The Inertio-Elastic Planar Entry Flow of Low-Viscosity Elastic Fluids in Micro-fabricated Geometries

The non-Newtonian flow of dilute aqueous polyethylene oxide (PEO) solutions through microfabricated planar abrupt contraction-expansions is investigated. The contraction geometries are fabricated from a high-resolution chrome mask and cross-linked PDMS gels using the tools of soft-lithography. The small length scales and high deformation rates in the contraction throat lead to significant extensional flow effects even with dilute polymer solutions having time constants on the order of milliseconds. The dimensionless extra pressure drop across the contraction increases by more than 200% and is accompanied by significant upstream vortex growth. Streak photography and videomicroscopy using epifluorescent particles shows that the flow ultimately becomes unstable and three-dimensional. The moderate Reynolds numbers (0.03 ⤠Re ⤠44) associated with these high Deborah number (0 ⤠De ⤠600) microfluidic flows results in the exploration of new regions of the Re-De parameter space in which the effects of both elasticity and inertia can be observed. Understanding such interactions will be increasingly important in microfluidic applications involving complex fluids and can best be interpreted in terms of the elasticity number, El = De/Re, which is independent of the flow kinematics and depends only on the fluid rheology and the characteristic size of the device.NS

CN and HCN in Dense Interstellar Clouds

We present a theoretical investigation of CN and HCN molecule formation in dense interstellar clouds. We study the gas-phase CN and HCN production efficiencies from the outer photon-dominated regions (PDRs) into the opaque cosmic-ray dominated cores. We calculate the equilibrium densities of CN and HCN, and of the associated species C+, C, and CO, as functions of the far-ultraviolet (FUV) optical depth. We consider isothermal gas at 50 K, with hydrogen particle densities from 10^2 to 10^6 cm^-3. We study clouds that are exposed to FUV fields with intensities 20 to 2*10^5 times the mean interstellar FUV intensity. We assume cosmic-ray H2 ionization rates ranging from 5*10^-17 s^-1, to an enhanced value of 5*10^-16 s^-1. We also examine the sensitivity of the density profiles to the gas-phase sulfur abundance.Comment: Accepted for publication in ApJ, 33 pages, 8 figure

A simple vapor-diffusion method enables protein crystallization inside the HARE serial crystallography chip

Fixed-target serial crystallography has become an important method for the study of protein structure and dynamics at synchrotrons and X-ray free-electron lasers. However, sample homogeneity, consumption and the physical stress on samples remain major challenges for these high-throughput experiments, which depend on high-quality protein microcrystals. The batch crystallization procedures that are typically applied require time- and sample-intensive screening and optimization. Here, a simple protein crystallization method inside the features of the HARE serial crystallography chips is reported that circumvents batch crystallization and allows the direct transfer of canonical vapor-diffusion conditions to in-chip crystallization. Based on conventional hanging-drop vapor-diffusion experiments, the crystallization solution is distributed into the wells of the HARE chip and equilibrated against a reservoir with mother liquor. Using this simple method, high-quality microcrystals were generated with sufficient density for the structure determination of four different proteins. A new protein variant was crystallized using the protein concentrations encountered during canonical crystallization experiments, enabling structure determination from ∼55 µg of protein. Additionally, structure determination from intracellular crystals grown in insect cells cultured directly in the features of the HARE chips is demonstrated. In cellulo crystallization represents a comparatively un­explored space in crystallization, especially for proteins that are resistant to crystallization using conventional techniques, and eliminates any need for laborious protein purification. This in-chip technique avoids harvesting the sensitive crystals or any further physical handling of the crystal-containing cells. These proof-of-principle experiments indicate the potential of this method to become a simple alternative to batch crystallization approaches and also as a convenient extension to canonical crystallization screens

Expanding the Repertoire of Natural Product-Inspired Ring Pairs for Molecular Recognition of DNA

A furan amino acid, inspired by the recently discovered proximicin natural products, was incorporated into the scaffold of a DNA-binding hairpin polyamide. While unpaired oligomers of 2,4-disubstituted furan amino acids show poor DNA-binding activity, furan (Fn) carboxamides paired with N-methylpyrrole (Py) and N-methylimidazole (Im) rings demonstrate excellent stabilization of duplex DNA as well as discrimination of noncognate sequences, consistent with function as a Py mimic according to the Py/Im polyamide pairing rules

