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Spanish Rock Climbing
In Spanish Rock Climbing, we brought together language immersion, physics, and rock climbing. Campers spent two days at Denver's Ubergrippen Climbing Gym, as they learned about how to use Spanish language in order to rock climb. They used Spanish commands to belay each other on the wall, and learned the vocabulary of all their climbing gear. They also looked at mechanical advantage, and learned the physics of how you can belay someone much larger than you!


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This is from the Serial Killer Coloring Book #1.666(or issue #2) from 1999.
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Equilibrium Morphology of Face-Centered Cubic Gold Nanoparticles >3 nm and the Shape Changes Induced by TemperatureA. S. Barnard,*,, X. M. Lin,,, and L. A. Curtiss,Center for Nanoscale Materials, Materials Science DiVision, and Chemistry DiVision, Argonne National Laboratory, 9700 South Cass AVenue, Argonne, Illinois 60439 ReceiVed: August 2, 2005; In Final Form: October 24, 2005
Many of the unique properties of metallic nanoparticles are determined not only by their finite size but also by their shape, defined by the crystallographic orientation of the surface facets. These surfaces (and therefore the nanoparticles themselves) may differ in a number of ways, including surface atom densities, electronic structure, bonding, chemical reactivities, and thermodynamic properties. In the case of gold, it is known that the melting temperature of nanoparticles strongly depends on the crystal size and that the shape may alter considerably (and yet somewhat unpredictably) during annealing. In this work we use first principle calculations and a thermodynamic model to investigate the morphology of gold nanoparticles in the range 3-100 nm. The results predict that the equilibrium shape of gold nanoparticles is a modified truncated octahedron and that the (size-dependent) melting of such particles is preceded by a significant change in the nanoparticles morphology.
1. Introduction Metallic nanoparticles containing tens to thousands of atoms are attracting considerable interest, largely because the transition from molecule-like behavior to bulk properties occurs in this size regime. Research activities in this area have mainly focused on the size-dependent physical properties,1,2 motivated by possible applications as catalysts as well as electrical and optical components in nanodevices.3-6 However, the unique properties of metallic nanoparticles are determined not only by their finite size (resulting in a large fraction of atoms occupying the surfaces) but also on the particle shape, defined by the relative area of different surface facets.7 For instance, the plasmon excitation of gold or silver nanorods can span the entire visible wavelength by simply changing their aspect ratio.8 Compared with spherical particles, the rod-shaped particles show a much greater electromagnetic enhancement for molecular surface Raman scattering.9,10 Recent syntheses using a cationic surfactant cetryltrimethylammonium bromide (CTAB) have generated not only nanorods11 but also bipod and tripod structures that intuitively seem energetically unfavorable.12 These developments have prompted renewed interest in understanding the energy and stress of different crystal surfaces and how the surface ligand binds to different facets. In addition to surface chemistry, thermodynamic considerations are also known to play an important role in governing the morphology of gold nanoparticles. Although many bulk metals have the face-centered cubic (fcc) structure, small clusters (typically less than 3 nm) of the same materials may exhibit various structural and morphological modifications. Metallic clusters have been observed as cuboctahedral fcc structures,13 singly or multiply twinned fcc structures,14,15 twinned hexagonal* Current address: Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, U.K. Current e-mail: amanda.barnard@ materials.ox.ac.uk. Center for Nanoscale Materials. Materials Science Division. Chemistry Division.
close-packed (hcp) structures,16 icosahedral and truncated icosahedral (Ih) structures,15,17-20 as well as the Marks decahedral17,18 and truncated decahedral (Dh) structures.17,18 The majority of previous computational (and theoretical) studies on gold structures >3 nm in size have focused on the icosahedral and decahedral particles, since these have been found to be the lower energy morphology for small clusters (<3 nm).21-25 In the case of the icosahedral clusters, such studies have indicated that as the size of the cluster increases, the stability of the icosahedral structures decreases significantly,21,26,27 due to accumulated strain energy.22,23,25 In the case of decahedral particles, computational studies have shown that gold nanoclusters in the range 1-2 nm are more likely to form in three discrete cluster sizes belonging to the truncated Marks decahedral motif (with particular truncations), than any other shape.22,25 These and numerous other computational studies of decahedral and icosahedral gold nanostructure have been reviewed in ref 28. Samples of larger gold nanoparticles (over 5 nm) are known to have a far fewer fraction of particles with icosahedral or decahedral shapes, based on observations of a number of studies.13,29,30 However the exact shape of these particles, under either equilibrium or nonequilibrium conditions (such as during annealing), is currently unknown. To investigate this problem, we have used a multiscale thermodynamic model33 based on the Gibbs free energy of (arbitrary) nanoparticles as a function of size and shape to systematically compare various possible (nonequilibrium) shapes and to determine the minimum energy morphology of fcc gold nanoparticles for sizes ranging from 3 to 20 nm. The advantages of this type of thermodynamic modeling include the ability to compare nonequilibrium shapes, to optimize the morphology with respect to experimentally relevant parameters such as temperature, and to consider large nanoparticles at sizes traditionally inaccessible to all but atomistic level simulations. This study therefore represents the first investigation of gold nanoparticles at experimentally relevant sizes, based on electronic structure.
10.1021/jp054279n CCC: $30.25 2005 American Chemical Society Published on Web 12/02/2005
24466 J. Phys. Chem. B, Vol. 109, No. 51, 2005 As input into the model, the surface free energies and the surface stresses for the (111) and (100) surfaces have been calculated using scalar relativistic first principles methods. Following the examination of the equilibrium nanomorphology, we have used the model to investigate the effect of temperature on the shape of gold nanoparticles in the range 4-12 nm. It is known that the melting temperature of gold nanoparticles strongly depends on size, with the melting point of 2.5 nm particles being as much as 40% lower than that of (macroscopic) bulk gold.35 Our results predict that the size-dependent melting of the (equilibrium-shaped) fcc nanoparticles is preceded by a dramatic change in shape, the degree of which increases with increasing particle size. Using the shape versus temperature results in combination with the shape observed in real nanoparticles under the electron microscope, we have made an estimate of the temperature at which such nanoparticles are annealed due to exposure to the electron beams during imaging. Before embarking upon a theoretical analysis of the shape of large nanoparticles, it is first important to gain an appreciation of the shapes observed in real specimens. Previous experimental studies13,29,30,37 have tended to assign the truncated octahedral or cuboctahedral motif, without providing a detailed description of the exact fraction of {111} to {100} surface area. In section 2 we have analyzed the shapes of large (6 nm) particles from experiments. This information is particularly important here, if we are to accurately model the shape transitions of fcc gold nanoparticles approximately 3-20 nm in size. 2. Experimental Background Synthesis of highly monodispersed noble metal nanoparticles is well developed. We adopted a digestive ripening procedure to synthesize dodecanethiol ligated nanoparticles.36 This procedure yields highly monodispersed particles for each reaction with the standard particle size deviation <5%. From batch to batch, the size varies from 5 to 8 nm. We used high-resolution transmission electron microscopy (HRTEM) to examine the morphology of the particles, because it is much less ambiguous compared with techniques used to characterize small clusters, such as powder diffraction and pair distribution analysis.37 Figure 1 shows a HRTEM image of 8 nm gold nanoparticles, taken with a JEM-4000EXII high-resolution electron microscope at 400 keV accelerating voltage and 1.2 M magnification. The nanoparticles have been washed repeatedly prior to being dissolved in toluene and deposited on the TEM grid, so that the amount of ligand molecules on the nanoparticle surfaces has been minimized. Careful examination of these images shows that about one-third of the particles either contain a single twin plane or are decahedral. The remaining two-thirds are single fcc structured nanoparticles, some of which appear superficially spherical in shape and others exhibiting some degree of facetting. To elucidate more precisely the shape of these thiol-deficient gold nanoparticles, we have used an empirical shape-matching technique, which employs a set of eight candidate structures with varying morphology. The exact shape of each candidate structure depends on the degree of truncation in the 111 direction, beginning with an octahedron and ending with a cuboctahedron. The set was constructed by incrementally increasing this truncation or, alternatively, incrementally decreasing the {111} surface area (from 100% {111} to 40% {111}). To determine the shapes of real nanoparticles, each of the candidate structures was rotated to match the orientation of a given nanoparticle HRTEM image. To do this we adopted a simplified model which projects the candidate structures on the
Barnard et al.
Figure 1. HRTEM image of 8 nm gold nanoparticles, synthesized using a digestive ripening technique with dodecanethiol as ligand.
two-dimensional detector. Only the outline of the nanoparticle shape and visible atomic lattices are taken into account without detailed analysis of the phase contrast. The projection is then overlapped with real HRTEM images to select the candidate structure that best reproduced the cross sectional outline of the particle. This candidate structure was then assigned to the particle as the morphology-of-best-fit. This procedure was repeated for HRTEM images of 50 independent nanoparticles, some examples of which are given in Figure 2. Following the analysis outlined above, we found the fcc gold nanoparticles in our sample have truncated-octahedral motif and the crystal surface is dominated by {111} and {100} forms. In fact, even the more spherical-looking nanoparticles, such as the example shown in Figure 2d, may be described by a truncated octahedron. Statistically, the matching study revealed only a relatively small variation in the morphology of the nanoparticles, with a normal distribution centered around 77% {111} (23% {100}), with a width of 7.5% and a standard error of 1.9%. These results are in agreement with the experimental results of gold nanoparticles with fcc form in a similar size range13,29,30 and computational studies predicting a crossover from decahedra to fcc happen at the 500 atoms range.22,31 However, they are in sharp contrast with experimental results from Koga and Sugawara,32 in which icosahedron and decahedron are the dominant morphologies. It has been proposed, in the latter case, the formation of icosahedra is due to a kinetic trapping effect.28 In comparison, our sample prepared through a digestive ripening process appears to exhibit a morphology much closer to the thermodynamically equilibrium shape. 3. Methodology 3.1. Theoretical. The multiscale thermodynamic model33 mentioned above is based on a summation of the Gibbs free energy Gtotal of a nanoparticle of material x (x ) Au in this x current study). In the truncated version of the model used here, the energetic contribution from edges and corners have been
J. Phys. Chem. B, Vol. 109, No. 51, 2005 24467 faceted nanoparticles.33 Therefore, the volume dilation due to the surface stress, with the bulk modulus B0, is defined as
2 e)
fixi iB0R (3)
Figure 2. Examples (a-d) of the empirical shape-matching technique used to estimate the morphology of gold nanoparticles observed in HRTEM. The HRTEM image is shown to the left, and the final candidate structure assigned as the morphology-of-best-fit is shown to the right. The center columns show the projection of the candidate structure (center right) and an overlay of this projection with the HRTEM image (center left) to illustrate the matching of the lattice fringes and cross sectional outline.
