Dissociation energetics and mechanisms of leucine enkephalin (M+H)+ and (2M+X)+ ions (X=H, Li, Na, K, and Rb) measured by blackbody infrared radiative dissociation

The dissociation kinetics of protonated leucine enkephalin and its proton and alkali metal bound dimers were investigated by blackbody infrared radiative dissociation in a Fourier-transform mass spectrometer. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained. Protonated leucine enkephalin dissociates to form b(4) and (M-H(2)O)(+) ions with an average activation energy (E(a)) of 1.1 eV and an A factor of 10(10.5) s(-1). The value of the A factor indicates that these dissociation processes are rearrangements. The b(4) ions subsequently dissociate to form a(4) ions via a process with a relatively high activation energy (1.3 eV), but one that is entropically favored. For the cationized dimers, the thermal stability decreases with increasing cation size, consistent with a simple electrostatic interaction in these noncovalent ion-molecule complexes. The E(a) and A factors are indistinguishable within experimental error with values of ~1.5 eV and 10(17) s(-1), respectively. Although not conclusive, results from master equation modeling indicate that all these BIRD processes, except for b(4) --> a(4), are in the rapid energy exchange limit. In this limit, the internal energy of the precursor ion population is given by a Boltzmann distribution and information about the energetics and dynamics of the reaction are obtained directly from the measured Arrhenius parameters.     

Ordered ternary compounds of the rare earth sesquisulfides

Intermediate compositions were investigated in eight Ln₂S₃-Ln₂′S₃ systems and reaction products characterized by Raman spectroscopy. Raman spectra are reported for the ordered structures reported in earlier literature. Based on the Raman spectra, LaLuS₃ previously reported as isostructural with LaDyS₃ (the I-type structure) is actually a new ordered compound. It was indexed on an orthorhombic cell with a=7.304, b=6.659 and . A second previously unreported compound, Dy₃ScS₆, was identified by its Raman spectrum. Sharp Raman lines with a unique arrangement for each structure-type indicate that the ternary rare earth sulfides are well-ordered structures.     

Blue ferrocenium azurin: an organometalloprotein with tunable redox properties

A ferrocene derivative (2-[(methylsulfonyl)thio]ethylferrocene) (1) has been synthesized and incorporated into apo-azurin from Pseudomonas aeruginosa by covalent attachment to the highly conserved Cys112. The resulting artificial organometalloprotein (a protein containing organometallic compounds in the active site) has been characterized by UV-vis, electrospray mass spectrometry, and cyclic voltammetry (CV). Incorporation of 1 into azurin resulted in a higher solubility of the ferrocene group and improved stability of the ferrocenium species in aqueous solution, as shown by a more intense UV-vis absorption and a more reversible CV of the attached ferrocene group, respectively. The incorporation of 1 also increased the reduction potential of the complex from 402 to 579 mV (vs NHE), consistent with the ferrocene group being encapsulated inside the hydrophobic environment of the protein. Modulation of the reduction potential of ferrocene by residues near the secondary coordination sphere has also been demonstrated. Raising the pH from 4 to 9 resulted in a greater than 80 mV decrease in reduction potential of the protein-bound ferrocene (from 579 to 495 mV), while replacing Met121, an amino acid residue in close proximity to the ferrocene group with a positively charged Arg or negatively charged Glu, resulted in the predicted increase or decrease in reduction potential at all pH values. Similarly, substitution of Met121 with a more hydrophobic Leu raised the reduction potential. The increased solubility, stability, and tune-ability of this organometalloprotein make it an ideal choice for carrying out a number of biological reactions, such as long-range electron transfer or sensing. As an example of such applications, stoichiometric oxidation of ferrocytochrome c by the blue ferrocenium azurin was demonstrated.     

Novel 3-phenylprop-2-ynylamines as inhibitors of mammalian squalene epoxidase

The synthesis of a novel series of 3-phenylprop-2-ynylamines as selective mammalian squalene epoxidase inhibitors is described. Structure activity relationship studies led to the discovery of compound 19, 1-[3-(3,5-dichlorophenyl)-prop-2-ynyl]-3- methylpiperidine hydrochloride with an IC50 of 2.8 +/- 0.6 microM against rat liver squalene epoxidase. Against 23 strains of fungal squalene epoxidase compound 19 was found to be inactive.     

Discrete valuation overrings of Noetherian domains

We show that, given a chain of prime ideals in a Noetherian domain , there exist a finitely generated overring of and a saturated chain of primes in contracting term by term to the given chain. We further show that there is a discrete rank valuation overring of whose primes contract to those of the given chain.

     

Linked Bis(μ-Phosphido) and Related Ligands for Metallic Clusters. 2. Reaction of 1,2,3-Triphenyl-1,2,3-Triphosphaindane with Nonacarbonyldiiron

Abstract

The reaction of 1,2,3-triphenyl-1,2,3-triphosphaindane with nonacarbonyldiiron in benzene at 80 °C gives rise to a mixture of at least eight components, five of which have been isolated and characterized. Three of these are P₃Fe₃ species, of which two have been unambiguously identified by single crystal x-ray crystallography.     

Refractive-index-matched hydrogel materials for measuring flow-structure interactions

In imaging-based studies of flow around solid objects, it is useful to have materials that are refractive-index-matched to the surrounding fluid. However, materials currently in use are usually rigid and matched to liquids that are either expensive or highly viscous. This does not allow for measurements at high Reynolds number, nor accurate modeling of flexible structures. This work explores the use of two hydrogels (agarose and polyacrylamide) as refractive-index-matched models in water. These hydrogels are inexpensive, can be cast into desired shapes, and have flexibility that can be tuned to match biological materials. The use of water as the fluid phase allows this method to be implemented immediately in many experimental facilities and permits investigation of high-Reynolds-number phenomena. We explain fabrication methods and present a summary of the physical and optical properties of both gels, and then show measurements demonstrating the use of hydrogel models in quantitative imaging.     

Numerical simulation of contraction and expansion flows of Langmuir monolayers

Langmuir monolayers consist of amphiphilic molecules at the air–water interface and can be modeled as two-dimensional fluids. Earlier experiments [D.J. Olson, G.G. Fuller, J. Non-Newtonian Fluid Mech. 89 (2000) 187–207] on 4:1 contraction and 4:1 expansion flows have been simulated using an integral constitutive equation of the K-BKZ type, suitably modified to account for strain-thickening in the planar extensional viscosity. The model has been used to fit linear viscoelastic data (G′ and G″) and the shear viscosity (η_S), while the amount of strain-hardening is assumed, due to lack of experimental data. The simulations are in good agreement with the experiments on Newtonian monolayers, which show no vortices in the contraction but large inertial vortices in the expansion. For the viscoelastic monolayer (a poly-octadecyl methacrylate or PODMA), the opposite is true. The contraction flow shows vortices, while in the expansion flow the vortex activity is substantially reduced compared with the Newtonian one. The viscoelastic behavior is well captured by the model, provided that substantial strain-thickening is exhibited by the monolayer in planar extension. The latter behavior is very much like that for a branched LDPE melt, which also shows big vortices due to strain-hardening in planar as well as in uniaxial extension.