Synthetic studies directed toward the AB decalin common to HMP-Y1 and hibarimicinone

Efforts toward the synthesis of the decalin ring system common to the hibarimicin shunt metabolite HMP-Y1 and parent aglycone hibarimicinone are reported herein. An intramolecular Diels–Alder cyclization rapidly generated the decalin framework. Two approaches toward completion of the AB decalin were vetted. Incorporation of a phenylsulfonyl leaving group β- to both a ketone and a γ-lactone followed by base-induced elimination of sulfinate led to the undesired α,β-unsaturated lactone. Methanolysis of the γ-lactone followed by elimination produced the unexpected bridged cyclic ether by way of an intramolecular oxy-Michael addition of the endo oriented C13 alcohol.     

E-FiRST: Electric field responsive shear thickening fluids

A novel electrorheological (ER) effect is presented where the application of an electric field, orthogonal to the vorticity-flow plane, increases the critical hydrodynamic stress required to shear thicken concentrated, colloidal dispersions (the E-FiRST effect). The shear thickening behavior of a Brownian charge stabilized dispersion (226 nm silica in 4-methylcyclohexanol at 53, 50. and 41 vol.%) is studied in the presence of an electric field as a function of the field strength and coupling parameter ( ß) where the latter is a function of a.c. field frequency due to diffusion limitations on the polarization of the particles' double layer. A mechanism is proposed whereby the applied electric field suppresses the formation of the self-organized hydrocluster microstructure responsible for shear thickening, thus delaying the onset of shear thickening to higher applied shear stresses. A Mason-number type scaling law is found to scale the effect, which supports the proposed mechanism.     

Phosphate anion chelation and base-pairing. Design of receptors and carriers for nucleotides and nucleotide analogues

Abstract

A rational approach to the development of effective carriers for the through-membrane transport of GMP (guanosine 5′-monophosphate) at neutral pH is described. The approach detailed is a ditopic one predicated on the use of nucleic acid-base ‘nucleobase’ subunits to provide stabilizing hydrogen bonding interactions and the use of expanded porphyrin anion binding subunits to provide phosphate chelation. Appropriate background studies along with the synthesis of a functioning state-of-the-art system are reported. In addition, the reasons for preparing such GMP transport systems are presented in full.     

Extensional rheology of a shear-thickening cornstarch and water suspension

A filament-stretching rheometer is used to measure the extensional viscosity of a shear-thickening suspension of cornstarch in water. The experiments are performed at a concentration of 55 wt.%. The shear rheology of these suspensions demonstrates a strong shear-thickening behavior. The extensional rheology of the suspensions demonstrates a Newtonian response at low extension rates. At moderate strain rates, the fluid strain hardens. The speed of the strain hardening and the extensional viscosity achieved increase quickly with increasing extension rate. Above a critical extension rate, the extensional viscosity goes through a maximum and the fluid filaments fail through a brittle fracture at a constant tensile stress. The glassy response of the suspension is likely the result of jamming of particles or clusters of particles at these high extension rates. This same mechanism is responsible for the shear thickening of these suspensions. In capillary breakup extensional rheometry, measurement of these suspensions demonstrates a divergence in the extensional viscosity as the fluid stops draining after a modest strain is accumulated.     

Measurements of mean and fluctuating temperature in an underexpanded jet using electrostrictive laser-induced gratings

Instantaneous temperature measurements were obtained in an underexpanded jet using electrostrictive laser-induced gratings. Evaluation of the technique under static, low-pressure conditions provided a baseline uncertainty or precision for single-shot temperature measurements of 4.4% of the local mean temperature, which represents the minimum detectable temperature fluctuation. The underexpanded jet was operated at a nozzle pressure ratio of 2.39 and a fully expanded jet Mach number of 1.19. Data were acquired along the centerline and over two radial traverses through the shear layer. Mean temperature data agree well with expectations, describing the shock-cell structure and the compressible shear layer. The growth in shear-layer width with downstream distance can be identified in the mean and fluctuating temperature measurements. Temperature fluctuations are near the baseline detection limit in the jet core and surrounding ambient air, and reach a maximum in the shear layer. The temperature fluctuation measurements compare well with previous computational and experimental work, confirming the application of the technique to a turbulent, supersonic flow.     