where xi is the surface stress of the particular crystallographic surface i. Although the overall affect of e is small, inclusion of this term is particularly important, since it has been reported experimentally that small (4 nm) gold nanoparticles exhibit a lattice contraction, resulting in lattice parameters smaller than that of bulk gold.37 Therefore, this model requires explicit determination of the values of xi and xi for all surfaces i of interest (along with the value of B0). As mentioned above two surfaces have been found to be important, so that we have i ) (111) and (100). Since the surfaces of gold are nonpolar, this is equivalent to i ) {111} and {100}. These surfaces were modeled using 2 2 (surface) supercells consisting of nine and eight atomic layers perpendicular to the desired surface (with a total N ) 108 and 64 Au atoms), respectively. Periodic boundary conditions are applied in all three Cartesian directions, and the surfaces are exposed via an additional 10 38 of vacuum space. With these structures, the total energy for the surface slabs (Eslab) was calculated, N using the methods outlined in section 3.2. A value for the bulk energy per atom (Ebulk) was also obtained from separate supercell calculations of larger sizes but the same computational conditions. The surface free energies xi were then obtained (at T ) 0) from Ebulk and Eslab using the expressions N
ignored. A consequence of this is that results will only be valid for nanoparticles over 3 nm in diameter34 (since below this size the latter effects become significant and must be included); however, calculation of a complete set of these parameters is more computationally expensive than the explicit consideration of isolated <3 nm structures (which will be reported elsewhere). More information on the operating range of applicability and testing of this model may be found in refs 33 and 34. Therefore, for the purposes of studying gold nanocrystals >3 nm in size, Gtotal is described by a sum of contributions from x the nanoparticle bulk and surfaces, such that
xi )
Gx Ai
(4) (5)
1 Gx ) (Eslab - NEbulk) 2 N
This is then further defined in terms of the surface energy xi for each crystallographic surface i, weighted by the factors fi (where i fi ) 1). Hence
Gtotal ) fGo + x x
M (1 - e)[q Fx
fixi] i
where fGo is the standard free energy of formation of the x bulk (macroscopic) material (which for gold is zero by definition), M is the molar mass, Fx is the density, and e is the volume dilation induced by the surface stress. In general, the surfaceto-volume ratio q and the weighting factors fi must be calculated explicitly for each shape and the facets therein. In this model the size dependence is introduced by the surface-to-volume ratio q and the reduction of e as the crystal increases in size. The shape dependence is also introduced by q, as well as the weighted sums of the surface energies and the surface stresses.33 It has previously been shown33 that the Laplace-Young equation is suitable for approximating the volume dilation of
where Gx is the free energy of the slab, Ai is the area of a surface of the slab (in orientations i) (111) and (100)), and N is the number of atoms in the supercell of the slab. Similarly, the value of xi was obtained by applying a twodimensional dilation39 to the slab in the plane of the surface and calculating the free energy Gx as indicated in eq 5. At each dilation the change in free energy (Gx) was determined for a set of area dilations (Ai). When these results were plotted, an estimate of the surface stress was obtained from the expansion, as described in ref 39. The value of B0 has been determined by calculating the energy of a 108 atom bulk (periodic) supercell for a number of volume dilations ((1% to (5%) and then fitting the results to the Vinet equation of state.40 The final values of B0 ) 157 ( 1.9 GPa and B ) 4 ( 0.3 GPa are in reasonable agreement with the 0 experimental values of 167 and 5.5 GPa measured by Heinz and Jeanloz41 and B0 ) 167 GPa measured by Holzapfel et al.42 3.2. Computational. In determination of xi, xi, and B0, the calculations were undertaken from first principles using density functional theory (DFT) within the generalized-gradient approximation (GGA), with the exchange-correlation functional of Perdew and Wang (PW91).43 This has been implemented via the Vienna ab initio Simulation Package (VASP)44,45 which utilizes an iterative self-consistent scheme to solve the KohnSham equations using an optimized charge-density mixing routine. Each of the bulk and slab structures were fully relaxed, prior to the calculation of the total energies, using a 4 4 8
24468 J. Phys. Chem. B, Vol. 109, No. 51, 2005 and 4 4 1 Monkhort-Pack k-point mesh, respectively. The electronic relaxation technique used here is an efficient matrix-diagonalization routine based on a sequential band-byband residual minimization method of single-electron energies,46,47 with direct inversion in the iterative subspace, whereas the ionic relaxation involves minimization of the HellmannFeynman forces. This technique has been shown to give good results for gold in the past.38 The initial relaxations and the following static single point energy calculations were performed using the projected augmented wave (PAW) potentials,48,49 with a plane-wave basis cutoff of 250 and 350 eV (respectively), to an energy convergence of 10-4 eV. In all of the calculations we have included relativistic effects. The PAW potentials are generated relativistically (including mass velocity and Darwin terms), so that the radial wave functions are solutions of the scalar relativistic radial equation. In addition to this, spin polarization and spinorbit interaction (SOI) were included in the all-electron part of the PAW Hamiltonian, and the interpolation formula proposed by Vosko, Wilk, and Nusair50 was used for the correlation part of the exchange correlation functional. This procedure ensures that the spin directions couple to the crystalline structure. 4. Results and Discussion In the case of the (111) surface, a surface energy of Au(111) ) 0.523 J/m2 was calculated. This is in good agreement with the values of 0.487 J/m2 calculated by Needs and Mansfield using DFT LDA with scalar relativistic corrections,51 0.513 J/m2 calculated by Vitos et al. using full charge density linear muffintin orbitals (LMTO) in the atomic sphere approximation (ASA) without relativistic corrections,52 0.421 J/m2 calculated by Galanakis et al. using the full-potential linearized augmented plane wave method (FLAPW) and 0.522 J/m2 using the fullpotential screened Korringa-Kohn-Rostoker method (FKKR) with scalar relativistic corrections,53 and 0.655 J/m2 calculated by Kollar et al. using self-consistent exact muffin-tin orbitals (EMTO).39 Similarly, the surface stress of Au(111) ) 1.084 J/m2 calculated for the (111) surface is in good agreement with the previously reported values of 1.08051 and 0.999 J/m2 39 and the experimental values of 1.198 and 1.242 J/m2 measured by Solliard et al.54 In the case of the (100) surface, there have been comparatively fewer studies undertaken to compare with our calculated values of Au(100) ) 0.606 J/m2 and Au(100) ) 1.174 J/m2, respectively. The result for Au(100) is in good agreement with the calculated values of 0.660 J/m2 (using LMTO),52 0.499 J/m2 (using FLAPW)53 and 0.616 J/m2 (using FKKR).53 Note that surface energy anisotropy, described by (Au(100) - Au(111))/Au(111), computes to be 15.76%, in excellent agreement with the experimental value of 15.2 ( 0.9 measured by Flueli and Borel at 750 K.55 With these calculated values for Au(111), Au(100), Au(111), and Au(100) (along with B0 ) 157 GPa), as input for the model given in eq 2, a comparison has been made of the energetics of gold nanoparticles of different geometrically ideal shapes. These shapes include a cube (terminated completely by {100} surfaces), a truncated cube, a cuboctahedron, a truncated octahedron, and an octahedron (terminated completely by {111} surfaces); as illustrated in parts a-e of Figure 3, respectively. It might be intuitively expected that, since the {111} surfaces have a lower surface free energy, the octahedron would be the lowest energy shape, followed by the truncated octahedron, cuboctahedron, truncated cube, and then cube (with the Gtotal x increasing with increasing degree of {100} surface area);
Figure 3. Comparison of the energetics of gold nanoparticles of different geometrically ideal shapes including a cube (a), a truncated cube (b), a cuboctahedron (c), a truncated octahedron (d), and an octahedron (e). The relative energy, along with the optimized nanoscale morphology, is shown as a function of the number of atoms in (f).
however this was not found to be the case. The results of this comparison (shown at the bottom of Figure 3) revealed that the truncated octahedron (d) is most favorable among these shapes. This is followed by the octahedron (e), truncated cube (b), cuboctahedron (c), and cube (a), respectively. This order of morphologies results from the interplay between ifixi and the surface-to-volume ratio q. The cube (which is by far the highest energy shape) has the lowest relative value of q but is terminated by higher energy surfaces. By truncating the corners in the 111 directions to form the truncated cube, q is decreased slightly (relative to a cube), and ifixi decreases (due to the introduction of a some lower energy {111} surface area), resulting in a lower energy shape. Further truncation in the 111 directions yields a cuboctahedron, with a lower ifixi, but this is countered by an increase in q (making the contribution from Gsurface to Gtotal greater), resulting in a higher energy x x shape. In the case of the truncated octahedron, the balance between q and ifixi is optimal (resulting in the lowest energy shape), and for the octahedron the lowest value for ifixi is countered by the highest relative value of q, giving a slightly higher Gtotal. x Referring back to section 2 and the shape matching of the HRTEM images, the results of this comparison are not unexpected. The shape of the real specimens was estimated to be truncated octahedral with approximately 77% {111} surface area. This is very close to the ideal truncated octahedron used in the comparison above, which has 76% {111} surface area. 4.1. Optimizing Nanomorphology. The standard method for determining the equilibrium morphology of a material is to generate the Wulff construction56 using the surface energies. However, as the Wulff construction does not take into account the effects of surface stress and the desire for nanoparticles to minimize the total surface-to-volume ratio, it is possible that the morphologies of nanoparticles may deviate from the Wulff shape. Using the model described above, we have investigated this possibility by optimizing the nanoparticle shape, as a function of size. Figure 3 includes Gtotal for a shape referred to x as the optimized nanomorphology, which is lowest in energy
J. Phys. Chem. B, Vol. 109, No. 51, 2005 24469 types of irradiation used to probe the morphology of gold, and this may account for the observation of the (nonequilibrium) cuboctahedral shape in some experiments.37 4.2. Temperature-Induced Changes in Nanomorphology. In general, the structural (and morphological) instability of gold nanoparticles under electron irradiation (due to heat imparted to the sample by the beam) has been known for some time57 and has been examined in some detail.13,58 Similarly, recent studies have begun to investigate the morphological changes in larger (>10 nm) gold nanoparticles under optical irradiation.59,60 Link et al.59 performed a series of measurements, varying the excitation and output power of an amplified femtosecond laser system (100 fs pulses). During the experiments the shapes of gold nanorods were found to change (in addition to some fragmentation into nanodots). The final shape of irradiation products was found to be highly dependent on the energy and width of the laser pulse.59 In the study undertaken by Inasawa et al.,60 the shape of large (38 nm) gold colloidal nanoparticles was found to undergo a shape transformation from ellipsoidal to spherical when exposed to a single laser pulse (30 ps pulse width). This transformation occurred at approximately 940 C, some 124 C below the particle melting point (of 1064 C). Therefore, it is not surprising that temperature rather than size has been shown to be a decisive factor in affecting the final shape of gold nanoparticles.61 A number of simple expressions have been used here to describe the temperature dependence of xi, which was calculated above at T ) 0. First, we have used a semiempirical expression for determining of (T) proposed by Guggenheim,62,63
Figure 4. The Wulff construction (top) as predicted by the surface energies calculated using first principles scalar relativistic methods and schematic (bottom) showing the definition of the geometric parameters A (solid line) and B (dotted line) used for the optimization of this shape with respect to size or temperature.
