A stochastic probing algorithm for global optimization

Recently, simulated annealing methods have proven to be a valuable tool for global optimization. We propose a new stochastic method for locating the global optimum of a function. The proposed method begins with the subjective specification of a probing distribution. The objective function is evaluated at a few points sampled from this distribution, which is then updated using the collected information. The updating mechanism is based on the entropy of a move selecting distribution and is loosely connected to some notions in statistical thermodynamics. Examples of the use of the proposed method are presented. These indicate its superior performance as compared with simulated annealing. Preliminary considerations in applying the method to discrete problems are discussed.     

Remote asymmetric induction in an intramolecular ionic Diels-Alder reaction: application to the total synthesis of (+)-dihydrocompactin

The total synthesis of (+)-dihydrocompactin via an intramolecular ionic Diels-Alder reaction that proceeds with remote stereocontrol is described. This reaction proceeds by an intermediate vinyl-oxocarbenium ion (6), the conformational constraints of which lead to the observed asymmetric induction. The sense of asymmetric induction appears contrasteric and is explained by the proposed reactive conformation shown in Figure 1.     

Aqueous phosphoric acid as a mild reagent for deprotection of tert-butyl carbamates, esters, and ethers

Aqueous phosphoric acid (85 wt %) is an effective, environmentally benign reagent for the deprotection of tert-butyl carbamates, tert-butyl esters, and tert-butyl ethers. The reaction conditions are mild and offer good selectivity in the presence of other acid-sensitive groups, including CBZ carbamates, azetidine, benzyl and methyl esters, TBDMS, and methyl phenyl ethers. The mildness of the reaction is further demonstrated in the synthesis of clarithromycin derivative, in which a tert-butyl ester is removed in the presence of cyclic carbamate, lactone, ketal, acetate ester, and epimerizable methyl ketone functionalities. The reaction preserves the stereochemical integrity of the substrates. The reactions are high yielding, and the workup is convenient.     

In vivo fate of superparamagnetic iron oxides during sepsis

The enzymatic generation of nitric oxide (NO) in vivo has been reported to be modulated by ions, such as copper and iron. Superparamagnetic iron oxide (SPIO) or ferumoxides is a liver-specific magnetic resonance contrast agent that is taken up by the Kupffer cells, where NO is generated by inducible nitric oxide synthase (iNOS). Thus, it is important to evaluate SPIO in vivo under conditions, such as infectious disease, where significant amounts of NO are generated by iNOS. In this study, we monitored the pharmacokinetics of SPIO in the liver of septic-shock mice and rats. A significant decrease in the ferric iron EPR signal was observed during NO generation in septic-shock mice compared with control mice doped with only SPIO. These results were also confirmed in a model reaction system consisting of SPIO and the NO donor, S-nitroso-N-acetyl DL penicillamine (SNAP). We compared NO generation quantitatively in the liver of the septic-shock rats, either in the presence or absence of SPIO, and found that the presence of SPIO did not affect the NO-generating activity of NOS expressed in the liver. T2-weighted MR images of an agarose gel phantom containing different SPIO to NO donor (SNAP) ratios clearly demonstrated that the contrast enhancement by SPIO decreased with increasing NO at constant SPIO levels. The reduced contrast is most probably due to the reduction of ferric to ferrous irons, resulting in a decrease in paramagnetic relaxation of water protons. These results show that SPIO can be a versatile NO-sensitive indicator, especially employing MRI as a powerful tool to 'visualize' sites of NO generation.     

Synthetic studies toward phorboxazole A. stereoselective synthesis of the C(28)-C(46) side chain fragment

A stereoselective synthesis of the C(28)-C(46) fragment (3) of phorboxazole A is described. Key advances include an enantioselective allylation to establish the stereochemistry of the tetrahydropyran unit and a useful SmI(2)-mediated modification of the Barbier reaction of iodomethyloxazole 15 with aldehyde 14.     

Simulation of the indium profile in InGaAs/GaAs quantum-size heterostructures

A new approach to describe phenomena attendant on the growth of thin InGaAs epitaxial layers by hydride MOCVD in terms of which the boundary gas layer is considered as quasi-liquid is suggested. A numerical model for simulating the concentration profiles of the components in quantum-well heterostructures is developed. It is based on the assumption that a state close to thermodynamic equilibrium exists near the interface. The concentration profiles are simulated by jointly solving equations that describe heterogeneous equilibria and material balance at the interface. The indium profiles in InGaAs/GaAs quantum-size heterostructures are simulated at various parameters of the epitaxy process, such as temperature, initial component ratio in the gas phase, and boundary layer thickness. The results obtained agree well with the available experimental data.     

ESR imaging of polymers and solid materials

EPR imaging was applied to the study of several important processes in polymers and materials. The solvent diffusion and induced swelling was visualized in the water/DMF or toluene/DMF interactions with polycarbonate or polystyrene molded rods. The cross-sectional images revealed non-homogeneous solute/solvent diffusion, rod expansion and crack development. The ESR lineshapes in all cases above confirmed that the nitroxide imaging agent did not interact significantly with the polymer matrix; thus the paramagnetic distribution reflected bulk solvent distribution quite well. The diffusion of an electrolyte buffer (Krebs) solution containing a nitroxide spin probe was followed in a cross-sectional image of a polyacrylamide gel rod. A one-dimensional radial diffusion constant was calculated for the solvent piperidinol nitroxide spin probe, TEMPOL. Lastly, solid coal rods were monitored during mild pyrolysis at 150°C in air. Here the naturally occurring organic radical composition was imaged. Even with the increase in total ESR signal and subsequent decline to ca. the initial levels, the coal rod cross-section was essentially homogeneous in paramagnetic centers throughout the heating process. All of the imaging above utilized a homemade L-band, flat loop surface coil spectrometer.