Multi-scale interactions in a compressible boundary layer

The properties of spectral subranges of scales in a boundary layer at Mach=2.3 and friction Reynolds number Reτ = 570 are investigated by analysing DNS data. One major aim is to examine whether footprinting and modulation of small-scale near-wall motions by outer large structures, observed at high Reynolds numbers, also pertain to this low-Reynolds-number case, or whether the logarithmic layer simply contains a continuous hierarchy of motions without specific outer scales playing a distinctive role. To this end, the spectrum of scales is decomposed into modes by application of the “Empirical Mode Decomposition”. The properties of different scales are then investigated by means of spectra, maps of isotropy/anisotropy parameters, the premultiplied derivative of the second-order structure function, correlation coefficients and joint probability density function (PDF), the last constructed from conditionally sampled data for the small-scale motions within the large-scale footprints. A clear commonality is identified between interactions in high-Reynolds-number channel flow and the present low-Reynolds-number boundary layer.     

Large amplitude oscillatory shear rheology of three different shear-thickening particle dispersions

We present a large amplitude oscillatory shear rheology (LAOS) investigation of three different shear-thickening particle dispersions - fumed silica in polyethylene oxide (FLOC), fumed silica in polypropylene glycol (HydroC), and cornstarch in water (JAM). These systems shear-thicken by three different mechanisms - shear-induced formation of particle clusters flocculated by polymer bridging, hydrocluster formation, and jamming. The viscoelastic non-linearities of the three fluids were studied as a function of strain and strain-rate space through the use of Lissajous-Bowditch curves and local nonlinear viscoelastic moduli of an oscillatory shear cycle. The nonlinear behaviors of the three fluids were compared and contrasted to understand the nonlinear shear-thickening mechanism of each. Both HydroC and JAM dispersions were found to exhibit strong strain stiffening of the elastic moduli and strain thickening of the loss moduli behavior associated with possible hydrocluster formation and particle jamming. However, the FLOC dispersion, in contrast, showed strong strain softening and strain thinning behavior at large strain amplitudes associated with yielding of the microstructure. The expected thickening of the loss modulus of FLOC in LAOS with increasing strain was not observed even though viscosity of FLOC was found to shear-thicken in steady-shear measurements. This disagreement is likely due to very large strain amplitudes required for shear-thickening to occur by shear-induced polymer bridging mechanism. The hypothesis was confirmed through stress growth experiments. Conversely, the HydroC and JAM dispersions required relatively small applied strains for shear-thickening to occur by hydrocluster and jamming mechanism. The comparison of local intra-cycle nonlinearity through Lissajous-Bowditch plots and nonlinear viscoelastic parameters indicated that the elastic nonlinearities of all three systems are primarily driven by a strong dependence on the magnitude of the applied strain-rates within an oscillatory cycle rather than the amplitude of the applied strain. A close inspection of the LAOS data reveals strong differences in the viscoelastic nonlinearities of these three different shear-thickening dispersions which can be used to create a nonlinear rheological fingerprint for each and offers valuable new insights into the nonlinear dynamics associated with each of the shear-thickening mechanisms.     

Experimental validation of a dynamic resonant wall shear stress sensor

Experimental measurements are used to validate a numerical model of a dynamic resonant wall shear stress sensor. The numerical model consists of an unsteady two-dimensional boundary-layer model for the flow and a simple mechanical model for the sensor itself. The sensor’s sensitivity to wall shear stress is experimentally determined in a flat-plate boundary layer, and the results agree closely with those from the numerical simulations. Using the validated model, it is determined that the energy lost in each sensor oscillation due to the interaction between the sensor and fluid increases with increasing mean wall shear stress.     

Wave-modulated orbits in rate-and-state friction

A frictional spring-block system has been widely used historically as a model to display some of the features of two slabs in sliding frictional contact. Putelat et al. (2008) [7] demonstrated that equations governing the sliding of two slabs could be approximated by spring-block equations, and studied relaxation oscillations for two slabs driven by uniform relative motion at their outer surfaces, employing this approximation. The present work revisits this problem. The equations of motion are first formulated exactly, with full allowance for wave reflections. Since the sliding is restricted to be independent of position on the interface, this leads to a set of differential-difference equations in the time domain. Formal but systematic asymptotic expansions reduce the equations to differential equations. Truncation of the differential system at the lowest non-trivial order reproduces a classical spring-block system, but with a slightly different “equivalent mass” than was obtained in the earlier work. Retention of the next term gives a new system, of higher order, that contains also some explicit effects of wave reflections. The smooth periodic orbits that result from the spring-block system in the regime of instability of steady sliding are “decorated” by an oscillation whose period is related to the travel time of the waves across the slabs. The approximating differential system reproduces this effect with reasonable accuracy when the mean sliding velocity is not too far from the critical velocity for the steady state. The differential system also displays a period-doubling bifurcation as the mean sliding velocity is increased, corresponding to similar behaviour of the exact differential-difference system.