Pathwise rate- stability for input-output processes

An input-output processZ = {Z(t), t 0} is said to be-rate stable ifZ(t) = o((t)) for some non-negative function(t). We prove that the processZ is -rate stable under weak conditions that include the assumption that input satisfies a linear burstiness condition and Z is asymptotically average stable. In many cases of interest, the conditions for-rate-stability can be verified from input data. For example, using input information, we establish-rate stability of the workload for multiserver queues, an ATM multiplexer, and-rate stability of queue-length processes for infinite server queues.     

Acyl vs sulfonyl transfer in N-acyl beta-sultams and 3-oxo-beta-sultams

[reaction: see text] N-Acylsulfonamides usually react with nucleophiles by acyl transfer and C-N bond fission. However, the hydrolysis of N-acyl beta-sultams is a sulfonyl transfer reaction that occurs with S-N fission and opening of the four-membered ring. Similar to other beta-sultams, the N-acyl derivatives are at least 10(6)-fold more reactive than N-acyl sulfonamides. 3-Oxo-beta-sultams are both beta-lactams and beta-sultams but also hydrolyze with preferential S-N bond fission.     

A photochemical method for patterning the immobilization of ligands and cells to self-assembled monolayers

This work describes a chemically well defined method for patterning ligands to self-assembled monolayers (SAMs) of alkanethiolates on gold. This method begins with monolayers presenting a nitroveratryloxycarbonyl (NVOC)-protected hydroquinone which is photochemically irradiated to reveal a hydroquinone group. The resulting hydroquinone is then oxidized to the corresponding benzoquinone, providing a site for the Diels-Alder mediated immobilization of ligands. The rate constant for the photochemical deprotection is 0.032 s(-1) (with an intensity of approximately 100 mW/cm(2) between 355 and 375 nm), corresponding to a half-life of 21 s. The hydroquinone is oxidized to the benzoquinone using either electrochemical or chemical oxidation and then functionalized by reaction with a cyclopentadiene-tagged ligand. Two methods for patterning the immobilization of ligands are described. In the first, the substrate is illuminated through a mask to generate a pattern of hydroquinone groups, which are elaborated with ligands. In the second method, an optical microscope fit with a programmable translational stage is used to write patterns of deprotection which are then again elaborated with ligands. This technique is characterized by the use of well-defined chemical reactions to control the regions and densities of ligand immobilization and will be important for a range of applications that require patterned ligands for biospecific interactions.     

9,9-diphenyl-1,9,10,10a-tetrahydro-2H-phenaleno[1,9-bc]pyrans

Reaction between some naphtho[2,1-b]pyrans and 1,1-diphenylethene affords 9,9-diphenyl-1,9,10,10a-tetrahydro-2H-phenaleno[1,9-bc]pyrans.     

Retention, kinetics and thermodynamics profile of cadmium adsorption from iodide medium onto polyurethane foam and its separation from zinc bulk

The sorption behaviour of 2.5 × 10⁻⁵ M solution of Cd(II) on polyurethane foam (PUF) from iodide medium have been investigated. The conditions were optimized from aqueous solutions of different pH (1-10) and of acids of varied concentration (0.01-1.0 M). The maximum concentration of KI was found to be 0.24 M and equilibration time was established to be 20 min. The data successfully followed the Freundlich and Dubinin-Radushkevich (D-R) isotherms at low metal ion concentration while Langmuir isotherm followed at higher metal ion concentration. The Freundlich parameter 1/n = 0.66 ± 0.02 have been evaluated whereas D-R isotherm yields the sorption free energy E = 10.5 ± 0.1 kJ mol⁻¹ indicating ion exchange type chemisorption. The monolayer coverage (XL) constant of Langmuir isotherm was found to be 23.7 ± 0.4 mg g⁻¹. The numerical values of thermodynamics parameters enthalpy (ΔH), entropy (ΔS) and Gibbs free energy (ΔG) indicated the endothermic and spontaneous nature of sorption. The Scatchard plot analysis was tested to evaluate the binding sites of the PUF and stability constants of sorption were determined. On the basis of these parameters, the sorption mechanism was discussed. Among the foreign ions tested, Pb(II), Hg(II), cyanide and nitrite should be absent. The clean separation of Cd(II) from Zn(II) ions in the ratio 1:250, respectively, was achieved by column chromatography.     

