Direct coupling of intracerebral dialysis with flow injection analysis based on enzymatic/fluorescence detection of lactic acid

Rapid, specific measurement of the lactic acid content of the extracellular fluid of a conscious, freely-moving rat can be accomplished by direct combination of intracerebral dialysis and flow injection analysis with enzymatic/fluorescence detection. Basal levels of lactic acid, the end product of anaerobic glycolysis, can be measured by using lactate dehydrogenase to convert lactate to pyruvate with consequent generation of NADH, which is monitored fluorimetrically. The rapid response time of this system, 40 s, allows real-time measurement of transient changes in anaerobic metabolism in the striatum of the rat, as illustrated after electrically-induced seizures.     

Geometrical Solution to the Fermat Problem with Arbitrary Weights

The prime motivation for the present study is a famous problem, allegedly first formulated in 1643 by Fermat, and the so-called Complementary Problem (CP), proposed but incorrectly solved in 1941 by Courant and Robbins. For a given triangle, Fermat asks for a fourth point such that the sum of its Euclidean distances, each weighted by +1, to the three given points is minimized. CP differs from Fermat in that the weight associated with one of these points is –1 instead of +1. The geometrical approach suggested in 1998 by Krarup for solving CP is here extended to cover any combination of positive and negative weights associated with the vertices of a given triangle. Among the by-products are surprisingly simple correctness proofs of the geometrical constructions of Torricelli (around 1645), Cavalieri (1647), Viviani (1659), Simpson (1750), and Martelli (1998). Furthermore, alternative proofs of Ptolemy's theorem (around A.D. 150) and an observation by Heinen (1834) are provided.     

Higher-Order Terms in the Capillary Limit Approximation of Viscous-Capillary Flow

We propose a new approximation to the solution of the steady state equations describing two-phase immiscible flow in a porous medium. It is demonstrated that the general procedure contains the capillary equilibrium approximation as a special case. The solution is approximated by a perturbation series in a parameter related to the capillary number. The expansion of the solution results in a sequence of decoupled linear elliptic boundary value problems. This sequence is solved numerically by a Finite Element method, and the accuracy of the approximations is evaluated.     

Dual‐Function Cobalt–Nickel Nanoparticles Tailored for High‐Temperature Induction‐Heated Steam Methane Reforming

The tailored chemical synthesis of binary and ternary alloy nanoparticles with a uniform elemental composition is presented. Their dual use as magnetic susceptors for induction heating and catalytic agent for steam reforming of methane to produce hydrogen at temperatures near and above 800 °C is demonstrated. The heating and catalytic performance of two chemically synthesized samples of CoNi and Cu ? CoNi are compared and held against a traditional Ni‐based reforming catalyst. The structural, magnetic, and catalytic properties of the samples were characterized by X‐ray diffraction, elemental analysis, magnetometry, and reactivity measurements. For induction‐heated catalysts, the conversion rate of methane is limited by chemical reactivity, as opposed to the case of traditional externally heated reformers where heat transport limitations are the limiting factor. Catalyst production by the synthetic route allows controlled doping with miniscule concentrations of auxiliary metals.     

Polypeptide folding using Monte Carlo sampling, concerted rotation, and continuum solvation

An efficient concerted rotation algorithm for use in Monte Carlo statistical mechanics simulations is applied to fold three polypeptides, U(1-17)T9D, alpha(1), and trpzip2, which exhibit native beta-hairpin and alpha-helix folds. The method includes flexible bond and dihedral angles, and a Gaussian bias is applied with driver bond and dihedral angles to optimize the sampling efficiency. Solvation in water is implemented with the generalized Born (GBSA) model. The computed lowest-energy manifolds for the folded structures of the two beta-hairpins agree closely with the corresponding NMR structures. In the case of the alpha(1) peptide, the folded alpha-helical state, which is observed as oligomers in concentrated solution and crystals, is not stable in isolation. The computed preference for random coil structures is in agreement with NMR experiments at low concentration. The fact that native states can be located on high dimensional energy surfaces starting from extended conformations shows that the present methodology samples all relevant parts of the conformational space. The OPLS-AA force field with the GBSA solvent model was also found to perform well in leading to clear energetic separation of the correctly folded structures from misfolded structures for the two peptides that form beta-turns.     

Photochemical reaction mechanisms of 2-nitrobenzyl compounds: methyl ethers and caged ATP

The mechanism of methanol photorelease from 2-nitrobenzyl methyl ether (1) and 1-(2-nitrophenyl)ethyl methyl ether (2), and of ATP release from adenosine-5'-triphosphate-[P(3)-(1-(2-nitrophenyl)ethyl)] ester ('caged ATP', 3) was studied in various solvents by laser flash photolysis with UV-vis and IR detection. In addition to the well-known primary aci-nitro transients (A, lambda(max) approximately 400 nm), two further intermediates preceding the release of methanol, namely the corresponding 1,3-dihydrobenz[c]isoxazol-1-ol derivatives (B) and 2-nitrosobenzyl hemiacetals (C), were identified. The dependencies of the reaction rates of A-C on pH and buffer concentrations in aqueous solution were studied in detail. Substantial revision of previously proposed reaction mechanisms for substrate release from 2-nitrobenzyl protecting groups is required: (a) A novel reaction pathway of the aci-tautomers A prevailing in buffered aqueous solutions, e.g., phosphate buffer with pH 7, was found. (b) The cyclic intermediates B were identified for the first time as the products formed by the decay of the aci-tautomers A in solution. A recently proposed reaction pathway bypassing intermediates B (Corrie et al. J. Am. Chem. Soc., 2003, 125, 8546-8554) is shown not to be operative. (c) Hemiacetals C limit the release rate of both 1 (pH < 8) and 2 (pH < 10). This observation is in contrast to a recent claim for related 2-nitrobenzyl methyl ethers (Corrie et al.). Our findings are important for potential applications of the 2-nitrobenzyl protecting group in the determination of physiological response times to bioagents ('caged compounds').