Dynamical analysis of extreme precipitation in the US northeast based on large-scale meteorological patterns

This is the author accepted manuscript. The final version is available from Springer via the DOI in this record.Previous work has identified six large-scale meteorological patterns (LSMPs) of dynamic tropopause height associated with extreme precipitation over the Northeast US, with extreme precipitation defined as the top 1% of daily station precipitation. Here, we examine the three-dimensional structure of the tropopause LSMPs in terms of circulation and factors relevant to precipitation, including moisture, stability, and synoptic mechanisms associated with lifting. Within each pattern, the link between the different factors and extreme precipitation is further investigated by comparing the relative strength of the factors between days with and without the occurrence of extreme precipitation. The six tropopause LSMPs include two ridge patterns, two eastern US troughs, and two troughs centered over the Ohio Valley, with a strong seasonality associated with each pattern. Extreme precipitation in the ridge patterns is associated with both convective mechanisms (instability combined with moisture transport from the Great Lakes and Western Atlantic) and synoptic forcing related to Great Lakes storm tracks and embedded shortwaves. Extreme precipitation associated with eastern US troughs involves intense southerly moisture transport and strong quasi-geostrophic forcing of vertical velocity. Ohio Valley troughs are associated with warm fronts and intense warm conveyor belts that deliver large amounts of moisture ahead of storms, but little direct quasi-geostrophic forcing. Factors that show the largest difference between days with and without extreme precipitation include integrated moisture transport, low-level moisture convergence, warm conveyor belts, and quasi-geostrophic forcing, with the relative importance varying between patterns.National Science FoundationSwiss National Science Foundation (SNSF

Scope and Mechanistic Study of the Coupling Reaction of α,β-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways

The cationic ruthenium-hydride complex [(C6H6)(PCy3)(CO)RuH]+BF4– (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,β-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic C–H bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as follows: rate = k[1]1[propene]0[cinnamate]−1. A negligible deuterium kinetic isotope effect (kH/kD = 1.1 ± 0.1) was measured from both (E)-C6H5CH═C(CH3)CONHCH3 and (E)-C6H5CD═C(CH3)CONHCH3 with styrene. In contrast, a significant normal isotope effect (kH/kD = 1.7 ± 0.1) was observed from the reaction of (E)-C6H5CH═C(CH3)CONHCH3 with styrene and styrene-d8. A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C6H5CH═CHCO2Et with propene (13C(recovered)/13C(virgin) at Cβ = 1.019(6)), while a negligible carbon isotope effect (13C(recovered)/13C(virgin) at Cβ = 0.999(4)) was obtained from the reaction of (E)-C6H5CH═C(CH3)CONHCH3 with styrene. Hammett plots from the correlation of para-substituted p-X-C6H4CH═CHCO2Et (X = OCH3, CH3, H, F, Cl, CO2Me, CF3) with propene and from the treatment of (E)-C6H5CH═CHCO2Et with a series of para-substituted styrenes p-Y-C6H4CH═CH2 (Y = OCH3, CH3, H, F, Cl, CF3) gave the positive slopes for both cases (ρ = +1.1 ± 0.1 and +1.5 ± 0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, ΔH⧧ = 20 ± 2 kcal mol–1 and ΔS⧧ = −42 ± 5 eu. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies

Force-Extension Relation and Plateau Modulus for Wormlike Chains

We derive the linear force-extension relation for a wormlike chain of arbitrary stiffness including entropy elasticity, bending and thermodynamic buckling. From this we infer the plateau modulus $G^0$ of an isotropic entangled solution of wormlike chains. The entanglement length $L_e$ is expressed in terms of the characteristic network parameters for three different scaling regimes in the entangled phase. The entanglement transition and the concentration dependence of $G^0$ are analyzed. Finally we compare our findings with experimental data.Comment: 5 pages, 1 eps-figure, to appear in PR

Elasticity of Gaussian and nearly-Gaussian phantom networks

We study the elastic properties of phantom networks of Gaussian and nearly-Gaussian springs. We show that the stress tensor of a Gaussian network coincides with the conductivity tensor of an equivalent resistor network, while its elastic constants vanish. We use a perturbation theory to analyze the elastic behavior of networks of slightly non-Gaussian springs. We show that the elastic constants of phantom percolation networks of nearly-Gaussian springs have a power low dependence on the distance of the system from the percolation threshold, and derive bounds on the exponents.Comment: submitted to Phys. Rev. E, 10 pages, 1 figur

