At-sea measurements of sound penetration into sediments using a buried vertical synthetic array

Acoustic bottom penetration experiments were carried out in a medium-grain sandy bottom at a site in St. Andrews Bay, Florida. These investigations used a new buried, vertical, one-dimensional synthetic array system where a small hydrophone was water-jetted into the sediment to a depth of approximately 2 m. Once buried, this hydrophone was mounted to a vertical robotics stage that translated the hydrophone upward in 1-cm increments. A broadband (3 to 80 kHz) spherical source, positioned 50 cm above the sediment-water interface, was used to insonify the sediment. Measurements were made with insonification angles above and below the critical angle by changing the horizontal distance of the source relative to the insertion point. This new measurement system is detailed, and results are presented that include temporal, frequency, and wavenumber analysis for natural and roughened interfaces. The measured compressional sound speed and attenuation are shown to be self-consistent using the Kramers-Kronig relation. Furthermore, only a single fast compressional wave was observed. There was no observation of a second slower compressional wave as predicted by some applications of the Biot model to unconsolidated water-saturated porous media.     

Mechanistic studies of the phosphine-catalyzed homodimerization of ketoketenes

The mechanism of PBu₃-catalyzed homodimerization of ketoketenes has been explored and compared with that of the previously reported trialkylphosphite-mediated reactions. NMR studies of the PBu₃-catalyzed reaction implicated the involvement of tetravalent phosphonium intermediates. Phosphonium intermediates in the catalytic cycle were trapped through reaction with trimethylsilyl chloride and 4-chlorobenzaldehyde, and the resulting products were characterized. A method for the stoichiometric generation of phosphonium enolates was developed as a result of these studies. No evidence was obtained for the involvement of pentacovalent phosphorane intermediates in trialkylphosphine-catalyzed ketoketene homodimerization reactions, in contrast with the mechanism of the trialkylphosphite-mediated homodimerization of dimethylketene. An X-ray crystal structure analysis of methylphenylketene dimer showed that it possesses Z-geometry about the exocyclic olefin.     

Structural and Spectroscopic Characterization of Mer-[RhBr3(Me2pzH)3] (Me2pzH?=?3, 5-Dimethylpyrazole); Interpreting the Results with Density Functional Theory Calculations

Abstract  

Mer-RhBr₃(Me₂pzH)₃ (Me₂pzH = 3,5-dimethylpyrazole) (monoclinic, P2₁/n, a = 8.3300 (5) Å, b = 16.2889 (9) Å, c = 15.9299 (11) Å, α = 90°, β = 100.217 (5)°, γ = 90°; V = 2,127.2 (2) ų; Z = 4) has been characterized by X-ray diffraction, ¹H and ¹³C nuclear magnetic resonance spectroscopy, infrared spectroscopy, and electronic absorption spectroscopy, and modeled by density functional theory (DFT) and time-dependent density functional theory (TDDFT). Mer-RhBr₃(Me₂pzH)₃ is an octahedral complex with a HOMO → LUMO transition at 486 nm. The DFT and TDDFT calculations predicted mer-RhBr₃(Me₂pzH)₃ to be an octahedral complex with a HOMO → LUMO transition at 540 nm.     

A palladium-catalyzed multicomponent synthesis of imidazolinium salts and imidazolines from imines, acid chlorides, and carbon monoxide

A palladium-catalyzed multicomponent synthesis of imidazolinium carboxylates and imidazolines is described. The palladium catalyst [Pd(CH(R(1))N(R(2))COR(3))Cl](2), or [Pd(allyl)Cl](2), with P(t-Bu)(2)(2-biphenyl) can mediate the simultaneous coupling of two imines, acid chloride, and carbon monoxide into substituted imidazolinium carboxylates within hours under mild conditions (45 °C, 4 atm of CO). The reaction proceeds in good yield with aryl-, heteroaryl-, and alkyl-substituted acid chlorides, as well as variously functionalized imines. Imidazolines are formed via the initial generation of Mu?nchnone intermediates, followed by their cycloaddition with an in situ generated protonated imine. The addition of an amine base can intercept catalysis at Münchnone formation, which allows the subsequent cycloaddition of a second imine. The latter provides a route for the assembly of complex, polysubstituted imidazolinium carboxylates with independent control of all five substituents. The subsequent removal of the nitrogen substituent(s) provides an overall synthesis of imidazolines.     

Rate coefficients for reactions of OH radicals with CH3D,CH2D2, CHD3, and CD4

Fourier transform infrared (FTIR) smog chamber techniques were used to investigate the atmospheric chemistry of the isotopologues of methane. Relative rate measurements were performed to determine the kinetics of the reaction of the isotopologues of methane with OH radicals in cm³ molecule⁻¹ s⁻¹ units: k(CH₃D + OH) = (5.19 ± 0.90) × 10⁻¹⁵, k(CH₂D₂ + OH) = (4.11 ± 0.74) × 10⁻¹⁵, k(CHD₃ + OH) = (2.14 ± 0.43) × 10⁻¹⁵, and k(CD₄ + OH) = (1.17 ± 0.19) × 10⁻¹⁵ in 700 Torr of air diluent at 296 ± 2 K. Using the determined OH rate coefficients, the atmospheric lifetimes for CH_4–xD_x (x = 1–4) were estimated to be 6.1, 7.7, 14.8, and 27.0 years, respectively. The results are discussed in relation to previous measurements of these rate coefficients.     

Increasing the Weight of Minimum Spanning Trees

The problems of computing the maximum increase in the weight of the minimum spanning trees of a graph caused by the removal of a given number of edges, or by finite increases in the weights of the edges, are investigated. For the case of edge removals, the problem is shown to be NP-hard and an Ω(1/log k)-approximation algorithm is presented for it, where (input parameter) k > 1 is the number of edges to be removed. The second problem is studied, assuming that the increase in the weight of an edge has an associated cost proportional to the magnitude of the change. An O(n³m² log(n²/m)) time algorithm is presented to solve it.     

2‐Aminopyrimidine–3,3,3‐triphenylpropanoic acid (1/1)

The title bimolecular compound, C₄H₅N₃·C₂₁H₁₈O₂, constructed from 2‐aminopyrimidine and 3,3,3‐triphenylpropanoic acid, forms a tetramolecular hydrogen‐bonded motif via O—H...N, N—H...O and N—H...N contacts. This aggregate organizes to give crystal‐packing motifs with hydrophilic and hydrophobic regions.