}\sigma_{11}^3/\mu_0)^{1/2}$ and the magnetic
field strength $B$ is in $[\epsilon_{Y}\mu_{0}/(4\pi\sigma_{11}^3)]^{1/2}$, where
$\mu_{0}$ is the permeability of free space. For the simulation results presented here,
we have used in reduced units $\mu_{D} = 0.1$, $B = 10.0$, $\sigma_{11} = 1.0$, $\sigma_{22} = 0.4$.
$\kappa$ is varied over an experimentally relevant range, as discussed in the next section.

\vspace{0.5cm}
\begin{figure}[h]
\centerline{\includegraphics[width=12cm]{psfragged/fig0.png}}
\caption{The potential energy of two interacting dumbbells with $\kappa
\sigma_{11} = 20$ as a function of the separation between dumbbells $I$ and $J$,
$r_{IJ}$.  The other parameters are as given in the text. In panel (a), the
contributions from the Yukawa and dipolar interactions are shown separately.
Panel (b) shows the sum of the two contributions. In the
figures, we have assumed that the direction of the dipole moment is parallel to
the external field. $\theta$ is the angle
between the axes of dumbbells $I$ and $J$; the global minimum energy for
two dumbbells is located at $\theta \sim 118^\circ$. The inset in
panel (a) shows a schematic representation of the dumbbell building block,
where the point dipole perpendicular to the axis of the dumbbell is not drawn
to scale. }
\label{fig:hlxpitch}
\end{figure}

\subsection{Results}

For small clusters, the global optimisation results reveal a helical superstructure as the ground
state for an optimal asymmetry when a sufficiently strong external field is applied. The dumbbells
tend to align perpendicular to the field, to facilitate alignment of the dipoles.
An optimal asymmetry is critical for helix formation, because competition with a second length
scale, which controls the steric interactions, is the basis of the emergent chirality \cite{ChakrabartiFW09,ZerroukiBPCB08}.
A single helical strand is observed without any predetermined chirality for clusters up to at least
$N = 20$ for the set of parameters investigated.

Figure \ref{fig:hlxpitch} shows that the pitch length can be controlled by modulating the range of
the screened electrostatic interactions, which can be tuned experimentally by changing the salt
concentration of the medium \cite{LowenETAL05}. It is evident that the pitch of the helix changes by
nearly $30\%$ upon varying $\kappa$ over a range accessible in experiments for both $N = 9$ and
$N = 20$. The slight difference between the two sizes arises due to additional (attractive) dipolar
interactions when more dumbbells are present in the cluster. As $\kappa$ is increased (screening
length is decreased), the Yukawa potential is shorter in range and the equilibrium distance between
two dumbbells decreases. The change in pitch is primarily attributed to this varying equilibrium
separation, the change in twist angle being nominal. The limiting cases are insightful. For large
$\kappa$, the Yukawa potential approaches a hard-sphere interaction, and for $\kappa \to 0$, it
approaches the long-range Coulomb potential. Figure \ref{fig:hlxpitch2} shows that the range of the
screened electrostatic interactions directly affects the helix pitch length, but helix integrity is
preserved. Hence the design proposed here offers a route to helical nanostructures with controllable
pitch length.

As for the parameters, a reasonable estimate in physically relevant units can be obtained by setting
$\epsilon_{\rm Y} = 4.1 \times 10^{-21} \rm J$ (of the order of $k_{B}T$) and $\sigma_{11} = 10^{-6} \rm m$.
In the above analysis we have neglected the screening effect on the dipolar interactions in
the medium. This assumption is valid when magnetic dipoles are involved \cite{vanBlaaderenETAL13,ZerroukiBPCB08}.
In the absence of the screening effect for the magnetic interactions, the screened electrostatic and
magnetic interactions can be manipulated independently \cite{SmoukovGMV09}on The values in reduced units
used here correspond to a magnetic dipole moment $\mu_{D} \sim 2 \times 10^{-17}\,{\rm A\,m^{2}}$ and
a magnetic field strength $B  \sim 2 \times 10^{-4}\,{\rm T}$, well within the
experimentally accessible regime.

If we consider an aqueous medium for a monovalent electrolyte,
where the ionic strength $I$ is equal to the molar concentration, the Bjerumm length
$\lambda_{\rm B}$ of water is $0.7\,{\rm nm}$ at $298\,{\rm K}$, equivalent to a colloid charge
of $Z \sim 130$ for the larger lobe of the dumbbell when $\kappa\sigma_{11} = 20$ using the relationship
$\epsilon_{11}/(k_{\rm B}T) = Z^{2}(\lambda_{\rm B}/\sigma_{11})/(1+\kappa\sigma/2)^{2}$ \cite{IvlevLMR12}.
For the parameter range considered here,
the variation of the Debye screening length $\kappa^{-1}$ is between $20\,{\rm nm}$ and $80\,{\rm nm}$.
With concentrations as low as $\sim 1\,\mu M$ achievable in an experimental setup \cite{YethirajB03},
this range is well within the regime accessible in experiments, since the following relationship
holds: $\kappa^{-1} = 0.304\,I^{-1/2}$, where $\kappa^{-1}$ is in nanometres and $I$ is in moles per
litre \cite{Israelachvili11}.

\vspace{0.5cm}
\begin{figure}[h]
\centerline{\includegraphics[width=12cm]{psfragged/fig1.png}}
\caption{Helix length per particle as a function of the inverse screening length
for the predicted ground state structures. Results are shown for $N = 9$ and $N=20$.
Insets: the ($N=20$) helix configurations for (left) $\kappa\sigma_{11} = 14.3$ and
(right) $\kappa\sigma_{11} = 50.0$. The dipoles are not shown for clarity of presentation.}
\label{fig:hlxpitch2}
\end{figure}

\section{Clusters of Janus Particles}
\label{sec:Janus}

\subsection{Computational Model}

We have previously shown that very different interparticle potentials can
produce rather
similar preferred arrangements during aggregation \cite{fejer_self-assembly_2011},
as long as the overall pair potentials are sufficiently alike.
Current designs of spherical mesoscopic Janus building blocks generally involve a charged
hydrophilic hemisphere combined with a hydrophobic hemisphere
in an aqueous environment. Changing the ionic strength of the solution effectively changes the screening of the electrostatic repulsion,
and worm-like structures arise when the charges are well screened,
corresponding to short-ranged repulsive terms.
Potentials that have been used for Janus particle modelling therefore usually include three types of interaction:
hard sphere repulsion to prevent
overlap, hydrophobic interactions, and screened Coulombic repulsion \cite{janus_langmuir_2008}.
Most potentials employed to date are discontinuous, containing quasi-square well functions and
hard sphere interactions, which are not suitable for energy landscape studies
based on geometry optimisation. Recently, a
potential has been developed for soft Janus particles \cite{janus_softmatter_2012},
but it involves considerably longer-range
interactions than we consider in the present study.