for less than approximately 7000 atoms. The method used to determine this shape (as a function of size) is as follows. Beginning with the Wulff construction as the initial case (as shown in Figure 4a), the morphology of the gold nanoparticles was defined in terms of two independent length parameters A and B. In this case the side of the {111} form has been denoted A, and the vector in the 111 direction is denoted B, as indicated in Figure 4b. The degree of truncation may therefore be described by the size of B with respect to A (where 0 e B e 2A/3). When B ) 0, the shape is an octahedron, when B ) 2A/4, the shape is a cuboctahedron, and when B ) 2A/3, the shape is a cube. By defining all the geometric parameters such as the volume and surface area of the various facets in terms of the ratio B/A, the total free energy was minimized with respect to this new variable. The numerical minimization was performed using a conjugate gradient scheme. At small sizes (less than 20 nm) the model predicts a deviation of the B/A from that predicted by the Wulff construction. For particles of 3 nm in size, a ratio of B/A ) 0.167 is predicted (89.6% {111}), for 6 nm particles, B/A ) 0.163 (90.2% {111}), and for 9 nm particles, B/A ) 0.161 (90.3% {111}). This converges rapidly to that of B/A ) 0.160 predicted by the Wulff construction (90.5% {111}), becoming effectively equal at a size of 20 nm. Although this effect is very small, it is none the less a consequence of the nanoscale, due to the need for small particles to minimize the total surface stress (leading to e) and the total surface-to-volume q, as well as the total surface energy. In this regime, a reduction in q (even at a cost of higher ifixi), may lower the contribution of Gsurface to the total free energy of the particle, resulting in a x shape that is lower in energy than the Wulff construction. An important point to note here is that the fraction of {111} surface area predicted for the optimized nanomorphology and the macroscopic Wulff shape (90%) is not the same as that determined via the shape matching in section 2 (77%). This apparent discrepancy can be easily explained when we consider the fact that the nanoparticles in the electron microscope are not at zero temperature. The nanoparticles are heated by the electron beam and may (as a result) adopt a more nonequilibrium shape (at elevated temperatures). The same can be said for other
T Tc
where n is an empirical parameter (known to be unity for metals64) and Tc is the critical temperature at which the structure of the surface deteriorates or changes significantly from the structure in the bulk.65 This is known to be 1064.33 C for the {111} surfaces and 897 C for {100} surface.66 The value of Tc is usually taken as the bulk surface melting temperature, but since this has been shown to be size dependent,35 we have also employed the expression of Qi and Wang67
Tc ) T m 1 -
6Rr D
where Tm is the macroscopic surface melting temperatures, D is the diameter of the particle, r is the atomic radius, and R is a shape dependent factor defined as the ratio of the surface area of the particle divided by the surface area of a sphere of equivalent volume.67 In the present context the temperature dependence of xi has been described in the same way. Using these formulas xi(T) and xi(T) may be calculated and the shape of gold nanoparticles investigated via optimization of the ratio B/A for a given temperature range. Equation 7 also has the added advantage of introducing another degree of shape dependence,67 the effect of which will be to create a feedback loop during the optimization. The optimization of the nanoparticle shape at a given temperature will change Tc, which then affects the temperature dependence in eq 6, which then in turn further alters the shape. The optimization procedure has been performed at 5 C intervals of T in the range 300-1300 C, for a number of nanoparticle sizes. The collective results predict not only the size dependent melting of the particles, in agreement with
Barnard et al. containing 140-6708 atoms, was investigated by Shim and colleagues using molecular dynamics simulation in combination with the modified embedded-atom-method potential.68 Their results showed that the melting temperature of the gold nanoparticles decreases drastically with decreasing particle size and that the a premelting phenomenon involving the disordering of the surface atoms was observed (prior to the melting of the whole particle).68 The melting temperatures for various particle sizes listed in the paper are in excellent quantitative agreement with the results presented here. In a further study of the crystallization of a 4 nm gold particle (upon cooling), the same authors found that with decreasing cooling rate, the final structure of the nanoparticle changes from amorphous to crystalline (via an icosahedron-like structure). Their study concluded that fcc is energetically the most stable structure of the gold nanoparticle at large sizes.69 Similarly, the results of Baletto et al. comparing the total energy for ideal icosahedral, decahedral, and truncated octahedral fcc gold nanoparticles up to 40 000 atoms (using semiempirical potentials) also predict the fcc structure will dominate at sizes >500 atoms.25 In general, however, many molecular dynamics simulations have shown that smaller fcc gold nanoparticles transform into Mackay icosahedrons prior to melting. It was found that upon heating small fcc truncated octahedrons and truncated decahedrons underwent a transformation to the icosahedral structure by Cleveland et al.71 Later, the transformation to an icosahedral motif during simulated freezing of gold nanoparticles up to almost 4000 atoms was also examined by Chushak and Bartell,70 and more recently, Wang et al.26 conducted similar molecular dynamic simulations showing that gold clusters between 600 and 3000 atoms crystallize into an icosahedron upon cooling from the liquid phase. In this study the surface facets of the icosahedral clusters were shown to soften, due to the increasing mobility of vertex and edge atoms with temperature. This led to interlayer and intralayer diffusion, shrinkage of the average facet size, and eventually to the change to a nearly spherical shape upon melting.26 The importance of size dependence to these results (showing a preference for gold to adopt an icosahedral motif prior to melting) was put into context in a recent study by Kuo and Clancy.27 As part of their own molecular dynamics study of the melting and freezing of supported and unsupported 2-5 nm particles (which also showed the structural transformation from the fcc to an icosahedral at elevated temperature), they found that large fcc particles transformed into a quasi-melting phase (before completely melting). In this region of the phase map, the high values of N, the fcc particles were found to bypass the icosahedral phase all together. They presented a T-N phase map, illustrating the relationship between phases for a given number of atoms (N). In our study, the particle size of interest (chosen to match the nanoparticles shown in Figure 1) will contain 15 000 atoms, and will fall within the high-N region of this phase map,27 as can be discerned by examining the precursor to this phase map proposed by Marks.17 Further, in the case of smaller nanoparticles, a direct route for the conversion of cuboctahedral nanoparticles to icosahedral nanoparticles has been identified,21 but no direct path has been found for a truncated octahedron to convert to an icosahedron. It is therefore entirely plausible to suppose that the truncated octahedron to cuboctahedron transition shown herein provides a preliminary step in the melting transitions, which will be subsequently followed by the cuboctahedron to icosahedron transition described in ref 21.
Figure 5. The calculated change in total free energy (a) and fraction of {111} surface area (b) as a function of temperature for 4, 6, 8, 10, and 12 nm gold nanoparticles. The onset of melting is indicated by the abrupt change in the slopes in (a) and by the dotted line bisecting the plots in (b). The shape transition (from truncated octahedron illustrated for point A to a more cuboctahedral morphology as illustrated for point C) is predicted prior to the onset of melting.
experiment, but also that the melting will be preceded by a significant change in nanoparticle morphology. Figure 5a gives the change in Gtotal as a function of temperature. For each of x the nanoparticles sizes examined, the onset of melting is evident, indicated by the abrupt changes in the slopes. The onset of melting shifts to higher temperatures as the nanoparticle size increases, and the slopes diminish as the particle melting temperature approaches the bulk melting temperature. The corresponding change in nanoparticle shape is illustrated in Figure 5b where the fraction of {111} surface area is plotted as a function of temperature for each particle size. Here again, the onset of melting is shown (by the dotted line bisecting the plots) following a smooth decrease in the {111} surface area (equating to an increase in the {100} surface area) or, equivalently, an increase in truncation of the underlying {111} octahedron. In short, the melting is preceded by a shape transition from a truncated octahedron to a more cuboctahedral-like nanoparticle. (Superficially, the latter of morphology can appear more spherical in cross section when viewed from different perspectives.) Given that the shape matching study indicated that the gold nanoparticles (such as those shown in Figure 1) exhibit approximately 77% {111} surface area, we can estimate that these particles have been annealed to 800 C by the electron beam. These results are in good agreement with previously reported computational studies examining the melting temperature and thermal stability of unsupported fcc gold nanoparticles.68,69 For example, the thermal stability of unsupported nanoparticles
Morphology of Gold Nanoparticles 5. Conclusion In summary, we have systematically investigated the morphology of fcc gold nanoparticles greater than 3 nm in size, using a shape-dependent thermodynamic model combined with surface energies and surface stresses calculated using first principles methods (with relativistic corrections). This is the first time that a study of gold nanoparticle morphology in this size regime has been undertaken using such a high level of theory. The results have shown that among the geometrically ideal shapes considered, the truncated octahedron is by far the most energetically favorable, in excellent agreement with experimental observations. Furthermore, it was found that an octahedral morphology and a truncated cubic morphology (respectively) are expected to be lower in energy than a cuboctahedron. We have also shown, by optimizing the shape of the gold nanoparticles with respect to size, that the equilibrium shape of small fcc gold nanoparticles (less than 20 nm) deviates slightly from that expected from the (macroscopic) Wulff construction. The evolution of this specific nanoscale morphology is due to the need for small particles to minimize the total surface stress and the total surface-to-volume ratio as well as the total surface energy. The same optimization procedure was used to examine the equilibrium nanomorphology of gold nanoparticles (of various sizes) as a function of temperature, using an semiempirical relationship between the critical temperature the surface energies and surface stresses. These results predict that a shape transformation will be observed prior to melting, characterized by an increase in the fraction of {100} surface area and the adoption of a more cuboctahedral morphology. This prediction is consistent with results from atomistic computer simulations68 and is reasonable in light of experimental observations of gold nanoparticles changing shape when exposed to optical59,60 or electron13,57,58 irradiation. This type of temperature-induced shape transition could account for the observation of the (otherwise metastable) cuboctahedral morphology often observed in large gold nanoparticles13,37 and provides a preliminary step before the transition to an icosahedral21 shape in small gold nanoparticles before the melting transition. Acknowledgment. This work has been supported by the U.S. Department of Energy, Basic Energy Sciences, under Contract W-31-109-ENG-38. Computational resources for this project have been supplied by Argonne National LaboratorysLaboratory Computing Resource Center, the MSCF in EMSL (a national scientific user facility sponsored by the U.S. DOE, OBER and located at PNNL), and the U.S. Department of Energy National Energy Research Scientific Computing Center. References and Notes(1) Halperin, W. P. ReV. Mod. Phys. 1966, 58, 533. (2) El-Sayed, M. Acc. Chem. Res. 2001, 34, 257. (3) de Heer, W. ReV. Mod. Phys. 1993, 65, 611. (4) Jensen, P. ReV. Mod. Phys. 1999, 71, 1695. (5) Moriarty, P. Rep. Prog. Phys. 2001, 64, 297. (6) Schiffrin, D. J. MRS Bull. 2001, 26, 1019. Kreibig, U.; Vollmer, M. Optical Properties of Metal Clusters; Springer-Verlag: Berlin, 1995. (7) Wang, Z. L. J. Phys. Chem. B 2000, 104, 1145. (8) Liu, M. Z.; Guyot-Sionnest, P. J. Phys. Chem. B 2004, 108, 5882. (9) Wang, D.-S.; Kerker, M. Phys. ReV. B 1981, 24, 1777. (10) Nikoobakht, B.; Wang, J.; El-Sayed, M. A. Chem. Phys. Lett. 2002, 366, 17. (11) Jana, N. R.; Gearheart, L.; Murphy, C. J. J. Phys. Chem. B 2001, 105, 4065. (12) Chen, S.; Wang, Z. L.; Ballato, J.; Foulger, S. H.; Carroll, D. L. J. Am. Chem. Soc. 2003, 125, 16186. (13) Bovin, J.-O.; Malm, J.-O. Z. Phys. D 1991, 19, 293. Hou, M. Phys. ReV. B 2000, 62, 10383.
Barnard et al.(69) Shim, J.-H.; Lee, S.-C.; Lee, B.-J.; Suh, J.-Y.; Cho, Y. W. J. Cryst. Growth 2003, 250, 558. (70) Chushak, Y. G.; Bartell, L. S. J. Phys. Chem. B 2001, 105, 605. (71) Cleveland, C.; Luedtke, W. D.; Landman, U. Phys. ReV. B 1999, 60, 5065.


