On Producing Multiple Solutions Using Repeated Trials

The number of trials that is required by an algorithm to produce a given fraction of the problem solutions with a specified level of confidence is analyzed. The analysis indicates that the number of trials required to find a large fraction of the solutions rapidly decreases as the number of solutions obtained on each trial by an algorithm increases. In applications where multiple solutions are sought, this decrease in the number of trials could potentially offset the additional computational cost of algorithms that produce multiple solutions on a single trial. The analysis framework presented is used to compare the efficiency of a homotopy algorithm to that of a Newton method by measuring both the number of trials and the number of calculations required to obtain a specified fraction of the solutions.     

Kinetics of the thermal dehydrations and decompositions of some mixed metal oxalates

Both isothermal and programmed temperature experiments have been used to obtain kinetic parameters for the dehydrations and the decompositions in nitrogen of the mixed metal oxalates: FeCu(ox)₂·3H₂O, CoCu(ox)₂·3H₂O and NiCu(ox)₂·3.5H₂O, [ox=C₂O₄]. Results are compared with those reported for the thermal decompositions of the individual metal oxalates, Cuox, Coox·2H₂O, Niox·2H₂O and Feox·2H₂O. X-ray photoelectron spectroscopy (XPS) was also used to examinee the individual and the mixed oxalates. Dehydrations of the mixed oxalates were mainly deceleratory processes with activation energies (80 to 90 kJ·mol⁻¹), similar to those reported for the individual hydrated oxalates. Temperature ranges for dehydration were broadly similar for all the hydrates studied here (130 to 180°C). Decompositions of the mixed oxalates were all complex endothermic processes with no obvious resemblance to the exothermic reaction of Cuox, or the reactions of physical mixtures of the corresponding individual oxalates. The order of decreasing stability, as indicated by the temperature ranges giving comparable decomposition rates, was NiCu(ox)₂>CoCu(ox)₂>FeCu(ox)₂, which also corresponds to the order of increasing covalency of the Cu−O bonds as shown by XPS. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

Utilization of cyclotron produced fast neutrons in the activation analysis for oxygen

The possible application of cyclotron-produced fast neutrons to activation analysis for oxygen based on the¹⁶O(n, p)¹⁶N reaction has been investigated. Neutrons were produced by bombarding a thick beryllium target with 22 to 45 MeV deuterons. It was found that the sensitivity increases rapidly with the energy of the deuterons. Using 45 MeV deuterons and a 10 μA beam current a sensitivity of about 20 counts per 1 μg oxigen could be achieved, enabling the determination of less than 1 μg oxigen. In a direct comparison it was experimentally established that the sensitivity for cyclotron-produced neutrons assuming a deuteron beam of about 10 μA, is up to two orders of magnitude higher than that achievable for 14 MeV neutrons with a flux of about 10¹⁰ n/s. The interference of fluorine is at about the same level for both the cyclotron-produced and 14 MeV neutrons. Using cyclotron-produced fast neutrons in the investigated energy range, sodium and magnesium can also interfere, but only to a very much lower extent.     

Kinetics of Desolvation of Related Organic Inclusion Compounds

Abstract

This study dealt mainly with the structure-reactivity relationship of selected organic inclusion compounds. The crystal structures of the inclusion compounds of three related hosts, 2,2′–bis(2,7–di-tert-butyl-9–hydroxy-9–fluorenyl)biphenyl, 2,2′–bis (2,7–dichloro-9–hydroxy-9–fluoienyl)biphenyl and 2, 2′–bis(2,7-dibromo-9–hydroxy-9–fluorenyl)biphenyl with 1,4–dioxane (Compound 1), 1,3–dioxane (Compound 2) and 1,3–dioxolane (Compound 3) respectively were elucidated, using single crystal X-ray crystallography. It was found that the guests were either located in channels or constricted channels (cavities), formed by the host framework. The kinetics of desolvation of these compounds were studied and their activation energies were compared.     

