Improved Eddy-Viscosity Modelling of Turbulent Flow around Porous–Fluid Interface Regions

Transport in Porous Media - The RANS modelling of turbulence across fluid-porous interface regions within ribbed channels has been investigated by applying double (both volume and Reynolds)...     

The first transannular [4+3] cycloaddition reaction: synthesis of the ABCD ring structure of cortistatins

A 14-membered macrocycle with an allene and a furan strategically located at across the ring from each other is synthesized using an allene ring closing metathesis reaction. Upon treatment of the macrocycle with a catalytic amount of Pd(OAc)₂ and other additives, the first transannular [4+3] cycloaddition occurred to yield 37% of a tetracyclic compound containing the ABCD ring structure of the natural products cortistatins.     

Design and evaluation of a testing machine for determining tensile properties of materials at moderate strain rates

A test fixture was designed and built to evaluate tensile properties at a specific rate of strain in the region from 0.01 to 25 in./in./sec. The specimen is of tubular section and loaded internally by fluid pressure. Details of the design and instrumentation are presented. Test results for annealed 1018 steel are given and compared with results of other investigators. This steel is shown to be strain-rate sensitive in the region tested.     

Mass spectrometric study of the effects of hydrophobic surface chemistry and morphology on the digestion of surface-bound proteins

Our previous work has demonstrated that reversed-phase chromatographic micro-beads can be used to capture proteins from complex biological matrices and the surface-bound proteins can be enzymatically digested for protein identification by mass spectrometry (MS). Here we examine the peptides generated from digestion of proteins bound to various types of micro-bead surfaces in order to determine the effects of surface chemistry and surface morphology on the digestion process. Detailed examinations of site cleavages and sequence coverage are carried out for a tryptic digestion of cytochrome c adsorbed on reversed-phase polystyrene divinylbenzene (Poros R2 beads) versus C(18) bonded-phase silica beads. It is shown that although the surface does not completely hinder the digestion of cleavage sites of the protein, the digestion products are clearly different than those obtained from a solution digest. Specifically, a partial digestion results from surface digestion, resulting in a greater number of missed cleavages than a comparable solution digest. Subsequent comparisons of peptide mass maps generated from the digestion of various proteins on surfaces with altering chemistry (C(4), C(8), C(18), and R2 beads), or with different surface morphology, were performed. The results reveal that surface chemistry plays only a minor role in affecting the peptide mass maps, and surface morphology had no noticeable effects on the resulting peptide mass maps. It is also shown that the mass spectrometric detection method used to analyze the digested peptides can significantly influence the information content on cleavage sites and the extent of sequence coverage. The use of a combination of MALDI, LC/off-line MALDI, and LC/ESI MS is demonstrated to be crucial in revealing subtle changes in the peptide mass maps.     

Nickel oxidation states of F(430) cofactor in methyl-coenzyme M reductase

Magnetic circular dichroism (MCD) spectroscopy and variable-temperature variable-field MCD are used in combination with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations to characterize the so-called ox1-silent, red1, and ox1 forms of the Ni-containing cofactor F430 in methyl-coenzyme M reductase (MCR). Previous studies concluded that the ox1 state, which is the precursor of the key reactive red1 state of MCR, is a Ni(I) species that derives from one-electron reduction of the Ni(II)-containing ox1-silent state. However, our absorption and MCD data provide compelling evidence that ox1 is actually a Ni(II) species. In support of this proposal, our DFT and TD-DFT calculations indicate that addition of an electron to the ox1-silent state leads to formation of a hydrocorphin anion radical rather than a Ni(I) center. These results and biochemical evidence suggest that ox1 is more oxidized than red1, which prompted us to test a new model for ox1 in which the ox1-silent species is oxidized by one electron to form a thiyl radical derived from coenzyme M that couples antiferromagnetically to the Ni(II) ion. This alternative ox1 model, formally corresponding to a Ni(III)/thiolate resonance form but with predicted S = 1/2 EPR parameters reminiscent of a Ni(I) (3dx2-y2)1 species, rationalizes the requirement for reduction of ox1 to yield the red1 species and the seemingly incongruent EPR and electronic spectra of the ox1 state.     

Isotope effects in aqueous systems. V. Partial molal enthalpies of solution of NaCl−H2O−D2O and related systems (5 to 75°C)1

Solvent isotope effects on differential heats of solution of NaCl in HOH and DOD have been measured between 0.01 and 4m and from 5 to 40°C. These data are supplemented by integral heats of solution measured at 0.465m and from 5 to 75°C, and with heats of dilution over the same temperature range. The integral heat measurements include studies on otheralkali halides (KCl, NaI, NaBr), and the dilution measurements include some data for KCl. In the NaCl studies, particular attention was paid to the low-concentration region. Values of the partial molal enthalpiesL ₁ adL ₂ are derived for solution in both isotopic waters, and new values for the isotope effect on the standard enthalpy of solution ΔL ₂ ^s = (ΔH ₂ ⁰ ) _d←w as a function of temperature are reported. Comparisons are made with previous work where possible. In contrast to statements made by earlier authors, examination of the low-concentration data reveals a \(\surd \overline m\) dependence within experimental error.     