Our design for a Janus building block tries to capture the net behaviour of
particles with strongly anisotropic short-range interactions in solution, aggregating around the
hydrophobic hemisphere. We use continuous and differentiable functional forms, and aim to keep the potential as simple as possible,
to extract the minimal conditions on the interparticle forces that correspond to particular target morphologies.
The Paramonov-Yaliraki (PY) potential \cite{paramonov05} has proved its
versatility for modelling a large number of anisotropic interactions \cite{fejer_self-assembly_2011,FejerCW10,ChakrabartiFW09},
and here we have used this
representation to create Janus-type particles by modifying just two interaction parameters in the pairwise energy.
Each Janus building block is composed of two rigidly linked spheres (A and B) represented by PY ellipsoids \cite{paramonov05,olesen_2013}
having the same orientation and shifted along the $z$ axis by 0.1 distance units from the origin, in opposite directions.
The building blocks interact within a rigid-body framework
using the angle-axis description for the orientational degrees of freedom \cite{Wales05,ChakrabartiW09}.
To allow for shorter-range interactions than the usual Lennard-Jones form,
we have increased the diameter of the spheres threefold, while keeping the range parameter $\sigma_0$ fixed at unity.
One sphere (ellipsoid A) is purely repulsive, while the other has a
higher interaction strength along the $z$ direction (attractive
semiaxis length $a_{23}=1.56$). The total interaction energy between building blocks is
\begin{align}
U_{12}=4\epsilon_{0}\sum_{i=1}^{2}\sum_{j=1}^{2}\left[\epsilon_{\rm rep,i}\epsilon_{\rm rep,j}\left(\frac{\sigma_{0}}
{r_{ij}-r_{ij}F_{1ij}^{-1/2}+\sigma_{0}}\right)^{12}\right.-\nonumber\\
\left.-\epsilon_{\rm attr,i}\epsilon_{\rm attr,j}\left(\frac{\sigma_{0}}
{r_{ij}-r_{ij}F_{2ij}^{-1/2}+\sigma_{0}}\right)^{6}\right],
\label{eq:paramonov}
\end{align}
where $F_{1ij}$ and $F_{2ij}$ are the
\lq repulsive' and \lq attractive' elliptic contact functions \cite{paramonov05},
calculated between ellipsoids $i$ and $j$, $\epsilon_{\rm rep}=1$
for both ellipsoids in the building block, and $\epsilon_{\rm attr,A}=0$, and $\epsilon_{\rm attr,B}=1$. The repulsive
semiaxes for both ellipsoids are $a_{11}=a_{12}=a_{13}=1.5$. The attractive semiaxes are not used for ellipsoid A (being
purely repulsive in character), while for ellipsoid B they are $b_{21}=b_{22}=1.5$, and $b_{23}=1.56$.
These semiaxes are employed for constructing the shape matrices, which define the repulsive and attractive
elliptic contact functions.

\subsection{Results}

\begin{figure}[ht]
            \centerline{\includegraphics[width=15cm]{psfragged/fig2.png}}
	\caption{(a) Schematic view and space-filling representation of the
generic Janus-type building block. Dashed circle and yellow: ellipsoid A (purely repulsive),
continuous circle and red: ellipsoid B (more attractive along its $z$ axis). $\Delta r_0=0.2$,
$r_{rep,A}=r_{rep,B}=1.5$.
(b) Potential energy surface of two parallel building blocks
confined in the $xz$ plane, with their principal axes aligned with the axes of that plane.
(c) Same as (b), but with an antiparallel alignment of the
$z$ axes. Note that the energy range represented in (b) is ten times smaller than that in (c),
and overlapping configurations with an interaction
energy outside this range are coloured uniformly with the colour at the top of the range (red).}
\label{fig:surfaces}
\end{figure}

In this section we introduce a building block composed of two overlapping ellipsoids that strongly favours assembly
into Bernal spirals (tetrahelices) \cite{boerdijk52,tubularpacking73}.
Our system behaves similarly to the experimental realisations of Janus particles
\cite{janus_2011} presented by Chen {\it et al.}, but the underlying energy landscape is likely rather different. In ref.~\cite{janus_2011}
the authors demonstrate that the tetrahelix structures observed at high salt concentrations probably arise due to kinetic
effects, and other tubular structures such as the 3(0,1,1) helix \cite{tubularpacking73} are not observed because the basic unit of the
tetrahelix (capped trigonal bipyramid, $N=7$) forms first and it is sufficiently long-lived to aggregate into
long chains. In contrast, our model ensures that tetrahelix structures are energetically favourable,
and the interaction profile between building blocks makes the formation of alternative low-energy tubular packings impossible.
Hence we propose a new design, which we predict will guide assembly towards well-defined small
helical structures very efficiently.

Figure \ref{fig:surfaces}a illustrates our Janus building block. Figures
\ref{fig:surfaces}b and c provide a two-dimensional
representation of the potential energy surfaces resulting from moving two building blocks in the $xz$ plane,
with their principal axes aligned,
and with the $z$ axes in parallel and antiparallel orientations, respectively. The potential is
highly attractive at the pole of ellipsoid B furthest away from ellipsoid A. The interaction
range is rather short, and the potential becomes isotropic and decays to zero rapidly as the distance between particles increases.
The displacement by 0.1 distance units of the two ellipsoids is analogous to the experimental method of
obtaining micrometre-sized Janus particles by coating silica spheres with gold \cite{Chen2011,janus_2011}, since in that case the gold
coating is thickest at the pole, and gradually decreases towards the equator. The
hydrophobic interaction itself is determined by the monomolecular layer of alkanethiol applied on the gold coating, and is therefore
constant on the surface of the patch. However, the net van der Waals interaction experienced by the particles is strongest around
the pole due to the greater thickness of the gold coating. The main difference between our model and the experimental setup is that
the deviation from the spherical shape at the poles is about 1\% for the experimental system, while in our case it is about 7\%.
Our potential is also softer than the usual hard sphere-square well representations for experimental colloidal Janus particles.
Since we did not modify the original PY potential to incorporate Coulombic repulsion,
our repulsive ellipsoid A has a short range, namely $r^{-12}$.
We find that this repulsion is sufficient to disfavour close contacts between two repulsive ellipsoids, and gives rise to a force that
tends to align two building blocks in an antiparallel fashion. The potential is continuous for every non-overlapping configuration. An
additional benefit of using the same potential to describe both \lq hemispheres' of the building blocks is that no explicit
smoothing is required, which would otherwise be necessary to make the interaction profile and its derivative continuous
around the hydrophobic-hydrophilic interface.
There are discontinuities and unphysical minima in the potential corresponding to highly overlapping configurations,
but moves that permit such overlaps are
diagnosed and discarded in our global optimisation and pathway search algorithms. Overlaps between ellipsoidal particles are
easily detected from
the same elliptic contact function that arises in the energy evaluation.
Such discontinuities and internal wells for overlapping configurations are common for anisotropic potentials \cite{paramonov05,gayberne}.