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Tom Horsburgh
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Hearst Entertainment & Syndication Leadership
Neeraj Khemlani is President and Group Head, Hearst Entertainment & Syndication
King Features, a division of Hearst, is looking for a Salesforce Administrator, who has proven experience managing Salesforce, to join its Syndication and Distribution team. We are looking for a professional with a "get it done" attitude, who takes initiative to further improve internal processes and data in our Salesforce platform. The candidate must have a focus on quality and best practices while having a goal-oriented mindset to drive solutions and lead change. An
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Design technical solutions and identify integration opportunities with applications
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Understanding of various pricing strategies, including SaaS and usage pricing and billing models
Salesforce.com Admin (ADM201 and ADM211) certified
Sales Cloud, Service Cloud and Developer certifications preferred
Nice To Have
Knowledge of SQL or Relational Databases
Experience with Conga, Pardot, and Docusign/Echosign; Conga Contracts is a plus
Hearst Technology, Inc
New York, New York, United States
📁 Information Technology (Internal)
Requisition #: 1902373
Home Office
New York, New York, United States
📁 Information Technology (Internal)
Requisition #: 1900611
Home Office
New York, New York, United States
📁 Information Technology (Internal)
Requisition #: 1900610
Hearst Entertainment & Syndication includes cable networks partnerships, television production, millennial digital video networks, comic strip and interactive game syndication and merchandise licensing operations
Hearst Entertainment has produced and now distributes an extensive award-winning movie library, representing nearly 200 films.
King Features is the world's premier distributor of comics, columns, editorial cartoons, puzzles and games, distributing in print and online some 150 features to nearly 5,000 newspapers and other outlets around the globe.
RBMA is the industry's premier provider of custom electronic pagination and editing services for newspapers.
Neeraj Khemlani is President and Group Head, Hearst Entertainment & Syndication


