On sparse spanners of weighted graphs

Given a graphG, a subgraphG' is at-spanner ofG if, for everyu,v V, the distance fromu tov inG' is at mostt times longer than the distance inG. In this paper we give a simple algorithm for constructing sparse spanners for arbitrary weighted graphs. We then apply this algorithm to obtain specific results for planar graphs and Euclidean graphs. We discuss the optimality of our results and present several nearly matching lower bounds.The work of G. Das and D. Joseph was supported by NSF PYI Grant DCR-8402375. The work of D. Dobkin was supported by NSF Grant CCR-8700917. The work of J. Soares was supported by CNPq proc 203039/87.4 (Brazil) and NSF Grant CCR-9014562. This research was accomplished while G. Das was a student at the University of Wisconsin-Madison. A preliminary version was presented at the Second Scandinavian Workshop on Algorithm Theory, Bergen, Norway, 1990, under the title Generating Sparse Spanners for Weighted Graphs, and proceedings appear in the series Lecture Notes in Computer Science, Springer-Verlag. The preliminary version also appears as Princeton University Technical Report CS-TR-261-90, and as University of Wisconsin-Madison Computer Sciences Technical Report 882.     

Hydrolytic protein cleavage mediated by unusual mononuclear copper(II) complexes: X-ray structures and solution studies

The crystal structures and redox and UV-vis/EPR spectroscopic properties of two new mononuclear copper(II) complexes, [Cu(HL1)Cl2] (1) and [Cu(L1)Cl] (2), prepared through the reaction between copper(II) chloride and the ligand 2-[(bis(pyridylmethyl)amino)methyl]-4-methyl-6-formylphenol (HL1) under distinct base conditions, are reported along with solution studies. Also, we demonstrate that these CuII complexes are able to cleave unactivated peptide bonds from bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active Cu(II) complexes described to date, since their cleavage activity is detected in minutes and evidence is here presented for a hydrolytic mechanism mediating protein cleavage by these complexes.     

Characterization of Sol-gel bioencapsulates for ester hydrolysis and synthesis

Candida rugosa lipase was entrapped in silica sol-gel particles prepared by hydrolysis of methyltrimethoxysilane and assayed by p-nitrophenyl palmitate hydrolysis, as a function of pH and temperature, giving pH optima of 7.8 (free enzyme) and 5.0–8.0 (immobilized enzyme). The optimum temperature for the immobilized enzyme (50–55°C) was 19°C higher than for the free enzyme. Thermal, operational, and storage stability were determined with n-butanol and bytyric acid, giving at 45°C a half-life 2.7 times greater for the immobilized enzyme; storage time was 21 d at room temperature. For ester synthesis, the optimum temperature was 47°C, and high esterification conversions were obtained under repeated batch cycles (half-life of 138 h).     

The partial hydrogenation of benzene to cyclohexene by nanoscale ruthenium catalysts in imidazolium ionic liquids

The controlled decomposition of an Ru(0) organometallic precursor dispersed in 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI.PF(6)), tetrafluoroborate (BMI.BF(4)) or trifluoromethane sulfonate (BMI.CF(3)SO(3)) ionic liquids with H(2) represents a simple and efficient method for the generation of Ru(0) nanoparticles. TEM analysis of these nanoparticles shows the formation of superstructures with diameters of approximately 57 nm that contain dispersed Ru(0) nanoparticles with diameters of 2.6+/-0.4 nm. These nanoparticles dispersed in the ionic liquids are efficient multiphase catalysts for the hydrogenation of alkenes and benzene under mild reaction conditions (4 atm, 75 degrees C). The ternary diagram (benzene/cyclohexene/BMI.PF(6)) indicated a maximum of 1 % cyclohexene concentration in BMI.PF(6), which is attained with 4 % benzene in the ionic phase. This solubility difference in the ionic liquid can be used for the extraction of cyclohexene during benzene hydrogenation by Ru catalysts suspended in BMI.PF(6). Selectivities of up to 39 % in cyclohexene can be attained at very low benzene conversion. Although the maximum yield of 2 % in cyclohexene is too low for technical applications, it represents a rare example of partial hydrogenation of benzene by soluble transition-metal nanoparticles.     

Addition of carbon nucleophiles to cyclic N-acyliminium ions in SDS/water

The acid-catalyzed addition of 1,3-dicarbonyl compounds and activated olefins (silyl enol ethers and ethyl vinyl ether) to N-Boc-2-methoxypyrrolidine (1a) and N-Boc-2-methoxypiperidine (1b) in SDS/water medium is described. Good yields of the corresponding 2-substituted N-Boc pyrrolidines were generally observed from 1a while moderate yields prevailed from 1b.     

A comparative study for elastic electron collisions on the isoelectronic CNN, NCN, and CCO radicals

In this work, we present a theoretical study on elastic electron collisions from three isoelectronic free radicals (CNN, NCN, and CCO) in the low incident energy range. More specifically, calculated differential, integral, and momentum transfer cross sections are reported in the 1-30 eV energy range. Calculations are performed in the static-exchange and static-exchange-polarization levels. The iterative Schwinger variational method is used to solve the scattering equations. Our study reveals that the calculated cross sections for the three targets are significantly different at incident energies below 10 eV. Above that energy, a remarkable similarity among the calculated results is seen.     

Generic fast gradient liquid chromatography/tandem mass spectrometry techniques for the assessment of the in vitro permeability across the blood-brain barrier in drug discovery

Rapid, generic gradient liquid chromatography/tandem mass spectrometry (LC/MS/MS) assays, designed to accelerate sample analyses, have been developed to keep pace with the productivity of advanced synthetic procedures. In this study, LC/MS/MS was combined with an in vitro, cell-based, blood-brain barrier (BBB) model to evaluate the potential of new chemical entities (NCEs) to cross the BBB. This in vitro assay provides the permeability of discovery compounds across a monolayer of a primary culture of bovine brain microvessel endothelial cells in a fraction of the time that is required for in vivo studies (brain/plasma concentrations), using only 2 mg of the compound. The results are consistent with in vivo brain/plasma concentration ratio data.     

Generation and reactivity of 3‐carbethoxy‐5‐phenyl‐5H,7H‐thiazolo[3,4‐c]oxazol‐4‐ium‐1‐olate

3‐Carbethoxy‐5‐phenyl‐5H,7H‐thiazolo[3,4‐c]oxazol‐4‐ium‐1‐olate was generated from (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazolidine‐4‐carboxylic acid and its reactivity studied. This münchnone showed low reactivity as dipole although from the reaction with dimethyl acetylenedicarboxylate the corresponding (3R)‐3‐phenyl‐17H,3H‐pyrrolo[1,2‐c]thiazole‐5,6,7‐tricarboxylate could be isolated. The thermolysis of (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazolidine‐4‐carboxylic acid in refluxing acetic anhydride led to the synthesis of N‐(1‐ethoxycarbonyl‐2‐phenylvinyl)‐2‐phenyl‐4‐thioxo‐1,3‐thiazolidine. The structure of methyl (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazoliddine‐4‐carboxylate was determined by X‐ray crystallography.