\begin{figure}[tp]
            \centerline{\includegraphics[width=1.0\textwidth]{psfragged/fig3.png}}
\caption{Energy per particle for the predicted global minima in
clusters containing between 4 and 26 Janus particles. The \lq sawtooth' pattern showing a
preference for even number clusters is due to the strongly bound dimer.
Inset: lowest energy structures for small clusters
($N=4$ to 8). 4: tetrahedral, 5: trigonal bipyramidal, 6: capped trigonal bipyramidal (CTBP),
7: pentagonal bipyramid, 8: Bernal spiral.}
\label{fig:globalminima}
\end{figure}

Our model Janus building blocks strongly prefer to interact {\it via} their attractive poles.
Since the well depth is not uniform
over the attractive half of the particle, dimerisation is favourable. An additional particle
orients its attractive pole towards the dimer, but the short range and strong directionality of the interaction makes it impossible to
form a strongly bound cluster.
The most favourable geometry for the trimer therefore lacks a $C_{3}$ symmetry axis, and the geometry is
slightly distorted (intercentre distances between the second ellipsoids of each building block are 3.02, 3.08 and 3.08, respectively).
However, when the number of particles in the cluster is even, a complete set of dimers is possible.
This pattern results in hierarchical assembly, where
the dimers themselves behave as larger building blocks,
stacking along their attractive ellipsoids and rotated by 90 degrees.
When highly symmetric clusters are possible, the strong dimer interactions
can be disrupted if the extra stabilisation from the additional contacts can compete with the dimerisation energy.
This situation arises for $N=4$ and 5,
with global minima corresponding to tetrahedral and trigonal bipyramidal structures, respectively.
Increasing the cluster size further destabilises
high symmetry configurations, and assemblies of dimers tend to be preferred. For example,
the global minimum for $N=6$ is a capped trigonal bipyramid (CTBP), not an octahedron, and starting from $N=8$,
the predicted global minima for every structure with an even number of particles are tetrahelices up to $N=20$.
We emphasise that
these are not perfect tetrahelix structures, since the tetrahedral units are themselves somewhat distorted,
the largest difference between the
edges being around 7\%. The strong preference for dimerisation gives rise to a characteristic
\lq sawtooth'-pattern in the energy per particle
{\it versus} cluster size (Figure \ref{fig:globalminima}). The global minima for $N>20$ are ring-like
structures. There is recent experimental evidence for Janus particles preferring assembly into clusters with even numbers
in two dimensions \cite{Iwashita2013}, and computational studies on a different Janus building block also show such a
preference \cite{Preisler2013}, giving rise to similar \lq sawtooth' patterns.

Since there are essentially two types of interactions between the Janus building blocks in a tetrahelix,
namely a stronger and a weaker attraction, assembly of such systems is intrinsically hierarchical through
(i) dimerisation and (ii) association of dimers. Building blocks at
either end of a finite strand are more weakly bound, so in a bulk system strand growth is preferred if
there are free dimers available in solution. However,
increasing the number of particles also allows for certain ring-like structures to arise, built up from tetrahedral units.
For example, the predicted global
minimum for 24 particles is \lq doughnut'-shaped, corresponding to the first cyclic structure with high symmetry ($D_{6d}$).
Interestingly, such structures have not yet been observed in experiment \cite{janus_2011}, although
the main repeating unit in a tetrahelix is the
CTBP structure \cite{janus_2011}, as in the cyclic global minimum predicted for 24 building blocks.

We have explored the energy landscape more extensively for clusters composed of 20 and 24 particles,
using discrete path sampling \cite{Wales02,Wales04,Wales06} to grow databases of local minima
and the transition states that connect them. The disconnectivity graphs constructed for the
two cluster sizes are shown in Figures \ref{fig:disconn20} and \ref{fig:disconn24}, respectively.
We have used the same energy range, and
positioned the tetrahelical minimum in the same part of the graph, so that the two landscapes can be compared visually.
Enantiomers are lumped together in these graphs.

\begin{figure}[ht]
            \centerline{\includegraphics[width=1.0\textwidth]{psfragged/fig4.png}}
        \caption{Disconnectivity graph for $N = 20$ Janus building blocks. The global minimum is a Bernal spiral ({\bf A}), which is very flexible.
In this graph, more
than 30 minima around the global minimum
exhibit bent structures,
which interconvert {\it via} \lq hinge' motions.
The lowest energy kinetic trap ({\bf B}) corresponds
to a symmetric cyclic structure, while the second-lowest ({\bf C}) is a dimer of a low-energy minimum for $N=10$.}
        \label{fig:disconn20}
\end{figure}
For $N=20$, we find that the tetrahelical global minimum is very flexible,
with single transition state rearrangements resulting in bent
structures that correspond to similar energies. The mechanism is a simple bending motion around a pair of particles
strongly bound to each other in
the helical structure, with the dimer acting as a hinge. Only strongly bound dimers act as hinges,
with their attractive poles almost antiparallel.
Kinetically this is a favourable rearrangement, with relatively low barriers below $0.25\,\epsilon_0$.
Such \lq hinge'-rearrangements are characteristic low-energy transitions between worm-like structures,
and are preferred due to the fact that the binding pattern of
dimers does not change, i.e.~no dimeric binding configuration is disturbed.
The identified \lq hinge'-rearrangements resemble those found for sodium chloride clusters \cite{DoyeW99},
where such rearrangements have relatively high barriers.