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Maps Navigation Normal & Night Version Map Mods Addons for ATS
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Clerical Assistant
- Recruiter
- Location
- California (US)
- Posted
- 07 Jun 2019
- End of advertisement period
- 05 Aug 2019
- Ref
- 4832
- Job Type
- Professional Services, Administrative
- Contract Type
- Permanent
- Hours
- Full Time
Caltech is a world-renowned science and engineering institute that marshals some of the world's brightest minds and most innovative tools to address fundamental scientific questions. We thrive on finding and cultivating talented people who are passionate about what they do. Join us and be a part of the diverse Caltech community.
Job Summary
Assist laboratory with scanning and archiving various documents and lab notebooks. Other organizational tasks may be assigned as needed.
Job Duties
- Scan data from lab notebooks and save on hard drives
- Organize files, notebooks and other data
Basic Qualifications
- Must have strong attention to detail and excellent organizational skills
- Working knowledge of basic office equipment
- Basic computer skills
Required Documents
- Resume


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Established in 1911, Douglas Elliman Actual Estate is the biggest brokerage within the New York Metropolitan area and the third largest residential real estate company nationwide. Lesar, who additionally served as Halliburton's chief government till last 12 months, is offering money to again the resort and retail improvement, in line with business data and officials at Whitefish metropolis government and Halliburton. He additionally has a longstanding relationship with the Zinkes. In 2014, he and his wife, Sheryl, gave $10,400, the utmost allowed by regulation, to Zinke's first House campaign. His solely other federal contributions that year have been to Halliburton's PAC and the campaign of Rep. Liz Cheney, whose father, Dick, ran the corporate earlier than becoming George W. Bush's vice president.
View our collection of brief movies highlighting current Cape Cod properties for sale, local towns and villages, attractions, happenings and vignettes of our coastal life-style. Actual estate brokers and gross sales brokers help shoppers purchase or promote real estate. New brokers will face competitors from nicely-established, extra experienced brokers and brokers. Because income depends on gross sales, newcomers could have trouble sustaining themselves within the occupation during periods of slower exercise.
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Patrick Newport, IHS Markit executive director of U.S. economics, and Susan Wachter, University of Pennsylvania Wharton actual estate professor, focus on the leap in new residence gross sales in May. All the expansion in new home sales is within the south the place housing is reasonably priced. Brokers and gross sales brokers earn most of their revenue from commissions on sales. The commission varies by the type of property and its worth. Commissions usually are divided among the buying agent, selling agent, brokers, and firms.
See Listing of home varieties for an entire listing of housing types and layouts, actual estate traits for shifts in the market, and home or home for extra common info. Some real estate brokers and sales agents work in a typical workplace atmosphere, whereas others work out of their properties. In each circumstances, actual estate workers spend much of their time away from their desks, exhibiting properties to customers, touring to see properties for sale, and assembly with prospective clients.


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Question about Washing Machines
Posted by leanne_berry on
Could b drain hose, pump or main seal. could also b tub to pump hose. u need to find the leak first to repair it. does your machine have 3 screws holding the front panel to the frame or can u look underneath and see the pump.the screws r down the bottom at the front. please reply 4 more help.
Posted on May 04, 2010
Hi there,
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Pixie Mood Sophie Wallet
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Style #37354


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Category: 201802
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Single Family Detached
- 3 beds
- 2 baths
- $202,900 price
- 2074460 mls id
- Square Feet: 1,472 sqft
1 level ranch w 3 bedrooms. 9 Ft. ceilings. Kitchen island overlooks great room Covered deck. Split bedrooms. Master suite w/ walk in closet and tiled shower. This is A copyrighted floor plan of Hawkins Homes.
- Site Link
- Style Other Style
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299 Eagles Bluff Clarksville, TN


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Event Services
If you are wanting to have a fabulous event and not have a lot of hassle when planning it, then we are the company for you. From securing your venue and decorating to helping secure professional vendors for services, you will be able to have a fabulous event without evening lifting a finger.
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I spent this past May in Europe; my first time travelling outside the United States. This trip consisted of a little working, a lot of exploring, and overall just enjoying life. I documented my trip on Instagram through photos and videos but many of you still had questions so I'm here to break it down. Bear with me as this will be a long post but will have everything you need to know about my month in Europe, so you can start planning your own adventure.
Italy was unlike anything I've experienced in my life. We covered almost the entire country by car in 7 Days: Rome, Positano & the Amalfi Coast, Venice, Tuscany, and Milan, where I stayed for an extended period of time between flights. Venice was my favorite by far, as it fulfilled every expectation that comes to mind when you think of Italy. Being up in the mountains of Amalfi was a close second. And Milan... Milan holds a special place in my heart. Before I get too nostalgic, let's jump into the good stuff:
-While in Milan I found a family to stay with using Couchsurfing. If you're careful about it, it's a really great experience to learn more about the culture of the place you're visiting, while making memories. The girl's name was Margherita if you're ever in Milan I highly recommend staying with her she loves making friends from all over the world!
-We also booked hostels in Milan, and Rome. My favorite of them was New Generation Hostel in Milan. They have a couple different locations right in the city center and very affordable!
-In Tuscany we were in a little village called Palaia. The house we stayed in through air bnb was so cozy, and had incredible views! When in the Amalfi Coast we stayed in Montepertuso, a neighboring village of Positano. I honestly couldn't say enough amazing things about this experience! The hosts were so hospitable (they even brought us food from the garden), and the house itself was beautiful and spacious with the most incredible views!
-Gondola in Venice
-Duomo in Milan
-the Galleria
-Roman colloseum (the most amazing restaurant right across the street with a buffet! Unfortunately I forgot the name)
-Trevi Fountain
-Hiking the mountains in Amalfi Coast
-Beach and Village of Positano
-Poppy fields in Tuscany
-Leaning Tower of Pisa
-McDonalds (I know, why would someone eat McDonald's in Italy. First off, we were road tripping across the entire country so fast food was essential on a couple of occasions. But, also I wanted to experience it to compare and guys...it's incredible. I had the fish and it's some of the freshest fish I have EVER tasted. The menu is also different depending what country you're in. In Italy specifically they have a full espresso bar and yes.. it's real espresso)
-White lace robe from Aporei
-Polka dot bikini from Swimsuits for All
-Two piece outfit from Bhavy J Designs (use code BHAVYJ25 for 25% off!)
-Luxy Hair Extensions 220g set in chocolate brown (discount code "ZAHRA")
I parted ways with Josie and her dad in Milan and continued my voyage to Barcelona, solo. I only had a little less than 48 hours in this beautiful city so I was barely able to scratch the surface but I'm already dreaming about going back and giving Barcelona the time and attention it deserves.
Again, I used Hostel World to stay in a budget friendly location. The bus ride into the city center gave me the opportunity to see alot of the city in a short period of time, but if you want the best experience I definitely recommend spending a little extra to book something closer to the heart of everything. I definitely plan to next time.
-LOTS of walking and wandering around
-dinner and wine at a newer little Tapas bar "la bodegueta del guinardo" (the owner was amazing and such yummy food! Not to mention the rustic vibes were a perfect impression my first night in Barcelona.
-Barceloneta beach
-Mr Robinson for coffee one day was so good I had to come back for brunch the next morning! highly recommend.
-the Gothic Quarter is a must see!
...took my breath away. And it was even more magical than i expected. Ready to hop on a flight back to this pretty little city the next chance I get!
-Hotel Residence Foch had the most Parisian view I could have asked for (without having an Eiffel Tower view), and super cute interior! They also have 24 hour reception which isn't the case with alot of places and is what ultimately saved me from having to sleep at McDonalds (it's a long story lol), so if you're getting in later this is a good thing to note!
-Trendy Hostel: farther from the city center than I would prefer BUT super affordable and accomodating and only a block away from the metro station and the BEST cafe I went to during my time in Paris.
-Something to note about Paris: there are cafes EVERYWHERE (at least 3 on every block). In other words I was in heaven.
-One cafe in particular to mention is Le Tourville, only a few blocks from eiffel tower with a Gatsby-esque interior and an extensive menu.
-Visited the Eiffel Tower multiple times, but the first time in the park I picked up a nutella waffle from a street truck on my way. (So tumblr.)
-Arc de Triopmhe after walking the Champs Elysees
-Since I tried McDonalds in Italy and was very pleased I had to test it out in Paris.. they had Macrons.
-Probably the most memorable experience of my life was visiting Notre Dame.
-Photo ops at the Louvre and l'Opera
-rode the metro (a lot)
-My only regrets from Paris was not going inside the Louvre or any other art museums, and not visiting the Catacombs. Definitely making these things happen next time!
-found the cutest berets at a street shop 3 for 10 euro! I got one in black (pictured), tan, and dusty pink
-LBD from American Apparel
-Skirt once again from Bhavy J Designs
(don't forget that discount code!)
What do you want to see from me next? Submit your requests here. xo


