Average distribution of prime ideals in families of number fields

We view an algebraic curve over ℚ as providing a one-parameter family of number fields and obtain bounds for the average value of some standard prime ideal counting functions over these families which are better than averaging the standard estimates for these functions.      

Synthesis of Novel Ethyl (substituted)phenyl‐4‐oxothiazolidin‐3‐yl)‐1‐ethyl‐4‐oxo‐1,4‐dihydroquinoline‐3‐Carboxylates as Potential Anticancer Agents

A series of ethyl (substituted)phenyl‐4‐oxothiazolidin‐3‐yl)‐1‐ethyl‐4‐oxo‐1,4‐dihydroquinoline‐3‐carboxylates ( 7a , 7b , 7c , 7d , 7e , 7f , 7g ) has been prepared from reactions between aminoquinolones 6 with arenealdehydes and mercaptoacetic acid. The critical intermediates, 6 a and 6b , were obtained from appropriate amines by a sequence of steps involving (i) reaction with diethylethoxymethylenemalonate, (ii) thermal cyclization in diphenyl ether, (iii) ethylation and (iv) Pd/C catalyzed reduction. New compounds 7a , 7b , 7c , 7d , 7e , 7f , 7g were fully identified and characterized by NMR (¹H and ¹³C) and specifically for 7d by X‐ray crystallography. Compounds 7b , 7c , 7d , 7e , 7f were found not to exhibit activity at 10 uM concentrations against gastric ascitis (AGP‐01), gastric adenocarcinoma kind intestinal (ACP‐02), colon (HCT‐116) and murine melanome (B16F10) cancer cells. However, none exhibited cytotoxicity against normal cells human fibroblast (MRC‐5), murine fibroblast (NIH3T3) and normal human melanocyte (Melan‐A).     

Photosensitizing Activity of Endogenous Eye Lens Chromophores: An Attempt to Unravel Their Contributions to Photo‐Aging and Cataract Disease

UVA‐visible light has been proposed as a risk factor in the photo‐aging of the human eye lens, as well as in the etiology of cataract disease. There is accumulating evidence indicating that photosensitizing reactions mediated by endogenous chromophores, which are generated during human eye lens aging, can play an important role in the generation of these processes. These reactions can lead to protein impairment by inducing non‐enzymatic post‐translational modifications such as protein oxidation and crosslinking. Although numerous chromophores have been characterized as both bound to human eye lens proteins and as unbound low‐molecular‐mass compounds, their contribution to eye lens photoaging and cataract disease is not completely understood. In this article we discuss the photochemical contribution of UV‐filters derived from tryptophan catabolism and advanced glycation end products (AGEs) to human eye lens aging and cataract disease. We also discuss the recently described photosensitizing capacity of chromophores derived from newly discovered glucose and ascorbate degradation as a parallel pathway to their role in AGEs generation.     

Rheology and microstructure of gluten and soya-based o/w emulsions

Highly concentrated oil-in-water (o/w) emulsion stabilised by means of gluten and soya protein isolate (SPI) at low pH have been characterized by means of linear dynamic viscoelasticity and droplet size distribution analysis (DSD). The microstructure of these emulsions has been characterized at a colloidal level by using confocal laser scanning microscopy (CLSM) and light microscopy (LM). These emulsions always exhibited a behaviour characteristic of highly flocculated emulsions with a mechanical spectrum showing a well-developed plateau region. DSD results generally showed log normal bimodal profiles. Microstructure images revealed occurrence of a close packing of droplets with a broad distribution of sizes participating in the formation of a three dimensional flocculated network. The Mason model of elasticity of compressed emulsions has been used to correlate viscoelastic and microstructural parameters giving adequate fitting but underestimating the elastic properties obtained for the highest concentration of gluten. These deviations may be explained in terms of an enhancement of the elastic network formed in the aqueous phase in which the glutenin fraction must play an important role. Paper presented at the Annual European Rheology Conference (AERC) 2005, April 21-23, Grenoble, France.     

Intriguing Differences in the Gas-Phase Dissociation Behavior of Protonated and Deprotonated Gonyautoxin Epimers

The aim of this study was to investigate the unusual gas-phase dissociation behavior of two epimer pairs of protonated gonyautoxins (GTX) following electrospray ionization in comparison to their deprotonated counterparts. The chemical structures of the investigated GTX1-4 variants vary in their substitution pattern at N-1 and the stereochemical orientation of the hydroxysulfate group at C-11 (11α for GTX1/2 versus 11β for GTX3/4). The direct comparison of mass spectra in positive and negative ion modes illustrated two distinct features: first, an intriguing difference between protonated 11α and 11β species, where 11α conformations exhibited almost complete dissociation of [M + H]⁺ ions via facile SO₃ elimination, while 11β species remained mostly intact as [M + H]⁺; and second, the lack of such differences for the deprotonated counterparts. In this study, we propose an acid-catalyzed elimination mechanism from density functional theory calculations, initiated by a proton transfer of a guanidinium proton to the hydroxysulfate group with simultaneous SO₃ release, which is only possible for the 11α conformation based on intramolecular distances. The same mechanism explains the lack of a comparable SO₃ loss in the negative ion mode. CID experiments supported this proposed mechanism for GTX1 and GTX2. Computational modeling of product ions seen in the CID spectra of GTX3 and GTX4 established that the lowest energy dissociation pathway for the 11β epimers is elimination of water with the possibility for further SO₃ release from the intermediate product. Experimental data for structurally analogous decarbamoyl gonyautoxins confirmed the evidence for the GTX compounds as well as the proposed elimination mechanisms.     