\lq Hinge' rearrangement mechanisms are preferred during chirality inversion as well.
Figure \ref{fig:inversion24} and Supplementary Movie 2
illustrate one of the fastest pathways between a left-handed and a right-handed $N=24$ helix. All such pathways involve exclusively
\lq hinge'-motions and a minimum of five transition
states. Such sequential rearrangements have been observed experimentally for smaller clusters \cite{janus_2011},
and we see exactly the same type
of cooperative pathways, resulting in propagation of the change in handedness along the chain.
\begin{figure}[ht]
            \centerline{\includegraphics[width=1.0\textwidth]{psfragged/fig5.png}}
        \caption{Predicted fastest pathway for inversion of a 24-particle tetrahelix structure,
consisting exclusively of \lq hinge' rearrangements. The fourth minimum in the path is in fact
a dimer composed of a left-handed and a right-handed $N=12$ helix.}
         \label{fig:inversion24}
\end{figure}

The disconnectivity graph for $N=20$ contains many kinetic traps, the lowest of which is a ring structure with a symmetry plane ({\bf B}).
Other low-energy minima that appear as traps are again aggregates of dimers,
and contain two or more CTBP units. The structure {\bf C} depicted in Figure \ref{fig:disconn20}
is in fact a dimer of the second-lowest potential energy minimum predicted for the $N=10$ cluster.

\begin{figure}[ht]
            \centerline{\includegraphics[width=1.0\textwidth]{psfragged/fig6.png}}
        \caption{Fastest pathway between the tetrahelix global minimum and a low-energy closed ring structure.
The rearrangements with energy barriers of about $0.25\,\epsilon_0$ are all \lq hinge'-motions.
Structures for selected minima and the highest
energy transition state are also shown.}
        \label{fig:pathway20}
\end{figure}
The fastest pathway between the helical global minimum and the ring structure
predicted to act as a kinetic trap
also proceeds through low-energy \lq hinge' mechanisms
(Figure \ref{fig:pathway20}, see also Supplementary Movie 1) up to a point, and the high energy of
the fifth transition state and the fifth
minimum along the pathway is due to the torsional strain introduced when the attractive interactions
between two adjacent dimer units are lost
(rotation of a dimer around the intercentre vector defined by two loosely bound neighbour particles).
The final rearrangement in the overall pathway is again a \lq hinge' mechanism.

\begin{figure}[ht]
            \centerline{\includegraphics[width=1.0\textwidth]{psfragged/fig7.png}}
        \caption{Disconnectivity graph for $N = 24$ Janus building blocks.
The global minimum is a ring structure with $D_{6d}$ symmetry.}
        \label{fig:disconn24}
\end{figure}
\begin{figure}[ht]
            \centerline{\includegraphics[width=1.0\textwidth]{psfragged/fig8.png}}
        \caption{Fastest pathway between the \lq doughnut'-shaped global minimum of $D_{6d}$ symmetry and the tetrahelix structure.
The rearrangements
involved with energy barriers of about $0.25\,\epsilon_0$ all correspond to \lq hinge' mechanisms.
Structures are shown for selected minima. The
inset shows a part of the cluster in the high energy transition state involving change in the dimerisation pattern.}
        \label{fig:pathway24}
\end{figure}
Helical structures are much higher in energy for $N=24$ clusters
than the \lq doughnut'-shaped global minimum. Although they exhibit
the same flexibility as for $N=20$, the energetic separation from the rest of the landscape is not as pronounced,
and these structures
can easily undergo ring closures. However, the highly symmetric global minimum cannot be reached through
simple low-energy \lq hinge' rearrangements. At
least one step involving a change in dimerisation pattern has to occur at one end of the helix, during which the particles in
two adjacent dimers rotate cooperatively to change the strong bonding into a weak interaction and {\it vice versa}.
Such particle rotations result in
an energy barrier of about 1\,$\epsilon_0$ at the end of the chain, which would be much higher if they
occurred within the chain. The fastest overall pathway between the helical structure and the global minimum
is shown in Figure \ref{fig:pathway24} and Supplementary Movie 3.

It would be interesting to investigate how the helical clusters of Janus building blocks designed in ref.~\cite{janus_2011} behave
in dilute solutions, where chain growth is less likely.
Although chirality inversion has been observed for such helices, all other reported transformations involve
chain growth. The \lq hinge' mechanisms observed experimentally hint at other possible rearrangements for longer helices. In our
model system, the lowest energy transformations involve only \lq hinge' motions. By increasing the temperature,
barriers could be overcome for the less favoured rearrangements (similar to those described above),
and in dilute solutions highly symmetric rings might form.

It remains to be seen how our model building blocks behave in a bulk phase. Based on the global optimisation data
and on the energy landscape analysis for $N=20$ and $24$, a kinetically controlled seeded growth of helices is likely
above 20 particles, by sequential addition of dimers or CTBP units. Assembly of short helices containing even numbers of particles
will be thermodynamically preferred.

\section{Conclusions}

We have presented two contrasting
theoretical designs for self-assembling helical nanostructures. First
we described the assembly of charged asymmetric dipolar dumbbells into a helix subject to an
external magnetic field. Here, helix formation is due to the competition between screened
electrostatic repulsion and magnetic dipolar interactions. We demonstrate that significant control
over the helical pitch length (around $30\%$) can be achieved by tuning the balance between
these two interactions. This tuning is achieved by varying the range of the screened
electrostatic interactions, which can be realised experimentally by modulating the salt
concentration of the medium.

We then analysed a model Janus building block that dimerises, where the dimers self-assemble into Bernal spirals, simply by allowing for
a strong short-range interaction close to the attractive pole of the particle. Large-scale rearrangement mechanisms of such spirals involve sequential \lq hinge' motions.

In agreement with previous work, we find that the formation of complex mesoscopic structures is primarily driven by the anisotropy of building block shape and
interactions \cite{FejerCW10,fejer_self-assembly_2011}. Our model of rigidly linked ellipsoids can capture a wide range of anisotropy, and the
self-assembling behaviour for certain sizes is a direct consequence of the building block properties. The model can easily be parameterised to allow
for larger overlap between building blocks, in order to model \lq softer' Janus particles.

The two models presented here provide two very different approaches to self-assembly
of helical structures from anisotropic building blocks on the colloidal length scale. In
both models, helicity is the direct consequence of the shape and interaction anisotropies of
the building blocks. The overall interaction strength between two particles depends on their
relative orientation, and on the balance between the repulsive and attractive forces, which
can be tuned experimentally, for example by varying the ionic strength of the solution. The
dumbbell model illustrates that varying such experimental conditions makes it possible to
directly control the helical pitch, while the Janus model provides an example of a
building-block design that facilitates hierarchical self-assembly into helical structures.
Both models are relatively simple, and we believe that they are
should be realisable experimentally.

\section{Acknowledgements}
SNF is a John von Neumann Fellow supported by the European Union and
the State of Hungary, co-financed by the European Social Fund in the framework of
T\'AMOP-4.2.4.A/ 2-11/1-2012-0001 \lq National Excellence Program'.
DJW gratefully acknowledges support from the EPSRC and the ERC.

\section{Supplementary Movie 1 Legend}

This movie shows the fastest rearrangement mechanism between a 20 particle Bernal spiral and a symmetrical cyclic structure,
which is a kinetic trap on the energy landscape for 20 particles. The first four rearrangements along the pathway are low-energy
\lq hinge' motions.