Elastic turbulence in curvilinear flows of polymer solutions

Following our first report (A. Groisman and V. Steinberg, \sl Nature $\bf 405$, 53 (2000)) we present an extended account of experimental observations of elasticity induced turbulence in three different systems: a swirling flow between two plates, a Couette-Taylor (CT) flow between two cylinders, and a flow in a curvilinear channel (Dean flow). All three set-ups had high ratio of width of the region available for flow to radius of curvature of the streamlines. The experiments were carried out with dilute solutions of high molecular weight polyacrylamide in concentrated sugar syrups. High polymer relaxation time and solution viscosity ensured prevalence of non-linear elastic effects over inertial non-linearity, and development of purely elastic instabilities at low Reynolds number (Re) in all three flows. Above the elastic instability threshold, flows in all three systems exhibit features of developed turbulence. Those include: (i)randomly fluctuating fluid motion excited in a broad range of spatial and temporal scales; (ii) significant increase in the rates of momentum and mass transfer (compared to those expected for a steady flow with a smooth velocity profile). Phenomenology, driving mechanisms, and parameter dependence of the elastic turbulence are compared with those of the conventional high Re hydrodynamic turbulence in Newtonian fluids.Comment: 23 pages, 26 figure

Simulations of extensional flow in microrheometric devices

We present a detailed numerical study of the flow of a Newtonian fluid through microrheometric devices featuring a sudden contraction–expansion. This flow configuration is typically used to generate extensional deformations and high strain rates. The excess pressure drop resulting from the converging and diverging flow is an important dynamic measure to quantify if the device is intended to be used as a microfluidic extensional rheometer. To explore this idea, we examine the effect of the contraction length, aspect ratio and Reynolds number on the flow kinematics and resulting pressure field. Analysis of the computed velocity and pressure fields show that, for typical experimental conditions used in microfluidic devices, the steady flow is highly three-dimensional with open spiraling vortical structures in the stagnant corner regions. The numerical simulations of the local kinematics and global pressure drop are in good agreement with experimental results. The device aspect ratio is shown to have a strong impact on the flow and consequently on the excess pressure drop, which is quantified in terms of the dimensionless Couette and Bagley correction factors. We suggest an approach for calculating the Bagley correction which may be especially appropriate for planar microchannels

Switching the stereochemical outcome of 6-endo-trig cyclizations; Synthesis of 2,6-Cis-6-substituted 4-oxopipecolic acids

A base-mediated 6-endo-trig cyclization of readily accessible enone-derived α-amino acids has been developed for the direct synthesis of novel 2,6-cis-6- substituted-4-oxo-L-pipecolic acids. A range of aliphatic and aryl side chains were tolerated by this mild procedure to give the target compounds in good overall yields. Molecular modeling of the 6-endo-trig cyclization allowed some insight as to how these compounds were formed, with the enolate intermediate generated via an equilibrium process, followed by irreversible tautomerization/neutralization providing the driving force for product formation. Stereoselective reduction and deprotection of the resulting 2,6-cis-6-substituted 4-oxo-L-pipecolic acids to the corresponding 4-hydroxy-L-pipecolic acids was also performed

Measurement of 222Rn dissolved in water at the Sudbury Neutrino Observatory

The technique used at the Sudbury Neutrino Observatory (SNO) to measure the concentration of 222Rn in water is described. Water from the SNO detector is passed through a vacuum degasser (in the light water system) or a membrane contact degasser (in the heavy water system) where dissolved gases, including radon, are liberated. The degasser is connected to a vacuum system which collects the radon on a cold trap and removes most other gases, such as water vapor and nitrogen. After roughly 0.5 tonnes of H2O or 6 tonnes of D2O have been sampled, the accumulated radon is transferred to a Lucas cell. The cell is mounted on a photomultiplier tube which detects the alpha particles from the decay of 222Rn and its daughters. The overall degassing and concentration efficiency is about 38% and the single-alpha counting efficiency is approximately 75%. The sensitivity of the radon assay system for D2O is equivalent to ~3 E(-15) g U/g water. The radon concentration in both the H2O and D2O is sufficiently low that the rate of background events from U-chain elements is a small fraction of the interaction rate of solar neutrinos by the neutral current reaction.Comment: 14 pages, 6 figures; v2 has very minor change