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Moving Forward
Moving Forward
Greetings from Spring Tarot Tour Northeast!
Hello, friends! It's your intrepid tarot traveler, reporting from Spring Tarot Tour Northeast 2019!
I want to thank those of you whom I have had the privilege to work with since my arrival last week. I am also happy to welcome some new subscribers to this newsletter.
I will be available for readings by appointment at True Bikram Yoga in Madison, CT through April 8, as well as house calls and psychic house parties in Connecticut, Massachusetts and Rhode Island.
I'll be back in my Palm City office April 11. Of course, I am available to work with you by phone, Skype, FaceTime or Messenger no matter where in the world I am!
Simply call or text 561-655-1160 to book your appointment with me, no matter where in the world you are.
Once I am back at my Palm City office you will begin to receive the full weekly Tarot Topics newsletter, rather than this abbreviated travel edition.
Traveling always reminds me of one of the greatest lessons of the Tarot Fool; that life is a journey, not a destination.
The journey of life can sometimes feel like an adventure, but sometimes it feels more like a dangerous trail to be carefully navigated. There are pitfalls, heartaches and disappointments along the way, just as there are joys, discoveries and blessings.
A tarot reading is a good tool to help give us a roadmap of the journey, and to offer an opportunity to chart our course for the best possible experience along the way.
When we find ourselves on a particularly bumpy part of life's path, it is important to remember that sometimes we simply must keep our head up, our eyes forward and our feet moving.
As we move forward, we move through our difficulties, and toward something brighter. This process happens more easily when we anticipate, and work to manifest, a smoother road ahead.
Oils, Intuition and Manifestation this Sunday in New Haven
Please join Robin Brace and me for an exciting workshop at True Bikram Yoga's New Haven location this Sunday evening at 7 pm.
We will explore some different essential oils and discuss their role in enhancing intuition, and how we can use them in helping to manifest our dreams and goals.
This will be a hands-on workshop. All materials will be provided.
You can register online, or simply join us Sunday evening.
The Week in Review
This week I shared a tip for tarot readers on my Community Blog. When you see a card in a reading that references a particular thing, how can you be sure it isn't additionally a reference to something more?
From Around the Web
Here's a post from Vice about a topic that is getting a lot of attention recently. Can tarot help with mental health issues? Here is more evidence that it can!
Something that often comes up at the tarot table is the question of when it is time to say goodbye to your beloved pet. Here's an article from the New York Times about that.
Tarotist Joy Vernon lays down some wisdom about how it works when you have multiple tarot readings.
Cards for Your Consideration
My Very First Divination Deck
Since I am writing this from Connecticut, the place where I began my tarot career so long ago, I think it is appropriate to share with you my very first divination deck.
I received this early edition of the Gypsy Witch Fortune Telling Playing Cards in my Christmas stocking when I was just eight years old. My mother loved a good novelty gift, and, to her, divination was nothing more than a novelty.
Little did she know that this particular gift would turn out to be so very prophetic!
I remember finding truth in the cards even then.
As a young adult, I encountered I Ching and then, finally, tarot. I remembered back to my childhood experiences with divination, and how profound that had felt. I had no idea what had become of that little deck of cards that had first introduced me to the idea of card reading.
After my mother passed away, I found she had saved them in a box of some of my childhood belongings. Now, they sit on my tarot shelf, surrounded by my extensive collection of tarot and oracle decks.
I've learned that the Gypsy Witch Fortune Telling Playing Cards are quite similar to the Lenormand cards, and are still available today from US Games Systems, Inc. Surprisingly, they still come in the same orange box!
Tarot Topics Newsletter
Volume 2 Issue 14
April 3, 2019


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As a gluten free, wholefoods bakery, Honest Goods Co. has always taken a holistic approach to creating our baked goods. We're not just picky on keeping the nasties out of our food - we're also really picky about what stays in. We're less about ticking off certain macros, more about creating food that nourishes, satisfies and delights, while also being as gut-friendly as possible.
The Wholefoods Approach
The wholefoods mindset is fundamentally holistic, taking into account where the food comes from, the taste, the enjoyment of eating, and the nutritional benefits. It's an understanding that gluten free doesn't necessarily equal healthy; paleo products are often full of shitty starches; and vegan products might be good for the environment but they can be horrible for your health if the substitutes are full of chemicals and low quality fats. It's not just about what's been left out. What's left in should be high quality, nutritious and tasty.
Wholefoods are as unprocessed/unrefined as possible, and should be free from chemicals and additives. In a way, this puts companies like ours at a disadvantage in the marketplace, as products made without chemicals and preservatives don't last as long, and are usually more expensive to make. This is why it's so important for customers to vote for what they want with their wallets - supporting local wholefoods businesses ensures that we can keep filling the shelves (and cafes) with the products you want!
Why Wholefoods Matter
Less processing means more of the original fibre and nutritional value is retained in the end product. This is one occasion where size doesn't matter! Wholefoods tend to be more nutrient dense than highly processed foods, with fewer empty calories, so you may eat less in volume but feel more satisfied and sustained.
Wholefoods are often also local, or at least contain a higher ratio of local ingredients than more refined comparable products. This means lower food miles, which is better for the environment and better for the local economy. Many foodies will also claim that wholefoods just taste better. It's a highly subjective claim, but we're sticking by it. The pecans that we source for our Cinnamon Pecan Butter from South West W.A. just taste different (and, we think, better) than pecans flown in from the other side of the world.
Baking and Wholefoods
What does it mean to be a wholefoods bakery? Well, we start with our motto - no nasties, just the good stuff. We don't do chemicals or preservatives, no artificial colours and no artificial flavours. When we make banana bread, we start with bananas. When we make our paleo pumpkin bread, we roast local pumpkin, shred fresh zucchini, and turn it into loaves. Of course some of our ingredients are processed - you can't get almond meal without processing almonds, for example. But we select ingredients that are as close to their original form as possible. We source local suppliers when we can (it's not always doable, but we try!). We use safe and nutritious oils. And we never, ever send out a product until it's passed the final test - tastes uh-mazing!
Are we doing this wholefoods thing perfectly? Probably not, but we're definitely aiming for it! If you have any feedback or ideas about how we can keep improving, comment below or drop us a line via our enquiry page, we'd love to hear from you!
Interested in learning more about wholefoods?
This New York Times article on holistic eating vs. nutritionism is a great 15 min read.


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Mississippi River View building lots in the city limits of Guttenberg with all city utilities and new sudivision. Lots located just off Acre Street on the bluff above town.
The IDX information being provided by the Northeast Iowa Regional Board of REALTORS® is exclusively for consumers' personal, non-commercial use, and it may not be used for any purpose other than to identify prospective properties consumers may be interested in purchasing. The data is deemed reliable but is not guaranteed accurate by the MLS.
Listing information last updated on October 20th, 2019 at 4:38am CDT.


