The influence of fluorinated molecules (semiochemicals and enzyme substrate analogues) on the insect communication system

Can the introduction of fluorine atoms affect the bioactivity of natural semiochemicals? Can fluorine contribute in the creation of specific enzyme inhibitors to interrupt or disrupt the insect communication system? The first step for the bioactivity of a molecule is interaction with the biological sensor. Hydrogen and fluorine are almost bioisosteric and the receptor site of the enzyme can still recognize and accept the fluoro analogue of its natural substrate. However, the peculiar electronegativity of the fluorine atom can affect the binding, absorption, and transport of the molecule. The differences in the molecule's electronic properties can lead to differences in the chemical interactions between the receptor and the fluorinated substrate. Fluorine introduction can modify the metabolic stability and pathway of the semiochemicals in many different ways. Fluorinated analogues can show synergism, inhibition, or hyperagonism effects on insect behaviors, that is, the activity of the nonfluorinated parent compounds can be mimicked, lost, or increased. In any case, the fluorinated molecules can interact with the bioreceptors in a new and disrupting way. The semiochemicals are olfactory substances: fluorine can affect their volatility or smell. Production of semiochemicals from exogenous substances, perception at antennal receptors, and processing of biological responses are the main steps of communication among insects. In the production step, the fluorinated molecules can interact with enzymes that catalyze the biosynthesis of the natural pheromones. In the perception step, fluorinated semiochemicals can interact with the olfactory receptor cells; this often leads to totally unpredictable behaviors. Fluorinated molecules have been developed as probes to elucidate the complex chemorecognition processes of insects. Many of these molecules have been tested to find highly effective behavior-modifying chemicals. New analogues have been synthesized to investigate the metabolic pathway of a pheromone molecule and many of them are promising disrupting agents. Despite such titanic research efforts, the results have often been random, rational trends in the induced behaviors have sometimes been impossible to find, and practical applications of the fluorinated semiochemicals are still uncertain.     

Influence of air abrasion preparation on microleakage in glass ionomer cement restorations

The aim of this study was to assess microleakage in class V cavities prepared by air abrasion or high-speed dental bur and restored with different glass ionomer cements. Sixty bovine incisors were equally divided into 6 groups: I, II and III (preparation by high-speed) and IV, V and VI (preparation by air abrasion). Groups I and IV were restored with Fuji IX; groups II and V with Ketac Molar; and groups III and VI with Vitremer. After 24 h (37 °C), specimens were thermocycled, isolated with nail varnish, immersed in a 0.2% Rhodamine B solution for 24 hours, sectioned longitudinally and analyzed for microleakage using an optical microscope connected to a digital camera and a computer. The images were digitized and a software allowed the quantitative evaluation of microleakage in millimeters. Data were analyzed by Wilcoxon and Kruskal-Wallis tests. It was observed that there were significant differences (p ≤ 0.05) between incisal (enamel) and cervical (dentine/cementum) margins, mainly for Ketac Molar; there was no difference (p ≥ 0.05) between preparation methods, except for group II (high-speed/Ketac Molar) that showed higher infiltration; regarding the materials, Ketac Molar demonstrated the highest microleakage values (p ≤ 0.05), and only Vitremer sealed completely both margins of restorations. It was concluded that air abrasion preparation did not influence microleakage in class V restorations with the employed glass ionomer cements.     

Liquid chromatography with mass spectrometry in tandem mode applied for the identification of wine markers in residues from ancient Egyptian vessels

Presented in this paper is a new method for the identification of tartaric acid as a wine marker in archaeological residues from Egyptian vessels using liquid chromatography with mass spectrometry in tandem mode (LC/MS/MS). Owing to the special characteristics of these samples, such as the dryness and the small quantity available for analysis, it was necessary to have a very sensitive and highly specific analytical method to detect tartaric acid at trace levels in the residues. Furthermore, an alkaline fusion was carried out to identify syringic acid derived from malvidin as a red wine marker, in a deposit residue from a wine jar found at the tomb of king Tutankhamun. Malvidin-3-glucoside, the main anthocyanin that gives young wines their red color, polymerizes with aging into more stable pigments. However, the presence of malvidin in ancient residues can be proved by alkaline fusion of the residue to release syringic acid from the pigment, which has been identified, here for the first time, by using the LC/MS/MS method revealing the red grape origin of an ancient Egyptian wine residue.     

Uniqueness and reciprocity in the boundary-initial value problem for a mixture of two elastic solids occupying an unbounded domain

Summary In this paper two uniqueness theorems for an anisotropic mixture of two linear elastic solids are established: The former concerns the mixed boundary-value problem, the latter the displacement problem. These theorems are proved for unbounded domains in the absence of artificial restrictions upon the behaviour of the unknown fields at infinity. A reciprocity theorem is also given.     