\section{Supplementary Movie 2 Legend}

This movie shows the fastest pathway for inverting the chirality of a left-handed $N=24$ helical structure. The rearrangement
proceeds exclusively through low-energy \lq hinge' motions.

\section{Supplementary Movie 3 Legend}

This movie shows the transformation of a 24-particle spiral into a highly symmetric \lq donut'-structure, which is the global
minimum for this number of particles. The second rearrangement along the pathway has a high energy barrier, and corresponds to a
change in dimerization pattern between the four particles at the lower end of the helix. All other motions are low-energy
\lq hinge' rearrangements.

\end{document}

redpajama_set_name: RedPajamaArXiv


text:
Robert de Castella AO MBE
Caroline Buchanan is a cyclist and Olympian who was awarded a Scholarship within the 2011 Sport Australia Hall of Fame Scholarship and Mentoring Program, she was paired with Robert de Castella AO MBE as her Mentor.
Caroline was born in Canberra in 1990 and specialises in Mountain Bike and BMX cycling. She made her mark in 2012 when she won the BMX World Cup Series and competed at the London Olympic Games.
In 2013, she was named People's Choice Australian Cyclist of the Year, AIS Australian Athlete of the Year and Australian Cyclist of the Year after winning the national championships and the world championships in BMX. She followed this with gold in 4 Cross at the Mountain Bike World Championships.
Caroline would win another 4 BMX world championships and many more World Cup races in BMX. In 2014, she was named BMX Rider of the Year at the Inter Bike Awards and took the overall title at the BMX World Cup Series, before returning to Australia in 2015 to claim one of her four national titles in BMX. She would also win 4 Australian titles in Mountain Biking throughout her career and was named BMX Australian Cyclist of the Year five times.
Training and racing continued in 2016, and so did the victories. Caroline was the World Champion in the Time Trial as well as the World Champion in 4 Cross again. She was the Australian Mountain Bike Cyclist of the Year, an Olympian for the second time, and even won an award for 'sickest moves' on a bike.
Caroline then became Mountain Bike World Series Pumptrack Champion at Crankworx in 2017, the same year she won another 4 Cross world title and was a finalist in the AIS Personality of the Year award.
2011: Sport Australia Hall of Fame Scholarship Holder.
2012: London Olympic Games – BMX Time Trial Winner.
2012: London Olympic Games – BMX Racing Finalist.
2012: BMX World Cup Series – Winner.
2012: Unbeaten by The Clock in 6 Consecutive UCI Time Trials.
2013: Mountain Bike World Champion – 4 Cross.
2013: UCI BMX World Champion.
2013: AIS Australian Athlete of the Year.
2013: Australian Cyclist of the Year.
2013: Australian National BMX Champion.
2013: People's Choice Australian Cyclist of the Year.
2014: BMX World Cup Series Champion.
2014: BMX World Championships – Silver, time trial.
2014: BMX Rider of the Year – Inter Bike Awards.
2014: BMX World Cup, Berlin & Manchester – Winner.
2016: BMX Australian National Champion.
2016: Nickelodeon Kids Choice Awards winner – "Sickest Moves".
2016: Australian BMX Cyclist of the Year.
2016: UCI MTB World Champion – 4 Cross.
2016: UCI MTB World Champion – Time Trial.
2016: UCI MTB World Championships – Silver.
2016: BMX World Cup, Manchester – Winner.
2016: BMX World Cup, Argentina – Winner.
2016: Australian Mountain Bike Cyclist of the Year.
2016: LinkedIn Power Profile Award – Top 7 Viewed Sports Industry Profiles.
2017: UCI Mountain Bike World Champion – 4 Cross.
2017: Australian Institute of Sport (AIS) Personality of the Year Finalist.
2017: Overall Crankworx Mountain Bike World Series Pumptrack Champion.
2017: UCI BMX World Championships – Silver.
Website | Instagram | Twitter | Facebook | LinkedIn


NEW DELHI, Jan 20: Sugar prices settled steady at the wholesale market in the national capital today on adequate position of stocks against current demand.
Marketmen said besides sporadic buying activities, comfortable position of stocks mainly kept sugar prices unmoved.
Sugar retail markets – Rs 34.00-37.00 per kg.
Sugar ready: M-30 Rs 3,330-3,560, S-30 Rs 3,320-3,550.
Mill delivery: M-30 Rs 3,150-3,320, S-30 Rs 3,140-3,310.


text:
Q: Database value being truncated at special character I've exported my database from MySQL Workbench locally and I've just tried to run it on my live server and everything inserts successfully.
Some of the fields are being truncated whenever there is a special character, so 'This is a £ test' becomes 'This is a '.
I'm assuming this is an encoding issue however both the database on live and local have UTF8_unicode_CI as the collation.

A: Symptom of Truncation:
When SELECTing the text, it is not all there; in particular it is truncated before the first non-english character.
How you got in the mess:

*

*The client's bytes to be INSERTed into the table were encoded as latin1, and

*The charset for the connection was utf8 (eg, via SET NAMES utf8), and

*The table column was declared CHARACTER SET utf8
How to fix the text and the table:

*

*The text is not recoverable.

*The column is already utf8, so no change needed there.

How to fix the code:

*

*If you continue to have latin1-encoded text, then change the charset for the connection to latin1.

redpajama_set_name: RedPajamaStackExchange


QALAYE NIAZI, Afghanistan (Reuters) - U.S. warplanes killed over 100 people in a raid on a village in eastern Afghanistan, residents said Monday, as British troops arrived in the capital to take up peacekeeping duties. At least one fighter jet, a B-52 bomber and two helicopters Sunday morning swooped on the village of Qalaye Niazi, about 2.5 miles north of the city of Gardez, capital of eastern Paktia province, villager Janat Gul told Reuters.
There are also tensions within the administration, headed by Hamid Karzai, over the role of foreign forces on Afghan soil. But an advance column of about 50 British troops drove into Kabul Monday to take up peacekeeping duties, the vanguard of an international security force that was agreed with the new government. The new administration and Britain have initialed an agreement on deployment of the force, authorized by the U.N. Security Council to fill the security vacuum in Afghanistan after the collapse of the Taliban, a British official said on Monday. The force is eventually expected to number 3,000.
Janat Gul said 24 members of his family were killed in the pre-dawn U.S. bombing raid on Qalaye Niazi, and described himself as the sole survivor. ``People are very upset about what is going on here,'' he said.
Paktia province borders Pakistan and is southwest of the jagged canyons of Tora Bora -- one of the last stands of al Qaeda fighters. It was heavily bombed in early December when bin Laden was believed to be hiding there. At least 12 houses in Qalaye Niazi were razed. Amid the destruction, a Reuters Television cameraman saw scraps of flesh, pools of blood and clumps of what appeared to be human hair. Huge craters had been blasted out by the strike. A member of the local tribal shura, or council, said they had invited U.S. forces to the village to see the damage and to find out what had happened.