Thermodynamics of hydrogen solution and hydride formation in Pd-Mn alloys. 2. Ordered alloys

There are marked differences in H(2) solubilities between ordered and disordered Pd-Mn alloys with the largest difference found between the L1(2) and the disordered form of the Pd(3)Mn alloy. The thermodynamics of H(2) solution have been determined for the L1(2) form, the long-period superstructure (lps), and the disordered forms of the Pd(0.80)Mn(0.20) and Pd(0.75)Mn(0.25)(Pd(3)Mn) alloys. Relative partial molar enthalpies and entropies were determined mainly by reaction calorimetry over the range of H contents accessible from p(H)()2 approximately 10 Pa to approximately 0.3 MPa (303 K). The enthalpies for absorption of H(2) are more exothermic over most of the range of H contents for the L1(2) forms of the Pd(3)Mn and Pd(0.80)Mn(0.20) alloys than for their other forms. The reaction enthalpies are constant across a relatively wide range of H contents for the L1(2) form of the Pd(0.80)Mn(0.20) and Pd(3)Mn alloys indicating that there are two-phase coexistence regions (303 K). The H-H attractive interaction, which leads to hydride formation, is much greater for the L1(2) than for the other forms of the Pd(3)Mn alloy and for Pd itself. It has been found that the H-H interaction always decreases in magnitude and, accompanying this, the THS (terminal hydrogen solubility) always increases by alloying Pd.(1) The L1(2) ordered Pd(3)Mn alloy is an exception to this, and therefore, the generalization about THS must be restricted to disordered face centered cubic (fcc) Pd alloys.     

Freezing points,osmotic coefficients,and activity coefficients of some salts in ethylene carbonate: A high dielectric constant solvent without hydrogen bonding

The freezing points, conductivities, and densities of NaI, KI, CsI, Bu₄NCl, Bu₄NBr, Bu₄NI, Et₄NBr, and Pr₄NBr (where Et = ethyl, Pr = propyl, and Bu =n-butyl) in ethylene carbonate have been measured. Osmotic and activity coefficients were calculated from the results. All of the salts studied are strong electrolytes. The trends in the osmotic coefficients of the alkali metal iodides are NaI>KI>CsI, showing that Na⁺ is more solvated by ethylene carbonate than Cs⁺. For the tetraalkylammonium halides, the order of osmotic coefficients are Et₄NBrPr₄NBrBu₄NCl>Bu₄NBr>Bu₄NI. This is the same order as observed in two other high-dielectric-constant solvents, water andN-methylacetamide. The results indicate that the smaller anions are more solvated than the larger anions in ethylene carbonate in contrast to the usual behavior of dipolar aprotic (basic) solvents, such as dimethyl sulfoxide.     

Freezing temperatures and densities of solutions of some hydrocarbons and sodium oleate inN-methylacetamide. Evidence for a solvophobic interaction

The freezing temperatures and densities (at 31°C) of solutions of octane, nonane, decane, 3,3-diethylpentane, and sodium oleate inN-methylacetamide (NMA) have been measured. The molality of the freezing solution was calculated from the density. The solubilities of octane, nonane, and decane inN-methylacetamide are also reported. Apparent molal volumes calculated from the densities are close to the values in the pure hydrocarbons and are not strong functions of the concentration. This indicates the absence of any unusual packing effect. The calculated free energies of transfer of the hydrocarbons from pure hydrocarbon to NMA solution are much less negative than the corresponding values for water, showing that the bulk solvophobic interaction inN-methylacetamide is smaller than in water. This is consistent with the freezing temperatures of sodium oleate which show that micelles do not form below 0.1 mole-kg^–1. The osmotic coefficients of the hydrocarbons calculated from the freezing temperatures showed negative deviations from ideality that were larger for the hydrocarbons with the higher molecular weights. Two estimates of the pairwise solvophobic interaction inN-methylacetamide indicate that it is also smaller than in water. The solvophobic effect in this solvent does not include the large entropy and enthalpy effects found in aqueous solutions.     

Gold‐Catalyzed Transannular [4+3] Cycloaddition Reactions

Macrocyclic propargyl acetates containing a furan ring were prepared by using a CrCl₂‐promoted reaction. In the presence of either a Au^I or Au^III catalyst, a tandem 3,3‐rearrangement/transannular [4+3] cycloaddition reaction occurred to give propargyl acetates that are regio‐ and diastereospecific. The regiochemistry of the product is controlled by the position of the acetoxy group in the starting material and the stereochemistry of the reaction depends on the ring size.