Critical behaviour of the Rouse model for gelling polymers

It is shown that the traditionally accepted "Rouse values" for the critical exponents at the gelation transition do not arise from the Rouse model for gelling polymers. The true critical behaviour of the Rouse model for gelling polymers is obtained from spectral properties of the connectivity matrix of the fractal clusters that are formed by the molecules. The required spectral properties are related to the return probability of a "blind ant"-random walk on the critical percolating cluster. The resulting scaling relations express the critical exponents of the shear-stress-relaxation function, and hence those of the shear viscosity and of the first normal stress coefficient, in terms of the spectral dimension $d_{s}$ of the critical percolating cluster and the exponents $\sigma$ and $\tau$ of the cluster-size distribution.Comment: 9 pages, slightly extended version, to appear in J. Phys.

Abscess Formation Following Spilled Gallstones During Laparoscopic Cholecystectomy

A review of the English literature concerning spilled gallstones during laparoscopic cholecystectomy is compared with one institution's experience of four cases during 1,726 laparoscopic cholecystectomies performed over a four-year period. Strategies regarding management and treatment are discussed

Self-diffusion in binary blends of cyclic and linear polymers

A lattice model is used to estimate the self-diffusivity of entangled cyclic and linear polymers in blends of varying compositions. To interpret simulation results, we suggest a minimal model based on the physical idea that constraints imposed on a cyclic polymer by infiltrating linear chains have to be released, before it can diffuse beyond a radius of gyration. Both, the simulation, and recently reported experimental data on entangled DNA solutions support the simple model over a wide range of blend compositions, concentrations, and molecular weights.Comment: 10 pages, 2 figure

Associations Between High-Density Lipoprotein Particles and Ischemic Events by Vascular Domain, Sex, and Ethnicity A Pooled Cohort Analysis

Background: High-density lipoprotein (HDL) cholesterol concentration (HDL-C) is an established atheroprotective marker, in particular for coronary artery disease; however, HDL particle concentration (HDL-P) may better predict risk. The associations of HDL-C and HDL-P with ischemic stroke and myocardial infarction (MI) among women and Blacks have not been well studied. We hypothesized that HDL-P would consistently be associated with MI and stroke among women and Blacks compared with HDL-C. Methods: We analyzed individual-level participant data in a pooled cohort of 4 large population studies without baseline atherosclerotic cardiovascular disease: DHS (Dallas Heart Study; n=2535), ARIC (Atherosclerosis Risk in Communities; n=1595), MESA (Multi-Ethnic Study of Atherosclerosis; n=6632), and PREVEND (Prevention of Renal and Vascular Endstage Disease; n=5022). HDL markers were analyzed in adjusted Cox proportional hazard models for MI and ischemic stroke. Results: In the overall population (n=15 784), HDL-P was inversely associated with the combined outcome of MI and ischemic stroke, adjusted for cardiometabolic risk factors (hazard ratio [HR] for quartile 4 [Q4] versus quartile 1 [Q1], 0.64 [95% CI, 0.52-0.78]), as was HDL-C (HR for Q4 versus Q1, 0.76 [95% CI, 0.61-0.94]). Adjustment for HDL-C did not attenuate the inverse relationship between HDL-P and atherosclerotic cardiovascular disease, whereas adjustment for HDL-P attenuated all associations between HDL-C and events. HDL-P was inversely associated with the individual end points of MI and ischemic stroke in the overall population, including in women. HDL-P was inversely associated with MI among White participants but not among Black participants (HR for Q4 versus Q1 for Whites, 0.49 [95% CI, 0.35-0.69]; for Blacks, 1.22 [95% CI, 0.76-1.98];P-interaction=0.001). Similarly, HDL-C was inversely associated with MI among White participants (HR for Q4 versus Q1, 0.53 [95% CI, 0.36-0.78]) but had a weak direct association with MI among Black participants (HR for Q4 versus Q1, 1.75 [95% CI, 1.08-2.83];P-interactio