Sensing the physicochemical nature of he and ne in micropores by adsorption measurements

He and Ne in contact with molecular sieves in the form of crystalline A zeolites and amorphous carbon molecular sieves fibers (CMSF) were studied by adsorption measurements. Classification of the effective enclosure of zeolitic apertures and of graphitic constrictions, as determined by recent temperature-programmed desorption mass spectrometry (TPD-MS) studies of adsorption of He and Ne onto these materials, was utilized in making a prudent choice of samples and experimental conditions. In view of the former TPD information, the behaviors of adsorption and volumetric measurements reported herein are straightforwardly interpreted. The combined TPD, adsorption isotherms, and dead volume data deepen the understanding of the physicochemical nature of adsorbed gas, where gas adsorption in the vicinity of pore constrictions and/or apertures as well as on the inner surface areas of pores and/or cages could be resolved. Previous conclusions that the huge activation energies measured for Ne/CMSF at high temperatures are unlikely to characterize chemical desorption but reflect those required for overcoming the barrier of effectively constricted apertures were confirmed by the volumetric data presented here. At 77 K, considerable He adsorption was observed in the porous solids and found to be responsible for abnormal deduced values of dead volumes. The occurrence of significant adsorption of He onto A zeolites and CMSF at 77 K warrants the realization that in cases concerning porous materials, volumetrically deduced quantities should not be taken for granted, but should be carefully considered and uniquely interpreted in relation to the specific experimental conditions under which they are taken.     

Electron-impact induced rearrangements in isomeric pyridine aldoximes

The mass spectra of α-, β- and γ-pyridine aldoximes and the respective O-methyl ethers were studied. The mass spectral behaviour of α-pyridine aldoxime is characterized by the elimination of NO, while the molecular ion of the γ-isomer expels H₂ CN. In the case of the β-isomer the formation of the m/e 67 ion (C₄H₅N) in a concerted process is the main feature. In the α-pyridine aldoxime methyl ether, in sharp contrast to the hydroxy analog, the M-30 peak was found to be due to the elimination of CH₂O, the expulsion of NO being absent. The mechanism of the fragmentation reactions is discussed, the conclusion drawn being based on the high resolution measurements as well as on the spectra of the respective deuterioanalogs and on the metastable transitions.     

Multichannel homogeneous immunoassay for detection of 2,4,6-trinitrotoluene (TNT) using a microfabricated capillary array electrophoresis chip

A high-throughput homogeneous immunoassay for the sensitive detection of 2,4,6-trinitrotoluene (TNT) has been developed using radial capillary array electrophoresis microdevices. Samples consisting of equilibrium mixtures of anti-TNT antibody (Ab), fluorescein-labeled TNT, and various concentrations of unlabeled TNT were electrokinetically injected into 48 channels of a radial capillary array electrophoresis microchannel plate. The rapid electrophoretic separation allows us to analyze the equilibrium ratio formed by the competition between the labeled and the unlabeled TNT for Ab binding. The simultaneous parallel TNT separations facilitate determination of a calibration curve for the TNT assay, which has high sensitivity (LOD, 1 ng/mL) and a wide dynamic range (1-300 ng/mL).     

A new route of oxygen isotope exchange in the solid phase: demonstration in CuSO4.5H2O

Temperature-programmed desorption mass spectrometry (TPD-MS) measurements on [(18)O]water-enriched copper sulfate pentahydrate (CuSO(4).5H(2)(18)O) reveal an unambiguous occurrence of efficient oxygen isotope exchange between the water of crystallization and the sulfate in its CuSO(4) solid phase. To the best of our knowledge, the occurrence of such an exchange was never observed in a solid phase. The exchange process was observed during the stepwise dehydration (50-300 degrees C) of the compound. Specifically, the exchange promptly occurs somewhere between 160 and 250 degrees C; however, the exact temperature could not be resolved conclusively. It is shown that only the fifth, sulfate-associated, anionic H(2)O molecule participates in the exchange process and that the exchange seems to occur in a preferable fashion with, at the most, one oxygen atom in SO(4). Such an exchange, occurring below 250 degrees C, questions the common conviction of unfeasible oxygen exchange under geothermic conditions. This new oxygen exchange phenomenon is not exclusive to copper sulfate but is unambiguously observed also in other sulfate- and nitrate-containing minerals.     

Oxidation of Ascorbate by Ni(III) Complexes with Tetraaza-macrocyclic Ligands in Neutral Aqueous Solutions. A Pulse-Radiolysis Study

Abstract

The mechanisms and kinetics of oxidation of ascorbate, AH^?, by Ni(III)Lⁱ _aq and by LⁱNi(III) (HPO₄)₂ ^? complexes (L¹ = meso-(5,12)-7,7,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; L² = 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane) in neutral aqueous solutions have been investigated.