Low-density incomplete <Emphasis Type="Italic">LDL</Emphasis><Superscript><Emphasis Type="Italic">T</Emphasis></Superscript> factorizations

A particular class of incomplete factorizations is proposed as preconditioners for the linear system Ax = b where A is a symmetric, large and sparse matrix. The ILDL ^T< (p) factorization (p = 1,2,3, …) determines the density of the lower triangular matrix L selecting the p largest off-diagonal entries of each column during the Gaussian elimination process. This selection may be computationally expensive, but the effectiveness of the preconditioner allows us to choose very low-density factors to reduce both work time and storage requirements. This incomplete factorization can be performed reliably on H-matrices. When A is a positive definite matrix, but not an H-matrix, one can perform an incomplete factorization if positive off-diagonal entries are removed or reduced and diagonally compensated. Numerical results for a variety of problems and comparisons with other incomplete factorizations are presented. Received: August 2002 / Accepted: December 2002 RID="*" ID="*"This work was supported by the Spanish grant BFM 2001-2641.     

Continuous hyperspectral absorption measurements of colored dissolved organic material in aquatic systems

The majority of organic carbon in the oceans is present as dissolved organic matter (DOM); therefore understanding the distribution and dynamics of DOM is central to understanding global carbon cycles. Describing the time-space variability in colored dissolved organic matter (CDOM) has been difficult, as standard spectrophotometric methods for CDOM determination are laborious and susceptible to methodological biases. Previously, measurements of CDOM absorption in discrete water samples by use of a liquid-waveguide capillary cell (LWCC) compared favorably with measurements made with a benchtop spectrophotometer. Given this, we focused on automating the LWCC technique to improve our spatial and temporal sampling capabilities for CDOM. We found strong correlations between CDOM absorption spectra collected from discrete water samples using standard methods and selected corresponding CDOM spectra collected by the automated LWCC system. The near-continuous measurements by the LWCC system made it possible to map the temporal, spatial, and spectral variability of CDOM absorption along the ship track.     

Solid-phase microextraction liquid chromatography/tandem mass spectrometry to determine postharvest fungicides in fruits

A method to determine five postharvest fungicides (dichloran, flutriafol, o-phenylphenol, prochloraz, tolclofos methyl) in fruits (cherries, lemons, oranges, peaches) has been developed using solid-phase microextraction (SPME) coupled to liquid chromatography (LC) with photodiode array (DAD), mass spectrometry (MS), or tandem mass spectrometry (MS/MS) with ion trap detection. Extraction involved sample homogenization with an acetone/water solution (5:1), filtration, and acetone evaporation prior to fiber extraction. The pesticides were isolated with a fused-silica fiber coated with 50-microm Carbowax/template resin. The effects of pH, ion strength, sample volume, and extraction time were investigated, and their impact on the SPME-LC/MS was studied. Dynamic and static modes of desorption were compared and the variables affecting desorption processes in SPME-LC optimized. Static desorption provided the best recoveries and peak shapes. Recoveries at the limit of quantification (LOQ) levels were between 10% for prochloraz and 60% for o-phenylphenol, with relative standard deviations from 13.6% for prochloraz to 3.1% for o-phenylphenol. The versatility of the method was also exhibited by its excellent linearity in the concentration intervals between 0.0005 and 5 mg kg(-1) for dichloran and 0.01-10 mg kg(-1) for tolclofos methyl and prochloraz. LOQs ranged from 0.25 to 1 microg g(-1) using DAD, from 0.002 to 0.01 microg g(-1) using LC/MS, and from 0.0005 to 0.01 to microg g(-1) using LC/MS/MS. LOQs obtained in the present study using LC/MS and LC/MS/MS are lower than maximum residue limits established for all the fungicides in any matrix studied. The method enables to determine polar pesticides at low-microgram per gram levels in fruits.     

Permeation of naproxen from saturated solutions and commercial formulations through synthetic membranes

The release of naproxen through synthetic membranes, mounted in modified Franz-type diffusion cells, was evaluated, either from saturated solutions or from commercially available topical formulations containing 10% naproxen. The results obtained showed that the porous type synthetic membranes chosen (cellulose acetate and polyethersulphone) can be used for assessing product performance in quality control procedures. The formulations interacted with the solid membranes (silicone and EVA) to change their diffusional characteristics. However, transfer in the membrane, and not the formulation was rate controlling. These membranes could not therefore be used in assessing product release performance for quality control.     

Albumin adsorption on Cibacron Blue F3G-A immobilized onto oligo(ethylene glycol)-terminated self-assembled monolayers

Self-assembled monolayers can be tailored with specific ligands to a certain protein and at the same time prevent the non-specific adsorption of other proteins. Cibacron Blue F3G-A (CB-thiol) was successfully immobilized onto tetra(ethylene glycol)-terminated alkanethiol (CB-thiol). The affinity of human serum albumin (HSA) to immobilized Cibacron Blue F3G-A was studied using mixed thiolate self-assembled monolayers on gold with different n-alkyl chain lengths and functional terminal groups (CH₃-; OH- and tetra(ethylene glycol)). Surfaces were characterized using X-ray photoelectron spectroscopy and water contact angle measurements. Albumin adsorption and exchangeability of the adsorbed albumin molecules with other albumin molecules in solution were evaluated using ¹²⁵I-radiolabeled HSA. Competitive adsorption between albumin and fibrinogen to the different self-assembled monolayers (SAMs) was also investigated. Results showed that the incorporation of CB-thiol on the monolayers does not increase the HSA adsorption and reversibility on the SAMs. However, although specific adsorption of HSA to the immobilized Cibacron Blue F3G-A was not demonstrated, the presence of CB-thiol decreases the affinity of fibrinogen to the OH-terminated SAMs.