Molecular absorption lines toward star-forming regions : a comparative study of HCO+, HNC, HCN, and CN

Aims. The comparative study of several molecular species at the origin of the gas phase chemistry in the diffuse interstellar medium (ISM) is a key input in unraveling the coupled chemical and dynamical evolution of the ISM. Methods. The lowest rotational lines of HCO+, HCN, HNC, and CN were observed at the IRAM-30m telescope in absorption against the \lambda 3 mm and \lambda 1.3 mm continuum emission of massive star-forming regions in the Galactic plane. The absorption lines probe the gas over kiloparsecs along these lines of sight. The excitation temperatures of HCO+ are inferred from the comparison of the absorptions in the two lowest transitions. The spectra of all molecular species on the same line of sight are decomposed into Gaussian velocity components. Most appear in all the spectra of a given line of sight. For each component, we derived the central opacity, the velocity dispersion, and computed the molecular column density. We compared our results to the predictions of UV-dominated chemical models of photodissociation regions (PDR models) and to those of non-equilibrium models in which the chemistry is driven by the dissipation of turbulent energy (TDR models). Results. The molecular column densities of all the velocity components span up to two orders of magnitude. Those of CN, HCN, and HNC are linearly correlated with each other with mean ratios N(HCN)/N(HNC) = 4.8 $\pm$ 1.3 and N(CN)/N(HNC) = 34 $\pm$ 12, and more loosely correlated with those of HCO+, N(HNC)/N(HCO+) = 0.5 $\pm$ 0.3, N(HCN)/N(HCO+) = 1.9 $\pm$ 0.9, and N(CN)/N(HCO+) = 18 $\pm$ 9. These ratios are similar to those inferred from observations of high Galactic latitude lines of sight, suggesting that the gas sampled by absorption lines in the Galactic plane has the same chemical properties as that in the Solar neighbourhood. The FWHM of the Gaussian velocity components span the range 0.3 to 3 km s-1 and those of the HCO+ lines are found to be 30% broader than those of CN-bearing molecules. The PDR models fail to reproduce simultaneously the observed abundances of the CN-bearing species and HCO+, even for high-density material (100 cm-3 < nH < 104 cm-3). The TDR models, in turn, are able to reproduce the observed abundances and abundance ratios of all the analysed molecules for the moderate gas densities (30 cm-3 < nH < 200 cm-3) and the turbulent energy observed in the diffuse interstellar medium. Conclusions. Intermittent turbulent dissipation appears to be a promising driver of the gas phase chemistry of the diffuse and translucent gas throughout the Galaxy. The details of the dissipation mechanisms still need to be investigated

Correlations of Solar Neutrino Observables for SNO

Neutrino oscillation scenarios predict correlations, and zones of avoidance, among measurable quantities such as spectral energy distortions, total fluxes, time dependences, and flavor content. The comparison of observed and predicted correlations will enhance the diagnostic power of solar neutrino experiments. A general test of all presently-allowed (two neutrino) oscillation solutions is that future measurements must yield values outside the predicted zones of avoidance. To illustrate the discriminatory power of the simultaneous analysis of multiple observables, we map currently allowed regions of neutrino masses and mixing angles onto planes of quantities measurable with the Sudbury Neutrino Observatory (SNO). We calculate the correlations that are predicted by vacuum and MSW (active and sterile) neutrino oscillation solutions that are globally consistent with all available neutrino data. We derive approximate analytic expressions for the dependence of individual observables and specific correlations upon neutrino oscillations parameters. We also discuss the prospects for identifying the correct oscillation solution using multiple SNO observables.Comment: Accepted Phys Rev D. Included new figure. Related material http://www.sns.ias.edu/~jn