The oxidation of ascorbate by the LⁱNi(III) (HPO₄)₂ ^? and Ni(III)L¹ _aq proceeds via two consecutive reactions well separated in time. The products of the first reaction are the A^.? radical anion and the corresponding Ni(II) complex. The oxidations by the LⁱNi(III)(HPO₄)₂ ^? complexes proceed via the outer sphere mechanism, whereas the detailed mechanism of reaction of Ni(III)L¹ _aq cannot be determined. The rate of reaction decreases with the increase in the concentration of phosphate, thus indicating that LⁱNi(III)(HPO₄)(H₂O)⁺ and LⁱNi(III)OH²⁺ are stronger oxidizing agents than LⁱNi(III)(HPO₄)^? ₂.

The oxidation of ascorbate by Ni(III)L² _aq proceeds via three consecutive reactions which are well separated in time. Thus the results clearly point out that this process occurs via the inner sphere mechanism. The first transient observed is tentatively identified as L²(H₂O)Ni(II)(A^.?)²⁺, i.e., an unexpected complex of the ascorbate anion radical. Also in this process the last transient observed is the A^.? anion radical. The stabilization of the ascorbyl radical in a transient complex might be of biological significance.     

Scheduling programs with repetitive projects: A comparison of a simulated annealing,a genetic and a pair-wise swap algorithm

We address the problem of scheduling in programs involving the production of multiple units of the same product. Our study was motivated by a construction program for fast naval patrol boats. Other applications of this problem include procurement of multiple copies of aircraft, spacecraft, and weapon systems. In this problem we must decide how many units of the product to assign to each of a number of available crews (individuals, teams, subcontractors, etc.). These types of problems are characterized by two potentially conflicting considerations: 1) the need to complete each unit by its contractual due date, and 2) learning effects. Because of the first consideration, there is a tendency to use multiple crews for simultaneous production, so that meeting due dates is assured. However, the second consideration encourages assigning many units to a single crew so that learning effects are maximized. We study this scheduling problem with two different penalty cost structures and develop models for both versions. The models trade-off the penalty associated with late deliveries and the savings due to learning (and possibly incentive payments for early completion). We discuss different heuristic algorithms — simulated annealing, a genetic algorithm, and a pair-wise swap heuristic — as well as an exhaustive search to determine a baseline for comparisons. Our computational results show that the pair-wise swap algorithm is the most efficient solution procedure for these models.     

Propagation of avalanches in Mn12-acetate: magnetic deflagration

Local time-resolved measurements of fast reversal of the magnetization of single crystals of Mn12-acetate indicate that the magnetization avalanche spreads as a narrow interface that propagates through the crystal at a constant velocity that is roughly 2 orders of magnitude smaller than the speed of sound. We argue that this phenomenon is closely analogous to the propagation of a flame front (deflagration) through a flammable chemical substance.     

Multi-parameter evaluation of fast sol–gel process by terahertz measurements

We present a feasibility study to apply terahertz (THz) spectroscopy and THz imaging as non-destructive diagnostic tools for sol–gel analysis, manufacturing and quality control. By performing THz spectroscopy on liquid and solid samples we were able to follow several key parameters during the sol–gel formation process and of the final product. Sol–gel transformations were monitored by THz absorption, whereas density changes have been observed through changes in refractive indices. Time domain spectroscopy (TDS), both in transmission and reflection geometries, was used to monitor the properties of fast sol–gel resins. THz imaging of gold coated, thin-film sol–gel enables us to determine inhomogeneities and defects in their internal structure. We demonstrated that THz spectroscopy can be implemented as an online analytical tool for multi-parameter evaluation of the sol–gel process during fabrication, and of the final product.     

The measurement and analysis of normal incidence solar UVB radiation and its application to the photoclimatherapy protocol for psoriasis at the Dead Sea, Israel

The broad-band normal incidence UVB beam radiation has been measured at Neve Zohar, Dead Sea basin, using a prototype tracking instrument composed of a Model 501A UV-Biometer mounted on an Eppley Solar Tracker Model St-1. The diffuse and beam fraction of the solar global UVB radiation have been determined using the concurrently measured solar global UVB radiation. The diffuse fraction was observed to exceed 80% throughout the year. The application of the results of these measurements to the possible revision of the photoclimatherapy protocol for psoriasis patients at the Dead Sea medical spas is now under investigation. The suggested revision would enable the sun-exposure treatment protocol to take advantage of the very high diffuse fraction by allowing the patient to receive the daily dose of UVB radiation without direct exposure to the sun, viz. receive the diffuse UVB radiation under a sunshade. This would require an increase in sun-exposure time intervals, as the UVB radiation intensity beneath a sunshade is less than that on an exposed surface.