Sample-path optimization of convex stochastic performance functions

In this paper we propose a method for optimizing convex performance functions in stochastic systems. These functions can include expected performance in static systems and steady-state performance in discrete-event dynamic systems; they may be nonsmooth. The method is closely related to retrospective simulation optimization; it appears to overcome some limitations of stochastic approximation, which is often applied to such problems. We explain the method and give computational results for two classes of problems: tandem production lines with up to 50 machines, and stochastic PERT (Program Evaluation and Review Technique) problems with up to 70 nodes and 110 arcs. Sponsored by the National Science Foundation under grant number CCR-9109345, by the Air Force Systems Command, USAF, under grant numbers F49620-93-1-0068 and F49620-95-1-0222, by the U.S. Army Research Office under grant number DAAL03-92-G-0408, and by the U.S. Army Space and Strategic Defense Command under contract number DASG60-91-C-0144. The U.S. Government has certain rights in this material, and is authorized to reproduce and distribute reprints for Governmental purposes notwithstanding any copyright notation thereon. Sponsored by a Wisconsin/Hilldale Research Award, by the U.S. Army Space and Strategic Defense Command under contract number DASG60-91-C-0144, and the Air Force Systems Command, USAF, under grant number F49620-93-1-0068. Sponsored by the National Science Foundation under grant number DDM-9201813.     

Ancient silver extraction in the Montevecchio mine basin (Sardinia, Italy): micro-chemical study of pyrometallurgical materials

Different pyrometallurgical materials such as slags, refractory materials and thermally treated lead ores likely related to smelting and extractive processes and chronologically related to Punic and Roman periods (IV–III BC) have been found at Bocche di Sciria and Conca e Mosu in the Montevecchio mine basin (south western Sardinia, Italy), where archaeological findings and classical authors locate extractive metallurgy activities since pre-Roman times. By means of the combined use of X-ray diffraction (XRD), scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectrometry (EDS), selected-area X-ray photoelectron spectroscopy (XPS) and optical microscopy (OM), micro-chemical and micro-structural investigations have been carried out in order to identify the nature of the pyrometallurgical materials, to decipher the processes carried out there and their technological steps and to determine the technological level of competence reached by the ancient metallurgists. The results confirm that the findings can be associated with smelting and extractive processes carried out close to the metal ore deposits first for the argentiferous lead production and, then, for the silver recovery via a cupellation process. Finally, the results disclose the high level of technological competence of the ancient metallurgists able to carry out complex high-temperature processes to treat the argentiferous lead ores and to recover low amounts of silver via high-temperature lead-selective oxidation.     

Disilicon Complexes with Two Hexacoordinate Si Atoms: Paddlewheel‐Shaped Isomers with (ClN4)Si?Si(S4Cl) and (ClN2S2)Si?Si(S2N2Cl) Skeletons

The reaction of 1‐methyl‐3‐trimethylsilylimidazoline‐2‐thione with hexachlorodisilane proceeds toward substitution of four of the disilane Cl atoms during the formation of disilicon complexes with two neighboring hexacoordinate Si atoms. The N,S‐bidentate methimazolide moieties adopt a buttressing role, thus forming paddlewheel‐shaped complexes of the type ClSi(μ‐mt)₄SiCl (mt=methimazolyl). Most interestingly, three isomers (i.e., with (ClN₄)Si? Si(S₄Cl), (ClN₃S)Si? Si(S₃NCl), and (ClN₂S₂)Si? Si(S₂N₂Cl) skeletons as so‐called (4,0), (3,1), and cis‐(2,2) paddlewheels) were detected in solution by using ²⁹Si NMR spectroscopic analysis. Two of these isomers could be isolated as crystalline solids, thus allowing their molecular structures to be analyzed by using X‐ray diffraction studies. In accord with time‐dependent NMR spectroscopy, computational analyses proved the cis‐(2,2) isomer with a (ClN₂S₂)Si? Si(S₂N₂Cl) skeleton to be the most stable. The compounds presented herein are the first examples of crystallographically evidenced disilicon complexes with two Si? Si‐bonded octahedrally coordinated Si atoms and representatives of the still scarcely explored class of Si coordination compounds with sulfur donor atoms.     

Simultaneous high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) analysis of cyanide and thiocyanate from swine plasma

An analytical procedure for the simultaneous determination of cyanide and thiocyanate in swine plasma was developed and validated. Cyanide and thiocyanate were simultaneously analyzed by high-performance liquid chromatography tandem mass spectrometry in negative ionization mode after rapid and simple sample preparation. Isotopically labeled internal standards, Na¹³C¹⁵N and NaS¹³C¹⁵N, were mixed with swine plasma (spiked and nonspiked), proteins were precipitated with acetone, the samples were centrifuged, and the supernatant was removed and dried. The dried samples were reconstituted in 10 mM ammonium formate. Cyanide was reacted with naphthalene-2,3-dicarboxaldehyde and taurine to form N-substituted 1-cyano[f]benzoisoindole, while thiocyanate was chemically modified with monobromobimane to form an SCN-bimane product. The method produced dynamic ranges of 0.1–50 and 0.2–50 μM for cyanide and thiocyanate, respectively, with limits of detection of 10 nM for cyanide and 50 nM for thiocyanate. For quality control standards, the precision, as measured by percent relative standard deviation, was below 8 %, and the accuracy was within ±10 % of the nominal concentration. Following validation, the analytical procedure successfully detected cyanide and thiocyanate simultaneously from the plasma of cyanide-exposed swine.     

Controlling the early stages of pentacene growth by supersonic molecular beam deposition

The key role of the pentacene kinetic energy (Ek) in the early stages of growth on SiOx/Si is demonstrated: islands with smooth borders and increased coalescence differ remarkably from fractal-like thermal growth. Increasing Ek to 6.4 eV, the morphology evolves towards higher density of smaller islands. At higher coverage, coalescence grows with Ek up to a much more uniform, less defected monolayer. The growth, interpreted by the diffusion mediated model, shows the critical nucleus changing from 3 to 2 pentacene for Ek>5-6 eV. Optimal conditions to produce single crystalline films are envisaged.     

Network formation of tissue cells via preferential attraction to elongated structures

Vascular and nonvascular cells often form an interconnected network in vitro, similar to the early vascular bed of warm-blooded embryos. Our time-lapse recordings show that the network forms by extending sprouts, i.e., multicellular linear segments. To explain the emergence of such structures, we propose a simple model of preferential attraction to stretched cells. Numerical simulations reveal that the model evolves into a quasistationary pattern containing linear segments, which interconnect above the critical volume fraction of 0.2. In the quasistationary state, the generation of new branches offset the coarsening driven by surface tension. In agreement with empirical data, the characteristic size of the resulting polygonal pattern is density-independent within a wide range of volume fractions.