Total synthesis of (+)-xyloketal D, a secondary metabolite from the mangrove fungus Xylaria sp.

(+)-Xyloketal D was prepared in a one-pot multistep domino reaction by heating optically active 5-hydroxy-4-methyl-3-methylenepentan-2-one (R) in toluene with 2,4-dihydroxyacetophenone. The absolute configuration of the natural product was confirmed by preparation of the starting enone from a lactone of established absolute configuration.     

Facile synthesis and characterization of monocrystalline cubic ZrO2 nanoparticles

Crystalline ZrO₂ nanoparticles were prepared from zirconium isopropoxide by slow hydrolysis and subsequent hydrothermal treatment of solutions containing various amounts of sodium hydroxide at 180 °C. Whereas moderately basic solutions lead to the formation of nanoparticles of monoclinic ZrO₂ with plate-like morphology, and nanoparticles of the cubic ZrO₂ high-temperature polymorph with diameters of approx. 5 nm were obtained from strongly basic solutions. The morphology, structure and properties of as-synthesized nanoparticles were characterized using HRTEM, XRD, Raman spectroscopy, UV–vis, PL spectroscopy and BET measurements. The formation of both, the monoclinic and the cubic polymorph, was confirmed by electron microscopy and Raman spectroscopy. The crystallinity and morphology of the resulting ZrO₂ nanoparticles can be adjusted by the choice of the reaction conditions. The cubic ZrO₂ nanoparticles have a high surface area (300 m²/g) and exhibit a strong photoluminescence in the UV region.     

Sorptive potential of sunflower stem for Cr(III) ions from aqueous solutions and its kinetic and thermodynamic profile

The sorptive potential of sunflower stem (180-300 μm) for Cr(III) ions has been investigated in detail. The maximum sorption (≥85%) of Cr(III) ions (70.2 μM) has been accomplished using 30 mg of high density sunflower stem in 10 min from 0.001 M nitric and 0.0001 M hydrochloric acid solutions. The accumulation of Cr(III) ions on the sorbent follows Dubinin-Radushkevich (D-R), Freundlich and Langmuir isotherms. The isotherm yields D-R saturation capacity X_m = 1.60 ± 0.23 mmol g⁻¹, β = −0.00654 ± 0.00017 kJ² mol⁻², mean free energy E = 8.74 ± 0.12 kJ mol⁻¹, Freundlich sorption capacity K_F = 0.24 ± 0.11 mol g⁻¹, 1/n = 0.90 ± 0.04 and of Langmuir constant K_L = 6800 ± 600 dm³ mol⁻¹ and C_m = 120 ± 18 μmol g⁻¹. The variation of sorption with temperature (283-323 K) gives ΔH = −23.3 ± 0.8 kJ mol⁻¹, ΔS = −64.0 ± 2.7 J mol⁻¹ K⁻¹ and ΔG_298k = −4.04 ± 0.09 kJ mol⁻¹. The negative enthalpy and free energy envisage exothermic and spontaneous nature of sorption, respectively. Bisulphate, Fe(III), molybdate, citrate, Fe(II), Y(III) suppress the sorption significantly. The selectivity studies indicate that Cr(III), Eu(III) and Tb(III) ions can be separated from Tc(VII) and I(I). Sunflower stem can be used for the preconcentration and removal of Cr(III) ions from aqueous medium. This cheaper and novel sorbent has potential applications in analytical and environmental chemistry, in water decontamination, industrial waste treatment and in pollution abatement. A possible mechanism of biosorption of Cr(III) ions onto the sunflower stem has been proposed.     

Synthesis and extraction properties of new chromogenic azo-calix[4]dibenzothiacrown ethers

Two novel chromogenic cone calix[4]dibenzothiacrown ethers 3 and 4 in which nitrophenylazo groups attached at the phenyl ring of dibenzothiacrown unit were described. The extraction properties of 3 and 4 toward different transition metal ions have been studied using conductometric technique and found to exhibit Cu²⁺ and Hg²⁺ selectivity with very high stability constants range from log K _assoc = 5.19 to log K _assoc = 8.72.