A non-autonomous strongly damped wave equation: Existence and continuity of the pullback attractor

In this paper we consider the strongly damped wave equation with time-dependent terms

u_tt−Δu−γ(t)Δu_t+β_ε(t)u_t=f(u),     

Synthesis and application of imprinted polyvinylimidazole-silica hybrid copolymer for Pb determination by flow-injection thermospray flame furnace atomic absorption spectrometry

A novel ion imprinted polyvinylimidazole-silica hybrid copolymer (IIHC) was synthesized and used as a selective solid sorbent for Pb²⁺ ions preconcentration using an on-line solid phase extraction (SPE) system coupled to TS-FF-AAS. The ionic hybrid sorbent was prepared using 1-vinylimidazole and 3-(trimethoxysilyl)propylmethacrylate as monomers, Pb²⁺ ions as template, tetraethoxysilane as reticulating agent and 2,2′-azobis-isobutyronitrile as initiator. The best on-line SPE conditions concerning sorption behavior, including sample pH (6.46), buffer concentration (9.0 mmol L⁻¹), eluent (HNO₃) concentration (0.5 mol L⁻¹) and preconcentration flow rate (4.0 mL min⁻¹), were optimized by means of full factorial design and Doehlert matrix. The analytical curve ranged from 2.5 to 65.0 μg L⁻¹ (r = 0.999) with limit of detection of 0.75 μg L⁻¹; the precision (repeatability) calculated as relative standard deviation (n = 10) was 5.0 and 3.6% for Pb²⁺ concentration of 10.0 and 60.0 μg L⁻¹, respectively. From on-line breakthrough curve, column capacity was 3.5 mg g⁻¹. Preconcentration factor (PF), consumptive index (CI) and concentration efficiency (CE) were 128.0, 0.16 mL and 25.6 min⁻¹, respectively. The selective performance of the sorbent, based on relative selectivity coefficient, was compared to NIC (non imprinted copolymer) for the binary mixture Pb²⁺/Cd²⁺, Pb²⁺/Cu²⁺ and Pb²⁺/Zn²⁺. The results showed that ion imprinted polyvinylimidazole-silica hybrid polymer had higher selectivity for Pb²⁺ than NIC at 64.9, 16.0 and 8.8 folds. The developed method was successfully applied for highly sensitive and selective Pb²⁺ determination in different kinds of water samples, parenteral solutions and urine. Accuracy was also assessed by analyzing certified reference fish protein (DORM-3) and marine sediment (MESS-3 and PACS-2) with satisfactory results.     

Hydrogen-bond-mediated self-assembly of 26-membered diaza tetraester crowns of 3,5-disubstituted 1H-pyrazole. Dimerization study in the solid state and in CDCl3 solution

By using an improved synthetic method reported earlier, the cyclic stannoxanes obtained from RN-diethanolamine (R = Me, Bu) and dibutyltin oxide have been reacted with 1H-pyrazole-3,5-dicarbonyl dichloride to afford 26-membered diaza tetraester crowns (1, R = Me; 3, R = Bu) and 39-membered triaza hexaester crowns (2, R = Me; 4, R = Bu). The new structures were identified from their analytical and spectroscopic ((1)H and (13)C NMR, FAB-MS, and/or ESI-MS) data. Both diaza tetraester crowns (1 and 3), containing two 1H-pyrazole units, self-assemble into dimeric species through the formation of four hydrogen bonds involving the two NH pyrazole groups and the two tertiary amine groups of both crowns, as proved by X-ray crystallography and NMR analysis. Preliminary NMR, ESI-MS, MALDI-TOF-MS, and molecular modeling studies suggest that, in CDCl(3) solution, 1 interacts with ethyleneurea (ETU), affording 1:1, 2:1, and 2:2 1-ETU complexes.     

Confinement of halide ions within homologous inverse coordination hosts; modification of halide-ion selectivity

The structures of a series of spherical host-guest complexes [{MeE(PPh)(3)Li(4)·3thf}(4)(μ(4)-X)](-) (E = Al, [1X](-); E = Ga, [2X](-); E = In, [3X](-)) reveal that changing the halide ions (X = Cl, Br, or I) within their central tetrahedral Li(4) sites has negligible effect on the structural parameters.