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Over the years, I've been lucky to work with some amazing suppliers! Here's a list of those I've had fantastic experiences with, and am happy to recommend.
Sugar Bee Flowers
Poppy Culture
Bloom Boy
Ivy & Eve
As Daisy Does
Botanics of Melbourne
Mr Boutique
Little Buster Brown
The Baker Boys
Lark Music
Like This
The Royce Twins
Bridal Wear
Anna Campbell
One Day Bridal
Raffaele Ciuca
Eternal Bridal
Suzanne Harward
M.J. Bale
Oscar Hunt
Bell & Barnett
OTAA (accessories)
Celebrants, like most humans, are pretty unique. It's important to find one you connect with; one whom you're comfortable with, and one who can tell your story in front of your family and friends, your way.
Damon Hughes
Matt Finch
Sally Hughes
Megan Watson
Zena Lythgo
Samuel Miller
Josh Withers
DJ Lauren Mac
DJ Andrew McLelland
DJ Claire Elliott
Miss Dee
DJ Nathan Op de Coul
Music with Memories
Stones of the Yarra Valley
Yering Station
Emu Bottom Homestead
Mewburn Park Homestead
Max's Restaurant, Red Hill Estate
Tanglewood Estate
Jack Rabbit
Quat Quatta
Rupert on Rupert
Metropolis Events
Encore St Kilda
Abbotsford Convent
Crown Aviary
I can't recommend the guys below enough - I've shot alongside all of them several times, and we work well together. It's imperative that both videographer and photographer are creatively aligned to ensure the best outcome for you, so if you're considering a videographer not listed below (or if these guys happen to be booked), please consult with me before locking anything in. Trust me on this!
Tango Films
Apertura Studios
Bottlebrush Films
Nathan Kaso
Directors Edge
True Story Wedding Films
C2 Films
A word of advice: I strongly discourage you from engaging Popcorn Films. Read why here.
Miss Ladybird Cakes
Cake Ink
Peninsula Cake Art


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Keyword » puratos
Revealed: bakery trends shaping the market in 2019
Craft, freshness and the story behind bread and other baked goods are three of the biggest trends affecting bakery right now, according to supplier Puratos.
Puratos hires Vera Malhotra as marketing director
Ingredients supplier Puratos has appointed Vera Malhotra as marketing director.
Puratos rolls out savoury option in Satin mixes range
Puratos is hoping to encourage more bakers to develop savoury patisserie with the launch of a Satin Savoury Mix.
Puratos targets small firms with 10kg sourdough packs
Puratos is rolling out 10kg packs of its Sapore Medea and Sapore Rigoletto sourdoughs, targeted at smaller bakery businesses.
Revealed: five trends shaping bakery in 2018
Bakery supplier Puratos outlined some of the key trends shaping bakery in 2018 and beyond, as it celebrated the 25th anniversary of its Satin Crème Cake range last week (14 June).
Three new mixes from Puratos
Belgian bakery ingredients manufacturer Puratos has added three new products to its bakery range.
Puratos UK unveils £1.27m innovation centre
Bakery supplier Puratos UK today unveiled a £1.27m innovation centre at its UK Fringford Mill site near Bicester, Oxfordshire.
Video: Research on the Run - Inside the Puratos Sensobus
British Baker met Lydia Baines, marketing manager for Belgian ingredients manufacturer Puratos, who told us about the Puratos Sensobus.
Global study identifies key bakery trends
A global study for Belgian ingredients manufacturer Puratos has unveiled key trends in the baking, patisserie and chocolate markets.
Puratos extends ingredients offer with Italian acquisition
Ingredients and bakery firm Puratos has acquired Italian ingredients specialist Bakery Future Lines (BFL), as it plans to expand production and meet consumer demand.
My Account
Promotional Features
Most read
01 - 03 November, 2019
Cake International
12 - 14 November, 2019
European Pizza and Pasta Show
CakeWire News


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News - Corporate
Encirc furnace rebuild results in charity boost
More than £13,000 has been raised for three charities following a major redevelopment in the UK's leading complete beverage supply chain business.
Thank You DCE
Huge thank you to our corporate supporters, DCE
Camel Spiders escapades in the dessert
Flying the flag for Dreams Come True Charity across the line in 48th place, giving an overall result of 31st place.
DCE take on a new challenge
DCE are taking on a virtual Land's End to John O'Groats cycle challenge
Watch out for that big toe!
Commodity Appointments are off again! Their next ultra-running challenge is imminent.
Hamley's Dream Day Out
On Sunday the world's finest toy shop opened its doors exclusively to a very important guest list of dream families, supporters and volunteers from Dreams Come True.
Returning to Marathon Des Sables
Camel Spider endurance running team legacy lives on as we will return to another desert multi stage endurance foot race
Your spare change could make dreams come true
We are partnered with Pennies through our corporate partnership with Virgin Holidays. Pennies are the digital charity box.
Scrap Car Comparison customers are making Dreams Come True
We are delighted to be Scrap Car Comparison's Summer Charity!
Celebrating 3 Fantastic Years in Partnership with Savills
During the 3 years of working together, Savills has raised an amazing total of £270,000: enough to fulfil over 100 dreams.
Bags of Love Competiton
Win a personalised wallet for your Dad this Fathers' Day


text: Li Lu Department of Neuroscience Baylor College of Medicine Biography Publications Institution JoVE Articles Li Lu has not added a biography. If you are Li Lu and would like to personalize this page please email our Author Liaison for assistance. Publications Hippo Pathway Coactivators Yap and Taz Are Required to Coordinate Mammalian Liver Regeneration Experimental & Molecular Medicine. Jan, 2018 | Pubmed ID: 29303509 Large Tumor Suppressor Homologs 1 and 2 Regulate Mouse Liver Progenitor Cell Proliferation and Maturation Through Antagonism of the Coactivators YAP and TAZ Hepatology (Baltimore, Md.). 11, 2016 | Pubmed ID: 27531557 Construction of an Improved Multi-Tetrode Hyperdrive for Large-Scale Neural Recording in Behaving Rats Li Lu1, Briana Popeney1, J. David Dickman1, Dora E. Angelaki1 1Department of Neuroscience, Baylor College of Medicine JoVE 57388 Neuroscience


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Sidewalk Obstruction/Repair Request at 59–99 Coolidge St, Brookline
Closed over 4 years ago via iPhone
Citizens bank has huge amounts of snow blocking the sidewalk. Surely the town can enforce its laws with corporations or landlords.
request #: 9835status: Closed. Thank you for your recent request using the BrookOnline Notify Application. This has been given to proper enforcement department.
submitted: Thu Mar 12, 2015 02:09PM
opened: Thu Mar 12, 2015 02:09PM
closed: Fri Mar 13, 2015 09:02AM


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Route options
An alternative route to the one described is to follow the ascent from Telfs that goes via Mösern and Seefeld. Another option is to stay on the main road after Maurach am Achensee. This route back down into the Inn Valley is less steep and goes via Achenkanzel and Wiesing.
Burggraben 3
6020 Innsbruck


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Shop All Sale
Top Pet CalendarShop All Pets
Shop All Gifts
Shop All Sports
For those of you who aren't eternal optimists, let LIFE IS CRAP� be your anthem. Because the way we see it, the glass is usually half full... only sometimes it's half full of crap. Printed on matte paper, all calendar pages are printed on FSC certified paper with environmentally safe inks.