Homogeneous Catalytic Hydrogenation of Amides to Amines

Hydrogenation of amides in the presence of [Ru(acac)₃] (acacH=2,4‐pentanedione), triphos [1,1,1‐tris‐ (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)₃], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH₂(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ¹O)₂(H₂O)(triphos)], [Ru(OAc‐κ²O,O′)(CH₃SO₃‐κ¹O)(triphos)], [Ru(CH₃SO₃‐κ¹O)₂(H₂O)(triphos)] and [Ru₂(μ‐CH₃SO₃)₃(triphos)₂][CH₃SO₃], whereas other complexes, such as [Ru(OAc‐κ¹O)(OAc‐κ²O,O′)(triphos)], [Ru(CH₃SO₃‐κ¹O)(CH₃SO₃‐κ²O,O′)(triphos)], H[Ru(CH₃SO₃‐κ¹O)₃(triphos)], [RuH(CH₃SO₃‐κ¹O)(CO)(triphos)] and [RuH(CH₃SO₃‐κ²O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.     

Liquid membrane electrodes based on quaternary ammonium tetrakis(m-trifluoromethylphenyl)borates

Electrodes based on the appropriate salts give linear responses for 10^-1–10^-4 M tetramethylammonium and tetraethylammonium ions, with some selectivity against alkali metal ions. Use as indicator electrodes in titrations with tetraphenylborate solutions is outlined.     

Discrete and continuum modelling of excavator bucket filling

Two-dimensional discrete and continuum modelling of excavator bucket filling is presented. The discrete element method (DEM) is used for the discrete modelling and the material-point method (MPM) for continuum modelling. MPM is a so-called particle method or meshless finite element method. Standard finite element methods have difficulty in modelling the entire bucket filling process due to large displacements and distortions of the mesh. The use of a meshless method overcomes this problem. DEM and MPM simulations (plane strain) of bucket filling are compared to two-dimensional experimental results. Cohesionless corn grains were used as material and the simulated force acting on the bucket and flow patterns were compared with experimental results. The corn macro (continuum) and micro (DEM) properties were obtained from shear and oedometer tests. As part of the MPM simulations, both the classic (nonpolar) and the Cosserat (polar) continuums were used. Results show that the nonpolar continuum is the most accurate in predicting the bucket force while the polar and DEM methods predict lower forces. The DEM model does not accurately predict the material flow during filling, while the polar and nonpolar methods are more accurate. Different flow zones develop during filling and it is shown that DEM, the polar and the nonpolar methods can accurately predict the position and orientation of these different flow zones.     

Sample Introduction into the Inductively Coupled Plasma by Thermospray Injection

Thermospray vaporization. utilizing an electrically heated stainless steel capillary as a nebulization device. was studied as a means of sample introduction into the inductively coupled plasma. Vapor stripping thermospray vaporization. which included a heated spray chamber and condenser to remove excessive solvent vapor before injection into the plasma. resulted in an cight fold improvement in sensitivity.     

Total synthesis and mechanism of action of the antibiotic armeniaspirol A

Emerging antimicrobial resistance urges the discovery of antibiotics with unexplored, resistance-breaking mechanisms. Armeniaspirols represent a novel class of antibiotics with a unique spiro[4.4]non-8-ene scaffold and potent activities against Gram-positive pathogens. We report a concise total synthesis of (±) armeniaspirol A in six steps with a yield of 20.3% that includes the formation of the spirocycle through a copper-catalyzed radical cross-coupling reaction. In mechanistic biological experiments, armeniaspirol A exerted potent membrane depolarization, accounting for the pH-dependent antibiotic activity. Armeniaspirol A also disrupted the membrane potential and decreased oxygen consumption in mitochondria. In planar lipid bilayers and in unilamellar vesicles, armeniaspirol A transported protons across membranes in a protein-independent manner, demonstrating that armeniaspirol A acted as a protonophore. We provide evidence that this mechanism might account for the antibiotic activity of multiple chloropyrrole-containing natural products isolated from various origins that share a 4-acylphenol moiety coupled to chloropyrrole as a joint pharmacophore. We additionally describe an efflux-mediated mechanism of resistance against armeniaspirols.

The antibiotic armeniaspirol A depolarized bacterial and mammalian cell membranes through a protonophore activity, that accounts for its potent antibiotic effects. A total synthesis of (±) armeniaspirol A was achieved in six steps.     

Distribution coefficients and ion exchange behaviour of some elements with Purolite S-950 in hydrochloric acid

Equilibrium distribution coefficients, K_d, are presented for some elements in hydrochloric acid using the phosphonated polystyrene ion exchange resin Purolite S-950. A few possible separations using this resin are demonstrated by elution curves and separations of synthetic mixtures of some elements (Ru, Rh, Mo, I, Li, Te, Si, Y).