The design and synthesis of a new potentially C3-symmetric ferrocenylphosphine

A new potentially C₃-symmetric phosphine ligand ‘manphos’ has been obtained and fully characterized. The ligand which is a tri-ferrocenyl-tetra-phosphine is obtained in a simple and effective two step synthesis starting from 1,1′-dibromoferrocene via the intermediate compound tris-(1′-bromoferrocenyl)phosphine or alternatively via 1'-bromo-1-diphenylphosphinoferrocene. The iso-propylphosphino-analogue of manphos, tris-(1'-diisopropylphosphinoferrocenenyl)phosphine, has also been obtained, in addition to several functionalised derivatives of triferrocenylphosphine where the ferrocene rings have been substituted in the 1′-position.     

Flavonoids from Artocarpus lanceifolius

One new compound, 14-hydroxyartonin E (1), together with the known compound, artonin E (2), was isolated from Artocarpus lanceifolus. Their structures were elucidated by spectroscopic methods.     

The Playground Shade Index: A New Design Metric for Measuring Shade and Seasonal Ultraviolet Protection Characteristics of Parks and Playgrounds

Current shading strategies used to protect outdoor playgrounds from harmful solar radiation include the placement of artificial cloth weaves or permanent roofing over a playground site, planting trees in proximity to playground equipment, and using vegetation or surface texture variations to cool playground surfaces. How and where an artificial shade structure is placed or a tree is planted to maximize the shade protection over specific playground areas, requires careful assessment of local seasonal sun exposure patterns. The Playground Shade Index (PSI) is introduced here as a design metric to enable shade and solar ultraviolet exposure patterns to be derived in an outdoor space using conventional aerial views of suburban park maps. The implementation of the PSI is demonstrated by incorporating a machine learning design tool to classify the position of trees from an aerial image, thus enabling the mapping of seasonal shade and ultraviolet exposure patterns within an existing 7180 m² parkland. This is achieved by modeling the relative position of the sun with respect to nearby buildings, shade structures, and the identified evergreen and deciduous tree species surrounding an outdoor playground.     

Simulations of concentrated suspensions of rigid fibers: relationship between short-time diffusivities and the long-time rotational diffusion

Brownian dynamics simulations of the behavior of suspensions of fibers demonstrate that the scaling of the rotational diffusivity with respect to the number density (nL3) is a sensitive function of the thickness and the parameter L2D(R0)/D(T0), where D(R0) is the rotational diffusivity at infinite dilution, D(T0) is the average center-of-mass diffusivity at infinite dilution, and L is the fiber length. Existing theories for the long-time rotational diffusivities of rigid fibers in the semidilute and concentrated regimes fail to accurately account for the relationship with the dilute values of the rotational and translational diffusivities of the various physical models used to simulate the fibers. The concentration regime studied in this work ranges from a number density of nL3 approximately 0-150, which is below the transition from an isotropic to nematic state. The effect of the fiber thickness was studied by performing simulations of rods with aspect ratios (fiber length over diameter) of 25, 50, and 500, as well as performing projections for infinitely thin fibers. The excluded volume of the rods was enforced through the use of short-range potentials. For a rod with an aspect ratio of 50 with a parameter of L2D(R0)/D(T0)=9, which corresponds to a slender-body model of the individual fibers, the rotational diffusivity (D(R)) scales as D(R)/D(R0) approximately (nL3)(-1.9) in the concentration regime of 70 < or = nL3 < or = 150. Similarly with a parameter of L2D(R0)/D(T0)=4, corresponding to a rigid-dumbbell model, the rotational diffusivity scales as D(R)/D(R0) approximately (nL3)(-1.1) over the same range of concentrations. For rods with aspect ratios of 25, it is observed that a difference in the scaling is seen for L2D(R0)/D(T0) approximately < 8, with higher values of this ratio exhibiting essentially the same scaling. Additional values of the ratio L2D(R0)/D(T0) were investigated to determine the overall behavior of the suspension dynamics with respect to this parameter. These findings resolve discrepancies between simulation results for rotational diffusivities reported by previous investigators and provide new insights for the development of an accurate theory for the diffusivity of rigid rods suspended in solution.     

Probing the barrier for CH2CHCO --> CH2CH + CO by the velocity map imaging method

This work determines the dissociation barrier height for CH2CHCO --> CH2CH + CO using two-dimensional product velocity map imaging. The CH2CHCO radical is prepared under collision-free conditions from C-Cl bond fission in the photodissociation of acryloyl chloride at 235 nm. The nascent CH2CHCO radicals that do not dissociate to CH2CH + CO, about 73% of all the radicals produced, are detected using 157-nm photoionization. The Cl(2P(3/2)) and Cl(2P(1/2)) atomic fragments, momentum matched to both the stable and unstable radicals, are detected state selectively by resonance-enhanced multiphoton ionization at 235 nm. By comparing the total translational energy release distribution P(E(T)) derived from the measured recoil velocities of the Cl atoms with that derived from the momentum-matched radical cophotofragments which do not dissociate, the energy threshold at which the CH2CHCO radicals begin to dissociate is determined. Based on this energy threshold and conservation of energy, and using calculated C-Cl bond energies for the precursor to produce CH2CHC*O or C*H2CHCO, respectively, we have determined the forward dissociation barriers for the radical to dissociate to vinyl + CO. The experimentally determined barrier for CH2CHC*O --> CH2CH + CO is 21+/-2 kcal mol(-1), and the computed energy difference between the CH2CHC*O and the C*H2CHCO forms of the radical gives the corresponding barrier for C*H2CHCO --> CH2CH + CO to be 23+/-2 kcal mol(-1). This experimental determination is compared with predictions from electronic structure methods, including coupled-cluster, density-functional, and composite Gaussian-3-based methods. The comparison shows that density-functional theory predicts too low an energy for the C*H2CHCO radical, and thus too high a barrier energy, whereas both the Gaussian-3 and the coupled-cluster methods yield predictions in good agreement with experiment. The experiment also shows that acryloyl chloride can be used as a photolytic precursor at 235 nm of thermodynamically stable CH2CHC*O radicals, most with an internal energy distribution ranging from approximately 3 to approximately 21 kcal mol(-1). We discuss the results with respect to the prior work on the O(3P) + propargyl reaction and the analogous O(3P) + allyl system.     

ChemInform Abstract: Polymorph Engineering of TiO2: Demonstrating How Absolute Reference Potentials Are Determined by Local Coordination.

A multiscale quantum‐chemical approach is used for examining the electronic structure of eight known TiO₂ polymorphs and aligning their ionization potential and electron affinity relative to an absolute energy reference.