1,014 research outputs found
Theoretical prediction of airplane stability derivatives at subcritical speeds
The theoretical development and application is described of an analysis for predicting the major static and rotary stability derivatives for a complete airplane. The analysis utilizes potential flow theory to compute the surface flow fields and pressures on any configuration that can be synthesized from arbitrary lifting bodies and nonplanar thick lifting panels. The pressures are integrated to obtain section and total configuration loads and moments due side slip, angle of attack, pitching motion, rolling motion, yawing motion, and control surface deflection. Subcritical compressibility is accounted for by means of the Gothert similarity rule
Increasing structural and functional complexity in self-assembled coordination cages
Progress in metallo-supramolecular chemistry creates potential to synthesize functional nano systems and intelligent materials of increasing complexity. In the past four decades, metal-mediated self-assembly has produced a wide range of structural motifs such as helicates, grids, links, knots, spheres and cages, with particularly the latter ones catching growing attention, owing to their nano-scale cavities. Assemblies serving as hosts allow application as selective receptors, confined reaction environments and more. Recently, the field has made big steps forward by implementing dedicated functionality, e.g. catalytic centres or photoswitches to allow stimuli control. Besides incorporation in homoleptic systems, composed of one type of ligand, desire arose to include more than one function within the same assembly. Inspiration comes from natural enzymes that congregate, for example, a substrate recognition site, an allosteric regulator element and a reaction centre. Combining several functionalities without creating statistical mixtures, however, requires a toolbox of sophisticated assembly strategies. This review showcases the implementation of function into self-assembled cages and devises strategies to selectively form heteroleptic structures. We discuss first examples resulting from a combination of both principles, namely multicomponent multifunctional hostâguest complexes, and their potential in application in areas such as sensing, catalysis, and photo-redox systems
Defect turbulence in inclined layer convection
We report experimental results on the defect turbulent state of undulation
chaos in inclined layer convection of a fluid withPrandtl number .
By measuring defect density and undulation wavenumber, we find that the onset
of undulation chaos coincides with the theoretically predicted onset for
stable, stationary undulations. At stronger driving, we observe a competition
between ordered undulations and undulation chaos, suggesting bistability
between a fixed-point attractor and spatiotemporal chaos. In the defect
turbulent regime, we measured the defect creation, annihilation, entering,
leaving, and rates. We show that entering and leaving rates through boundaries
must be considered in order to describe the observed statistics. We derive a
universal probability distribution function which agrees with the experimental
findings.Comment: 4 pages, 5 figure
Ultrafast IR spectroscopy of photo-induced electron transfer in self-assembled donor-acceptor coordination cages.
Photo-induced processes in self-assembled coordination cages were studied by femtosecond infrared pump-probe spectroscopy. Densely packed, interpenetrated double cages were constructed from eight bis-monodentate redoxactive ligands bound to four Pd(ii) nodes. Two types of ligands consisting of electron rich phenothiazine (PTZ) or electron deficient anthraquinone (ANQ) chromophores were used to assemble either homo-octameric or mixed-ligand cages. Upon photoexcitation the homo-octameric acceptor cage undergoes intersystem crossing to a long-lived triplet state, similar to the free acceptor ligand. Excitation of the free donor ligand leads to a fluorescent state with intramolecular charge transfer character. This fluorescence is completely quenched in the homo-octameric donor double cage due to a ligand-to-metal charge transfer followed by back electron transfer on a ps timescale. Only for the mixed-ligand cage irradiation produces a charge separated state with an oxidized PTZ radical cation and a reduced ANQ radical anion as proven by their vibrational fingerprints in the transient IR spectra. In dichloromethane the lifetime of this charge separated state extends from tens of ps to >1.5 ns which is attributed to the broad distribution of mixed-ligand cages with different stoichiometry and/or stereo configurations
Localized transverse bursts in inclined layer convection
We investigate a novel bursting state in inclined layer thermal convection in
which convection rolls exhibit intermittent, localized, transverse bursts. With