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Craft Beer Pioneer, Lagunitas, Signs Up to Save $22.5M in Water, Wastewater, and Energy Costs with Cambrian Innovation's WEPA
In an industry first, Lagunitas installs Cambrian's onsite EcoVolt® solution at no upfront cost Boston, MA and Azusa, CA – December 7, 2016 – Cambrian Innovation, a commercial provider of distributed wastewater treatment and resource recovery solutions for industrial facilities, today announced that one of the nation's fastest growing craft breweries, Lagunitas Brewing Company, will… View Article
Matthew Silver, Founder & CEO of Cambrian Innovation, to Keynote 7th International Complex Systems Design & Management Conference
Talk addresses the challenges and opportunities associated with sustainable water and energy infrastructure Boston, MA and Paris, France – December 5 – Matthew Silver, Founder and CEO of Cambrian Innovation, will keynote the upcoming international Complex Systems Design & Management (CSD&M) conference in Paris, France next week. The conference, hosted by the French Center of… View Article
Cambrian Innovation Welcomes New Senior Director of Operations
Brian Hemphill brings over two decades of operations experience to Cambrian Boston – December 1, 2016 – Cambrian Innovation, a biotechnology company solving critical resource challenges for industry, announced today that Brian Hemphill joined the team as Senior Director of Operations. Brian, who has spent over two decades leading operations in the wine industry, will… View Article
Cambrian Innovation and Russian River Brewing Company Announce Installation of First Standalone EcoVolt MBR
Next-generation wastewater treatment solution removes 99 percent of contaminants, producing water suitable for discharge or reuse BOSTON, MA and SANTA ROSA, CA – November 16, 2016 – Cambrian Innovation, a biotechnology company solving critical resource challenges for industry, today announced a new partnership with Russian River Brewing Company. The Sonoma County craft brewery, famous for its strong… View Article
Bear Republic Brewing Company and Cambrian Innovation Announce Successful Operation of EcoVolt Solution
Bioelectrically-enhanced solution is exceeding treatment goals and generating renewable energy BOSTON, MA and CLOVERDALE, CA – October 25, 2016 – Bear Republic Brewing Company, a family-owned brewery known for their high-revving IPAs and environmental stewardship, and Cambrian Innovation, a biotechnology company solving critical resource challenges for industry, today announced the successful, long-term operation of the… View Article
Cambrian Innovation Pilots Self-Powered Water Treatment System with U.S. Army
UNCLASSIFIED: Distribution Statement A. Approved for public release; distribution is unlimited. Army tests Cambrian's advanced BioVolt™ system for off-grid applications BOSTON, MA and CARDEROCK, MD — June 7, 2016 — Cambrian Innovation, provider of advanced biotechnology products for water and energy management, today announced a partnership with the U.S. Army to demonstrate BioVolt™, a self-powered… View Article
Cambrian Innovation and Seismic Brewing Partner in Bid for Most Water-Efficient Brewery
New Sonoma County Brewery Announces Purchase of Cambrian's EcoVolt® Solution BOSTON and SANTA ROSA, Calif. — May 3, 2016 — Cambrian Innovation, provider of distributed water and wastewater solutions for industrial producers, today announced a partnership with a new Sonoma County brewery. Seismic Brewing Company is in the midst of construction on their state-of-the-art brewery in… View Article
Cambrian Innovation Welcomes Clean Energy Pioneer, David Buzby, to Its Board of Directors
BOSTON — February 23, 2016 — Cambrian Innovation, provider of advanced biotechnology products for industrial businesses, announced today that David Buzby joined the company as Independent Director. Drawing from nearly three decades of experience investing in, and growing, world-class clean energy companies, Mr. Buzby will be an important guiding voice as Cambrian continues the rapid… View Article
Northern United Brewing Company Installs Cambrian Innovation's EcoVolt MINI
Cambrian Launches Groundbreaking, Small-Scale Wastewater Treatment Solution BOSTON and DEXTER, Mich. — December 1, 2015 — Cambrian Innovation, provider of distributed water and wastewater solutions for industrial producers, today announced Northern United Brewing Company (NUBC) is the first customer to install Cambrian's EcoVolt® MINI. The EcoVolt MINI converts high-strength wastewater into reusable quality water in one simple… View Article
Cambrian Innovation Launches $30M Fund to Finance Distributed Clean Water Solutions
Water-energy purchase agreement eliminates upfront costs for onsite clean water and energy solutions BOSTON — November 18, 2015 — Cambrian Innovation, provider of biotechnology solutions for industrial partners, today announced the launch of a pioneering financing vehicle for distributed clean water and energy solutions backed by a $30M fund. Under the new financing mechanism, called… View Article


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Eros is the god of love, passion and physical desire in Greek mythology. He is also the protector of homosexual love. Known as an archer, Eros shot arrows at unsuspecting people, causing them to fall in love with the first person they saw. In various accounts, Eros is either the son of Aphrodite and Ares, Aphrodite's assistant or a primeval god who assisted in creation.
Eros shot arrows randomly, aiming for the heart of his target. Those hit with an arrow became confused and exhibited irrepressible feelings. Some of Eros' targets were other gods, including Apollo, who ridiculed Eros's archery skills. Eros retaliated by shooting Apollo with an arrow, which made Apollo fall in love with a nymph named Daphne.
One account of Eros states his mother, Aphrodite, was jealous of Psyche, a beautiful mortal princess. Aphrodite told Eros to shoot an arrow into Psyche and make her fall in love with the ugliest person on Earth. Instead, Eros fell in love with Psyche, and they became a couple. Later, Psyche betrayed Eros, and he abandoned her; eventually, the two reconciled, and Psyche became immortal. The two had a daughter named Hedone or Voluptus.
In Roman mythology, the god of love is Cupid.


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A former Barbados Labour Party (BLP) candidate is suggesting that the Opposition party needs former Prime Minister Owen Arthur now more than ever.
In fact, following Arthur's decision to quit the party back in 2014, Hudson Griffith believes that the Mia Mottley-led BLP does not stand a chance of winning the next election, constitutionally due by the middle of next year.
"[They are] only fooling themselves into believing that victory at the next general election is inevitable, having severed ties with former Prime Minister Owen Arthur," said Griffith, in an impassioned address to a United Progressive Party (UPP) meeting in Shorey Village, St Andrew last weekend.
Insisting that he was baffled by his former party's confidence of winning the next poll, the twice unsuccesful St John candidate argued that Arthur's controversial departure, which came at the height of his dissatisfaction with Mottley's leadership style, had left a major void that was yet to be filled.
Arthur, who was elected to the House of Assembly in 1984, served as Prime Minister during one of the more prosperous periods of the country's economic history from 1994 to 2008.
But Griffith, who recently quit the BLP in less than amicable circumstances and has since pledged his allegiance to the UPP, contended that Arthur was much more than just a good Prime Minister and was responsible for "rescuing the BLP".
"I can't see how the Barbados Labour Party is expecting to be returned to Government in 2018. What have they done? They don't have Owen Arthur, who rescued and rebuilt the BLP in 1994 when they only had three people in Parliament.
"Wunna remember when they get beat to three blind mice? It was Owen Arthur, Henry Forde and David Simmons and it was Arthur who rebuilt the Barbados Labour Party. So I am wondering why the Barbados Labour Party is thinking that they are capable of winning," Griffith stressed.
He further suggested that the birth of the UPP, who includes several BLP defectors, including leader Lynette Eastmond, was partly as a result of Arthur's departure.
The former BLP candidate for St John also charged that there were fundamental issues with Mottley's leadership.
"You feel that the UPP just start for the sake of starting? I never plan for this. Lynette Eastmond never plan to start the UPP," he told the small gathering of UPP supporters.
Griffith, who has also accused the current BLP hierarchy of "humiliating and betraying" him after turning in the party's best showing in St John in the 2013 general election, acknowledged that there were still some good people within that party and he suggested that they had a duty to expose the goings on in the BLP if they wished to see the 79-year-old party return to its former glory.
He specifically called on Member of Parliament for St Andrew George Payne, who is also the BLP chairman, to stand up and be counted.
"The MP [Member of Parliament] for St Andrew is a good man, I have nothing against him but he is keeping some secrets in a Pandora's box. We need to kick down that bloody box and break that lock and let we see what skeletons jump out of the Barbados Labour Party," said Griffith.


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Unique Floral Arrangements That Show Sympathy for Those You Love
When someone passes away, it is natural to want to show your respect and sympathy to those around you. The unique flower arrangements that Fort Lauderdale, FL, florists offer are perfect for expressing the occasion. Whether you are selecting an arrangement to honor someone you love, or simply want to show your sympathy to a friend, flower arrangements are a timeless form of endearment.
Wreaths can be created with real flowers or silk. One that is made with artificial or dried flowers can be kept by the family after the services are over, while fragrant real flowers are always a beautiful choice. Wreaths are displayed on an easel, and they can be adorned with a ribbon stating the relationship of the deceased to you and your family.
Living Baskets
Living baskets are simply containers filled with plants rather than cut flowers. The family members of the departed may take the plants home as a gift after the services are over. Many people feel more justified in purchasing something the loved ones can keep rather than investing in blooms. Both are beautiful, and the chosen plants can have a variety of colors other than just green.
Special Arrangements
You can also choose to have a traditional bouquet of cut flowers sent. Florists often arrange them in an elegant glass vase, basket, or some other type of container. You can request to have items included such as an angel figurine, a cross, a collectible, or an item that reflects the departed's passion.
Whether you choose a wreath, living basket, or another arrangement, the unique arrangements that Fort Lauderdale, FL, flower shops offer can help you show your love and sympathy in a traditional manner. These special designs are the perfect way to honor a loved one or show respect for a close friend.