Comm100 Live Chat Android App enables you to run Comm100 Live Chat Visitor Monitor on your Android devices, thus you can take chats and engage your clients while on the go.
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If your live chat on private deployment, you need to download the Andriod app from your own account with dedicated download link. In case you have any problem with that, please Chat with us now.
You can install the app in Google Play Store by searching for Comm100 Live Chat or install online at www.comm100.com/platform/livechat/agent-experience/androidchat/.
Log into the app and set for how long you will stay logged in when the Android App runs in background.
Log into the Android App and then click Menu >> Preference >> Stay Logged in for to select a proper time period option according to your needs.
Now you're set and you can monitor or chat with your website visitors while you're on the go.


Please follow PennDOT on Twitter at 511PANortheast and Like us on facebook at Pennsylvania Department of Transportation (PennDOT).
Please note: Central Scranton Expressway will be closed starting on Wednesday, April 18, 2018 from 8 p.m. to Monday, morning April 23 at 6 a.m. Please note that the car detour will be Moosic Street and the truck detour will be Davis Street for the start of the removal of the old Harris Avenue Bridge over the expressway.
Starting Wednesday, April 18 through the end of the month PennDOT will be conducting a pothole blitz across District 4.
There will traffic issues on SR 3019 (Spring Street in Moosic and SR3024 (Main Street) Moosic on Saturday April 21, 2018 for the Moosic Little League Parade from 8:30 a.m. to 9:30 a.m.
The Department of Transportation will have a public meeting on Thursday, April 19, 2018 at the Clifton Township Building 361 State Route 435, Clifton Township, PA for the 4th Street over Lehigh River County owned Bridge Replacement Project, Clifton Township, Lackawanna County starting at 6 p.m. The purpose of the meeting is to provide the project team an opportunity to explain the project and answer question on an informal basis. Preliminary design plans will be available for review.
SR 247-Church, Grassy Island-Jessup/Blakely-Moving-Sweeping-16-Apr-18-20-Apr-18-7 a.m. to 3 p.m.
SR 1025-Wemberly Road-Scott Twp.-Single-Pipe Replacement-Inlet/Endwall Repair-16-Apr-18-20-Apr-18-7 a.m. to 3 p.m.
SR 4002-Baylor's Lake-Benton Twp.-Single-Pipe Trench patch-16-Apr-18-20-Apr-18-7 a.m. to 3 p.m.


Please complete this survey if you are more than 59 years old and live in Wilson. For each question, please give your best answer.
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This survey may be anonymous. Fill in the information below only if you want to learn more about our programs or apply for services to older adults. If you prefer not to submit your name and contact information, you may also call the Senior Center at (252) 206-4059.


Towards the end of 2016, Wolves of Midgard emerged in the news as the new ARPG in town. Many of us were excited about what the game could be bringing to the table.
Wolves of Midgard is a breath of fresh air. The game started it's development life under developers Games Farm with publishers Kalypso from Russia.
The game revolves around the Viking mythology and from early game play footage and trailers, we were not disappointed. The ARPG combines hack and slash elements with history that looks really fun. As a mighty Viking, you'll take on hordes of undead and other beasts of Ragnarok.
Graphics and presentation looks really polished too. What intrigues me is possibility of spell crafting for the various different classes. There will be familiar progressions as seen in games like Diablo III. Therefore, expect to see talent trees, multiple difficulty tiers as well as legendary weapons.
Now in my opinion, the issue I have with Wolves of Midgard starts with the game's price. You can purchase the game on Steam for $39.99 as a pre-order currently. But what I really want to know is what does it do differently from free to play games like Path of Exile to warrant that price?
Path of Exile is seen as the spiritual successor to Diablo II and it's offered gamers so much joy over the past few years. Everything from gameplay to the combat is top notch, and the best part is it's free to play.
So it will be interesting to see if Wolves of Midgard can live up to their asking price on release. While I remain skeptical, I hope the game does do well. We could certainly benefit from more Action RPG games on the market! Are you looking forward to release? Let us know!


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Illustration : Jeanette Besmer, Amaina Bouajila, Virgine Bergeret, Paul Burckel, Tanguy Chesne, Guillaume Deloizon, Amélie Dufour, Marion Duval, Fräneck, Anne Laval, Céline Le Gouail, Nikol, Amélie Patin, Chloé Perarnau, Aurore Petit, Manu Poydenot, Fabien de Souza, Marie Weber.
Impression : couverture sérigraphiée, 1couleur, riso, 2 couleurs.
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Print : silkscreen printed cover 1 color, riso , two colors.
Format : A4, 18 illustrations recto, carton folder.
Shipping Europe and world : max 4 weeks.


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Insurance and certification
Road freight transport
ADR – dangerous goods transport
Chilled & frozen goods transport
Car & Truck wash
For shareholders
Departments and contact persons
Petra Růžičková to lead a new VCHD Cargo branch
VCHD / New-posts / Petra Růžičková to lead a new VCHD Cargo branch
Author klient
The Czech transport company VCHD Cargo has founded a new branch – VCHD Cargo České Budějovice – with the experienced logistics specialist Petra Růžičková at the helm. In her new position, she will be responsible for the company's activities in South Bohemia and beyond.
VCHD Cargo České Budějovice will be strategically focused on customers in the south of our country including many industrial and retail companies as well as customers in the cross-border regions of Austria and Germany. Ing. Petr Kozel, Chairman of the VCHD Cargo Board, explains: "By founding the new branch, we are strengthening our presence in a strategic part of the Czech Republic," adding: "What we found in Petra Růžičková is an experienced branch manager with logistics know-how and detailed understanding of the region. Having the town of České Budějovice as our base also allows us to serve our current and potential customers in Austria and Bavaria. Our travel time to these customers is now one to two hours and we believe that once the pandemic is over personal meetings will once again be an integral part of relationship management."
Born in České Budějovice, Petra Růžičková has worked in logistics for more than 16 years. She graduate from a business high school and earned an MBA in transport, communications and logistics. She has worked in logistics since 2004 when she got a job in the logistics department of Robert Bosch s.r.o. Between 2007 and 2010, she worked in DACHSER EST as sales manager and deputy head of branch. She has since progressed in her career serving as a manager in the transport company Unitrans Bohemia where she was responsible for strategic management and a team of nearly 100 employees. For the past eight years, she worked in DACHSER Czech Republic as a DIY segment solutions manager, shipping manager and branch manager.
Petra Růžičková speaks English and German and can communicate in Russia. In her free time, she likes to travel and enjoys sports.
15. 12. 2021VCHD Cargo has invested CZK 70 million in new vehicles. A second batch, with nearly the same price mark, has not been delivered yet
14. 12. 2021VCHD Cargo's Millionaires' Club hits the 2.5m km mark for the first time
10. 12. 2021Demand exceeding offer and current market situation
3. 12. 2021We are betting on the swap bodies
6. 8. 2021VCHD Cargo acquired the German forwarder Völker Logistik
Železárenská 315, 272 01 Kladno
info@vchd.cz
The company was founded in 1997 in Havlíčkův Brod and gradually developed its offer of truck transport and related services for carriers and motorists.
Order transport using the contact form.