increasing temperature difference, the bursts increase in duration and number
while exhibiting a characteristic wavenumber, magnitude, and size. We propose a
mechanism which describes the duration of the observed bursting intervals and
compare our results to bursting processes in other systems.Comment: 4 pages, 8 figure
Fractal Stability Border in Plane Couette Flow
We study the dynamics of localised perturbations in plane Couette flow with
periodic lateral boundary conditions. For small Reynolds number and small
amplitude of the initial state the perturbation decays on a viscous time scale
. For Reynolds number larger than about 200, chaotic transients
appear with life times longer than the viscous one. Depending on the type of
the perturbation isolated initial conditions with infinite life time appear for
Reynolds numbers larger than about 270--320. In this third regime, the life
time as a function of Reynolds number and amplitude is fractal. These results
suggest that in the transition region the turbulent dynamics is characterised
by a chaotic repeller rather than an attractor.Comment: 4 pages, Latex, 4 eps-figures, submitted to Phys. Rev. Le
Photoinduced host-to-guest electron transfer in a self-assembled coordination cage
A [Pd2L4] coordination cage, assembled from electron-rich phenothiazine-based ligands and encapsulating an electron-deficient anthraquinone-based disulfonate guest, is reported. Upon excitation at 400 nm, transient absorption spectroscopy unveils photoinduced electron transfer from the host's chromophores to the guest, as indicated by characteristic spectral features assigned to the oxidized donor and reduced acceptor. The structure of the hostâguest complex was characterized by NMR spectroscopy, mass spectrometry and single-crystal X-ray analysis. Spectroelectrochemical experiments and DFT calculations both agree with the proposed light-induced charge separation. A kinetic analysis of the involved charge transfer channels reveals, besides a guest-independent LMCT path, 44% efficiency for the hostâguest charge transfer (HGCT)
Wavy stripes and squares in zero P number convection
A simple model to explain numerically observed behaviour of chaotically
varying stripes and square patterns in zero Prandtl number convection in
Boussinesq fluid is presented. The nonlinear interaction of mutually
perpendicular sets of wavy rolls, via higher mode, may lead to a competition
between the two sets of wavy rolls. The appearance of square patterns is due to
the secondary forward Hopf bifurcation of a set of wavy rolls.Comment: 8 pages and 3 figures, late
Backbone-bridging promotes diversity in heteroleptic cages
The combination of shape-complementary bis-monodentate ligands LA and LB with PdII cations yields heteroleptic cages cis-[Pd2LA2LB2] by self-sorting. Herein, we report how such assemblies can be diversified by introduction of covalent backbone bridges between two LA units. Together with solvent and guest effects, the flexibility of these linkers can modulate nuclearity, topology, and number of cavities in a family of four structurally diverse assemblies. Ligand LA1, with flexible linker, reacts in CH3CN with its LB counterpart to a tetranuclear dimer D1. In DMSO, however, a trinuclear pseudo-tetrahedron T1 is formed. The product of LA2, with rigid linker, looks similar to D1, but with a rotated ligand arrangement. In presence of an anionic guest, this dimer D2 transforms and a hexanuclear prismatic barrel P2 crystallizes. We demonstrate how controlling a ligand's coordination mode can trigger structural differentiation and increase complexity in metallo-supramolecular assembly
Tunable fullerene affinity of cages, bowls and rings assembled by Pd(II) coordination sphere engineering
For metalâmediated host compounds, the development of strategies to reduce symmetry and introduce multiple functionalities in a nonâstatistical way is a challenging task. We show that the introduction of steric stress around the coordination environment of squareâplanar Pd(II) cations and bisâmonodentate nitrogen donor ligands allows to control the size and shape of the assembly product, from [Pd2L4] cages over [Pd2L3] bowlâshaped structures to [Pd2L2] rings. Therefore, bananaâshaped ligand backbones were equipped with pyridines, two different quinoline isomers and acridine, the latter three introducing steric congestion through hydrogen substituents on annelated benzene rings. Differing behavior of the four resulting hosts towards the binding of C60 and C70 fullerenes was studied and related to structural differences by NMR spectroscopy, mass spectrometry and single crystal Xâray diffraction. The three cages based on pyridine, 6âquinoline or 3âquinoline donors were found to either bind C60, C70 or no fullerene at all
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