Tetrakis(4-N,N-dimethylaminobenzene)porphyrinato]manganese(III) acetate as a novel carrier for a selective iodide PVC membrane electrode.

[5,10,15,20-Tetrakis(4-N,N-dimethylaminobenzene)porphyrinato]Mn(III) acetate (MnTDPAc) was applied as an ionophore for an iodide-selective PVC membrane electrode. The influences of the membrane composition, pH of the test solution and foreign ions on the electrode performance were investigated. The sensor exhibited not only excellent selectivity to iodide ion compared to Cl- and lipophilic anions such as ClO4- and salicylate, but also a Nernstian response with a slope of -59.4 +/- 1.2 mV per decade for iodide ions over a wide concentration range from 1.0 x 10(-2) to 7.5 x 10(-6) M at 25 degrees C. The potentiometric response was independent of the pH of the solution in the pH range of 2 - 8. The electrode could be used for at least 2 months without any considerable divergence in the potential. Good selectivity for iodide ion, a very short response time, simple preparation and relatively long-term stability were the silent characteristics of this electrode. It was successfully used as an indicator electrode in the potentiometric titration of iodide ions, and also in the determination of iodide from seawater samples and drug formulations.     

Fundamental reactions in TiO2 nanocrystallite aqueous solutions studied by pulse radiolysis

Reactions of the hydrated electron, H atoms, 2-propanol, and methanol radicals with the TiO₂ nano-particles have been studied either directly or by competition kinetics. The radicals were produced by radiolysis of 2-propanol, t-butanol, or methanol aqueous solutions in acid pH's. The reactions involve electron injection to the conduction band. As expected, the t-butanol radical is inert towards TiO₂ under our conditions, while the other reducing radicals react with TiO₂. The reactivity decreases in the order: e_aq⁻>H>CH₃COHCH₃>CH₂OH. Two TiO₂ nanocrystallite sizes, with average diameters of 1.0 and 4.7 nm were compared. For equal concentrations (in terms of TiO₂ molecules), the rate of electron injection shows relatively little dependency on particle size. The rates of interfacial electron transfer and transfer coefficient are also reported.     

Fairness in Scheduling

On-line machine scheduling has been studied extensively, but the fundamental issue of fairness in scheduling is still mostly open. In this paper we explore the issue in settings where there are long-lived processes which should be repeatedly scheduled for various tasks throughout the lifetime of a system. For any such instance we develop a notion ofdesiredload of a process, which is a function of the tasks it participates in. Theunfairnessof a system is the maximum, taken over all processes, of the difference between the desired load and the actual load.An example of such a setting is thecarpool problemsuggested by Fagin and Williams [IBM Journal of Research and Development27(2) (1983), 133–139]. In this problem, a set ofnpeople form a carpool. On each day a subset of the people arrive and one of them is designated as the driver. A scheduling rule is required so that the driver will be determined in a “fair” way.We investigate this problem under various assumptions on the input distribution. We also show that the carpool problems can capture several other problems of fairness in scheduling.     

Headspace SPME–GC Method for Acetone Analysis and its Biomedical Application

A new method for extraction and analysis of acetone in human urine based on headspace solid phase microextraction using a mixture of activated carbon and zeolite as sorbents in a PVC matrix coated on a silver wire and its application to the determination of ketone bodies is described. Unlike commercial fibers, which are coated on fused silica, the coating adheres strongly to the silver wire and is thermally stable up to 250 °C. After optimization of coating composition and microextraction conditions the fiber was used for the analysis of acetone in human urine.     

Comparison of dynamical heterogeneity in hard-sphere and attractive glass formers

Using molecular dynamics simulations, we have determined that the nature of dynamical heterogeneity in jammed liquids is very sensitive to short-ranged attractions. Weakly attractive systems differ little from dense hard-sphere and Lennard-Jones fluids. Particle motion is punctuated and tends to proceed in steps of roughly a single particle diameter. Both of these basic features change in the presence of appreciable short-ranged attractions. Transient periods of particle mobility and immobility cannot be discerned at intermediate attraction strength, for which structural relaxation is greatly enhanced. Strong attractions, known to dramatically inhibit relaxation, restore bimodality of particle motion. But in this regime, transiently mobile particles move in steps that are significantly more biased toward large displacements than those in the case of weak attractions. This modified feature of dynamical heterogeneity, which cannot be captured by conventional mode coupling theory, verifies recent predictions from a model of spatially correlated facilitating defects.     

Synthesis of 2,2-Dimethyl-1,2-Dihydro-3H-pyrrol-3-one Preliminary Communication

The title compound 3g is obtained via two different routes, either in a multistep synthesis starting from 2-amino-2-methylpropionic acid (methylalanine) or by light-induced, oxidative dealkylation of the corresponding N-isopropyl derivative 3c .     

Poly(N‐Bromobenzene‐1,3‐Disulfonylamide), N,N,N′,N′‐Tetrabromobenzene‐1,3‐Disulfonylamide and DABCO‐Bromine Complex: As Novel Reagents for the Oxidative Coupling of Thiols to Disulfides

An efficient method for the oxidative coupling of thiols to their corresponding disulfides by new reagents poly(N‐bromobenzene‐1,3‐disulfonylamide) PBBS , N,N,N′,N′‐tetrabromobenzene‐1,3‐disulfonylamide TBBDA and DABCO‐bromine complex is described. The reaction was applicable to a variety of thiols with high chemoselectivity.     

Photochemistry of 2-Allyl-3-oxo-2,3-dihydro-1H-pyrrole-2-carboxyalates

On acetone-sensitized irradiation the title compounds 3a–c are converted to 2-allyl-3-hydroxy-1H-pyrrole-2-carboxylates 4 in reasonable yields.