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Ottoman Ahmet Ali Efendi, the worlds' first black pilot
While American black people were still being treated as slaves or worse, Ottoman Muslim Air Forces member Ahmet Ali Efendi was the first black pilot of the world. He participated in a lot of air missions.
Ahmet Ali Effendi (Ahmet Ali Çelikten) was an Ottoman aviator who may have been the first black military pilot in aviation history. Ahmet born in 1883 in İzmir to his mother Zenciye Emine Hanım and father Ali Bey, of African Turkish descent. (His grandmother and grandfather are from Nigeria) He aimed to become a naval sailor and entered the Naval Technical School named Haddehâne Mektebi (literally "School of the Blooming Mill") in 1904. In 1908, he graduated from school as a First Lieutenant. And then he went to aviation courses in the Naval Flight School that was formed on 25 June 1914 at Yeşilköy. He was then a member of the Ottoman Air Force.
During World War I, he married Hatice Hanım who was an immigrant from Preveza. He became first black military pilot in aviation history when he started serving in November 1916. On 18 December 1917, Captain Ahmed Ali was sent to Berlin to complete aviation courses. He died in 1969.
source:rasoolurrahmah.wordpress.com
#Ottoman History,
#African Turks
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Meet the Cast of 'NCIS'
Here's everything you need to know about the stars of the CBS show before watching season 17.
By Kelly O'Sullivan
CBS Photo Archive
NCIS, CBS's long-running procedural, is entering its seventeenth season this fall. Its success has inspired two spin-offs—NCIS: Los Angeles and NCIS: New Orleans—and the crime drama consistently tops the ratings for scripted shows.
The series made headlines in 2017 when leading lady Pauley Perrette announced her exit after 15 years. Fans were devastated to see her character, Abby, go, and news of her replacement elicited mixed reactions. Ahead of NCIS's seventeenth season, there's even more cast drama—but this time, it's about one character's shocking return. Ziva, played by actress Cote de Pablo, surprised everyone when she appeared during last season's finale. Her comeback has inspired plenty of fan theories, but everyone has one question on their minds: Is Ziva back on NCIS for good? Only time will tell!
Here's everything you need to know about the new and returning cast of NCIS.
Mark Harmon as Special Agent Leroy Jethro Gibbs
Mark's film and television career has earned him multiple Emmy Award and Golden Globe Award nominations over the years. In addition to his work on various shows in the '70s, he is also known for his four-episode role in The West Wing. His NCIS character, Gibbs, commands a team for the Naval Criminal Investigative Service.
Cote de Pablo as Special Agent Ziva David
Everyone thought Cote's character was gone for good, until she appeared suddenly at the end of season 16. Now, Cote will return to her role as Ziva—a special agent on the NCIS team thought to be dead—for a four-episode arc in season 17.
Sean Murray as Special Agent Timothy McGee
Hocus Pocus fans might remember Sean as Thackery Binx. On NCIS, he plays Timothy McGee, a Senior Field Agent assigned to the main NCIS Major Case Response Team. And before you ask, no, he's not leaving.
Emily Wickersham as Special Agent Eleanor "Ellie" Bishop
Emily was promoted to a series regular on NCIS after a three-episode arc in 2013. Before joining the Naval Criminal Investigative Service as a Special Agent, her character Ellie—otherwise known as Ziva's replacement—was an analyst for the NSA.
Wilmer Valderrama as Special Agent Nicholas "Nick" Torres
Many will recognize Wilmer from his role as Fez on That '70s Show. On NCIS, he plays a highly skilled undercover agent who is also a member of the main NCIS Major Case Response Team.
Maria Bello as Special Agent Jacqueline "Jack" Sloane
Maria has appeared in a number of major films, including Coyote Ugly, The Cooler, and A History of Violence. Now, she stars as a Forensic Psychologist and another member of the NCIS Major Case Response Team.
Brian Dietzen as Dr. Jimmy Palmer
Brian is known on-screen as the "Autopsy Gremlin." He is also a member of the NCIS Major Case Response Team, and the assistant to NCIS Chief Medical Examiner Donald Mallard.
Diona Reasonover as Forensic Scientist Kasie Hines
Diona's character Kasie is a forensic scientist on NCIS. She had a recurring role before being promoted to a season regular after Pauley Perrette's exit.
Rocky Carroll as NCIS Director Leon Vance
Best known for his role as Joey Emerson on the FOX dramedy Roc, Rocky now stars as the long-serving director of the NCIS.
David McCallum as Dr. Donald "Ducky" Mallard
David rose to fame in the '60s for his role as Illya Kuryakin in the series The Man from U.N.C.L.E. Though the Medical Examiner almost left for good in season 16, he's now serving as the NCIS historian who can come and go as he pleases.
20 Funny Scary Movies to Make You Laugh and Scream
Kelly O'Sullivan Content Strategy Editor Kelly O'Sullivan is the content strategy editor for CountryLiving.com and also covers entertainment news, from standout moments on "The Voice" to the latest drama on "Chicago Fire."
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How Democrat Joe Biden's Catholic Faith Shaped His Life, Politics
By Asma Khalid
Published September 17, 2020 at 3:05 AM MDT
Joe Biden is known to carry a rosary in his pocket and to go to Mass every Sunday. If elected, he would be only the second Catholic president in American history. NPR's Asma Khalid reports on how his faith is central to how he sees the world and how it affects his politics.
ASMA KHALID, BYLINE: When you listen to Joe Biden, you'll notice how he peppers his speeches with references to God. Here he is earlier this week speaking to the Poor People's Campaign.
JOE BIDEN: All of you remind me of how Scripture describes the calling born out of the wilderness - a calling to serve, not to be served, a calling toward justice, healing, hope, not hate.
KHALID: It wasn't a one-off comment. This is how Biden talks.
BIDEN: I believe we'll be guided by the words of Pope John Paul II, words drawn from the Scriptures.
Faith sees best in the dark, and Lord knows these days are dark days.
And may God bless you. And may God protect our troops.
CHRIS COONS: It's part of who Joe is.
KHALID: Delaware Sen. Chris Coons has known Biden for decades.
COONS: Joe is someone for whom the ways in which he sees issues around racial justice, around the treatment of refugees and immigrants. All of that is connected to a view of other people, who he sees as neighbor, who he sees as being made in the image of God.
KHALID: Coons says Biden's political positions go back to his upbringing.
COONS: ...A deeply rooted sense of fairness that he learned from his parents and from the nuns and priests who educated and helped raise him. So - and I think one of the mistakes Democrats have made over decades is to be very private about the values that move them into public life.
KHALID: With Biden, allies say, it's obvious what drives him. Sister Carol Keehan is the former CEO of the Catholic Health Association.
CAROL KEEHAN: When Joe Biden talks about faith, he talks very much about things like the Gospel of Matthew. But what you've done to the least of my brother and you've done to me. You know, blessed are those who hunger and thirst for justice.
KHALID: Friends and staffers say Biden focuses on faith rather than religious doctrine. He prays with voters rather than proselytizes. And yet for some religious conservatives, all of that pales in comparison to the single issue of abortion. Earlier this week, a Catholic voter group released this ad.
UNIDENTIFIED PERSON #1: Joe Biden would force American Catholics to pay for abortions, sacrificing his Catholic values to kneel before the leftist mob.
KHALID: President Trump and his supporters have made religion into a cultural issue, painting Democrats as the party against religious freedom. Last month, President Trump accused Biden of being, quote, "against God." For its part, the Biden campaign has been expanding its faith outreach.
UNIDENTIFIED PERSON #2: Thank you for joining this Biden-Harris campaign Catholics For Biden national kickoff call.
KHALID: One speaker, Sister Simone Campbell, said Catholics need to be multi-issue voters if they're really following Pope Francis's teachings.
SIMONE CAMPBELL: Care for the unborn is critically important. Equally sacred is the care for the born, the marginalized, the poor, the immigrants, the earth.
KHALID: Joe Biden's campaign seems to think the personal is political. John McCarthy is national deputy political director.
JOHN MCCARTHY: It's about the vice president being who he truly is, which is a Catholic and a deeply devout person of faith. And why I think that that ultimately has electoral implications is because, at this moment, this election is obviously about a moral contrast.
KHALID: McCarthy says campaigns are obviously an extension of who the candidate is, and, because faith is such a core part of Biden's identity, it's become a core part of the campaign. But it's also a tightrope for religious Democrats to walk. Polling from the Pew Research Center shows the share of people who identify with no religion has jumped in recent years. They now make up almost 40% of Democratic voters.
Asma Khalid, NPR News. Transcript provided by NPR, Copyright NPR.
Asma Khalid
Asma Khalid is a political correspondent for NPR who co-hosts The NPR Politics Podcast.
See stories by Asma Khalid


