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 host–guest 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 $\approx 1$. 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 $t \propto Re$. 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

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

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 host–guest 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 host–guest charge transfer (HGCT)

Morphological control of heteroleptic cis- and trans-Pd2L2Lʹ2 cages

Control over the integrative self-sorting of metallo-supramolecular assemblies has recently generated significant interest as it opens up possibilities of introducing increased complexity and function into a single self-assembled architecture. Here, the relationship between the geometry of three ligand components and morphology of three self-sorted heteroleptic [Pd2L2Lʹ2]4+ cages is examined. Pd-mediated assembly of two bis-monodentate pyridyl ligands with native bite angles of 75° and 120° affords a cis-[Pd2L2Lʹ2]4+ cage while the same reaction with two ligands bearing bite angles of 75° and 60° forces an anti-conformation for latter ligand, leading to an unprecedented, self-penetrating structural motif; a trans-[Pd2(anti-L)2Lʹ2]4+ heteroleptic cage bearing a “doubly-bridged figure-eight” topology. Each heteroleptic assembly can be accessed through cage-to-cage conversion of their homoleptic precursors, and notably, morphological control of [Pd2L2Lʹ2] cages is achieved through selective ligand displacement transformations in a system of three ligands and at least six possible cage products