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Severance season 2 premiere date: Chances for more news
Severance December 15, 2022
Are there more opportunities to learn about a Severance season 2 premiere date in the near future? It absolutely feels that way, and it is thanks to one simple thing.
If you did not know, earlier this week the Golden Globe nominations were announced and luckily, the Adam Scott series did receive some love. There's also a chance that more is coming from the SAG Awards when that takes place. These shows serve, of course, have a chance to give the show a little bit more publicity, but there's something that extends beyond that. Think in terms of opportunities to announce some good stuff!
So what could we learn during the campaign process, or even the awards shows themselves? We do tend to think that the cast will be asked about premiere dates but truthfully, there is only so much that they can share. Apple TV+ may not know the premiere date yet, and they may not necessarily be that eager to pass that along to the cast and crew even when they do. In general, we know that a lot of networks and streaming services tend to be pretty protective of a lot of this information.
In the end, we do think this promotional tour (and the awards shows themselves) could give us a few more pieces of info as to what's coming up. However, a premiere date announcement is unlikely. We tend to think that this is something that could come out in the spring, potentially around the time that production wraps up in May. This could set the stage for getting some episodes in the summer or the fall. There is a little bit of variance here, as there are a number of factors including post-production and then also what works best for the Apple TV+ schedule at large.
Related – Check out some other news when it comes to Severance, including more on what could be coming up next
Do you think we could be getting more news when it comes to Severance season 2 over the days ahead?
Be sure to share right now in the comments, and also stick around for some other updates. (Photo: Apple TV+.)
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http://ChampionFoundation.com In this video, we will be demonstrating the installation of Champion's Helical Pier System.
The process begins by hand digging holes at each point to allow access to the footer. Once the footer is chiseled and prepared, it's time to place the spreader beam.
After the spreader beam has been placed, it's time to install the Helical Lead Section. The Helical Lead is a steel pipe with multiple twisted helix plates ranging in size from 8 inch to 16 inches in diameter.
The ULTRA bracket is now connected to the footer and foundation is ready to be lifted. The Fasteel ULTRA bracket is the industry's strongest foundation bracket, each series of brackets are tested at the manufacturer and provide an unparalleled holding capacity of up to 120,000 pounds.
Using a specially designed 20 ton jacking assembly, we begin to jack and slowly lift the home's foundation. As the house is lifted the weight of your homes foundation is shifted off the damaged soil structure and onto the helical pier.
Champion's patented state-of-the-art helical repair system provides the industry's strongest and longest lasting foundation repair.


In a world of industrialization, population, explosion, and environmental destruction the surfer somehow has managaed to establish a wonderful harmony with the oceans' waves and nature. "The Sunshine Sea" is a surfing video film about the changes that have raised the art of surfin from the limitations of the past to the free and easy harmony of today. Greg Macgillivray and Jim Freeman embark on a surfers' odyssey with champion surfers David Nuuhiwa, Nat Young, Mark Martinson, and Bill Hamilton in Portugal, France, Hawaii, and California. From the makers of the all time classic, "Five Summer Stories", comes "The Sunshine Sea", a reflection of the happiness of surfing.


A venue for cutting-edge contemporary and often socially relevant work. Features such well-known artists as Carrie Mae Weems, Iona Rozeal Brown, David Hammons and Gary Simmons.
Join Anne Collins Smith, Makeba Dixon-Hill, Curator of Education, and Holly Smith, Spelman College Archivist, for a discussion about the historical and contemporary presence of Black women in archives and museums.
A Day With(out) Art is an International Day of Action and Mourning in Response to the AIDS Crisis held in tandem with World AIDS Day.