Phototransformation of the herbicide sulcotrione on maize cuticular wax

Vegetation plays a key role in environmental cycling and the fate of many organic pollutants. This is especially the case for pesticides because plant leaves are their first reaction environment after application. It is commonly accepted that photochemical reactions of pollutants on plants predominantly take place in the cuticular wax coating of the leaves. Thus, we used films made of either cuticular wax extracted from maize or carnauba gray wax as a model support. Under simulated sunlight irradiation, sulcotrione (a new class of triketone herbicides) sorbed on cuticular wax films was photolyzed and mainly underwent an intramolecular cyclization. The photoproduct is a chromone derivative which was isolated and fully characterized. It is reported for the first time as a sulcotrione degradation product. The photoreactivity of formulated sulcotrione at the surface of cuticular waxes was investigated too. It photodegraded more rapidly than nonformulated sulcotrione. This study also shows that the rate of sulcotrione photolysis was much faster than the rate of penetration into the wax; photolysis should be, thus, a relevant process in real conditions.     

Simulated solar light irradiation of mesotrione in natural waters

Photolysis is expected to be a major degradation process for pollutants in surface waters. We report here the first photodegradation study on mesotrione, a new triketone herbicide for use in maize. In a first step, we investigated the direct photolysis of mesotrione at 365 nm from a kinetic and analytical point of view. Mesotrione sensitizes its own oxidation through singlet oxygen formation and sensitizes the oxidation of H-donors through electron or H-atom transfer. In a second step, irradiation experiments were performed under conditions prevalent in the aqueous environment. Mesotrione in submicromolar concentrations was exposed to simulated sunlight, in addition to Suwannee River natural organic matter and/or nitrates. Suwannee River natural organic matter sensitizes the oxidation of mesotrione through the intermediacy of singlet oxygen, and the rate of mesotrione transformation is significantly enhanced for Suwannee River natural organic matter concentrations equal to or above 10 mg/L. Nitrates played a negligible role in SRNOM solutions.     

Control of chaos in nonlinear systems with time-periodic coefficients

In this study, some techniques for the control of chaotic nonlinear systems with periodic coefficients are presented. First, chaos is eliminated from a given range of the system parameters by driving the system to a desired periodic orbit or to a fixed point using a full-state feedback. One has to deal with the same mathematical problem in the event when an autonomous system exhibiting chaos is desired to be driven to a periodic orbit. This is achieved by employing either a linear or a nonlinear control technique. In the linear method, a linear full-state feedback controller is designed by symbolic computation. The nonlinear technique is based on the idea of feedback linearization. A set of coordinate transformation is introduced, which leads to an equivalent linear system that can be controlled by known methods. Our second idea is to delay the onset of chaos beyond a given parameter range by a purely nonlinear control strategy that employs local bifurcation analysis of time-periodic systems. In this method, nonlinear properties of post-bifurcation dynamics, such as stability or rate of growth of a limit set, are modified by a nonlinear state feedback control. The control strategies are illustrated through examples. All methods are general in the sense that they can be applied to systems with no restrictions on the size of the periodic terms.     

Isorhizochalin: a Minor Unprecedented Bipolar Sphingolipid of Stereodivergent Biogenesis from the <Emphasis Type="Italic">Rhizochalina incrustata</Emphasis>

Isorhizochalin (1) was isolated as its peracetate from the EtOH extract of the sponge Rhizochalina incrustata. Its structure and absolute stereochemistry were elucidated as (2S,3R,26R,27R)-2,27-diamino-3-O-β-d-galactopyranosyl-oxy-26-hydroxyoctacosan-18-one by extensive NMR, MS studies, chemical transformations, including micromolar-scale Baeyer–Villiger oxidation, and by analysis of CD spectra of isorhizochalinin perbenzoate (2b). Isorhizochalin is an unprecedented C-2 epimer of rhizochalin having an erythro configuration at the glycosylated 2-amino-3-alkanol α-terminus in contrast with a canonical threo configuration for other representatives of this structural group. Probable biogenesis of 1 is discussed in the context of known sphingolipid biosynthesis beginning with condensation of alanine with a fatty acyl CoA thioester. The aglycone, isorhizochalinin (2a), shows cytotoxicity against human leukemia HL-60 and THP-1 cells with IC₅₀ values of 2.90 and 2.20 μM, respectively.     

Comparative risk assessment of residential radon exposures in two radon-prone areas, ?tei (Romania) and Torrelodones (Spain)

Radon and radon progeny are present indoors, in houses and others dwellings, representing the most important contribution to dose from natural sources of radiation. Most studies have demonstrated an increased risk of lung cancer at high concentration of radon for both smokers and nonsmokers. The work presents a comparative analysis of the radon exposure data in the two radon-prone areas, ?tei, Transylvania, (Romania), in the near of old Romanian uranium mines and in the granitic area of Torrelodones town, Sierra de Guadarrama (Spain). Measurements of indoor radon were performed in 280 dwellings (Romania) and 91 dwellings (Spain) by using nuclear track detectors, CR 39. The highest value measured in ?tei area was 2650 Bq m^− 3 and 366 Bq m^− 3 in the Spanish region. The results are computed with the BEIR VI report estimates using the age-duration model at an exposure rate below 2650 Bq m^− 3. We used the EC Radon Software to calculate the lifetime lung cancer death risks for individuals groups in function of attained age, radon exposures and tobacco consumption. A total of 233 lung cancer deaths were observed in the ?tei area for a period of 13 years (1994-2006), which is 116.82% higher than expected from the national statistics. In addition, the number of deaths estimated for the year 2005 is 28, which is worth more than 2.21 times the amount expected by authorities. In comparison, for Torrelodones was rated a number of 276 deaths caused by lung cancer for a period of 13 years, which is 2.09 times higher than the number expected by authorities. For the year 2005 in the Spanish region were reported 32 deaths caused by pulmonary cancer, the number of deaths exceeding seen again with a factor of 2.10 statistical expectations. This represents a significantly evidence that elevated risk can strongly be associated with cumulated radon exposure.     

The Crystallization of Ba-Substituted CsTiSi2O6.5 Pollucite Using CsTiSi2O6.5 Seed Crystals

Barium (Ba)-substituted CsTiSi₂O_6.5 materials of two types, Cs _x Ba_{1− x} TiSi₂O_{(7− x /2)} and Cs _x Ba_{(1− x )/2}TiSi₂O_6.5 were synthesized with the pollucite structure with 1≥ x ≥0.6. When the Ba-substituted precursor materials were heat treated to 850°C for 4 h, a mixture of amorphous and unidentifiable phases formed. However, with the addition of 10 wt% of crystalline CsTiSi₂O_6.5 to the Ba-containing precursors, nearly single-phase pollucite was obtained after 20 h at 750°C for x ≥0.6. The added crystalline CsTiSi₂O_6.5 particles act as nuclei that allow the Ba-containing materials to crystallize into the pollucite phase and to avoid the formation of unwanted phases that would otherwise nucleate and grow. These new materials can be used to study the stability of CsTiSi₂O_6.5 as a durable ceramic waste form, which could accommodate with time both Cs and its decay product, Ba.     

Influence of pre-strain and heat treatment on mechanical properties of aluminum sheet

In this work the alterations of mechanical properties of two 6xxx Aluminum alloys during different states of a production process are investigated. The mechanical properties are determined by means of the tensile test. Tensile tests are performed shortly after four steps in the production process: the shipment of the two alloys, a certain period of storage, uniaxial pre-stretching, and heat treatment that corresponds to the temperature profile during e-coating. Results are displayed as a function of orientation with reference to rolling direction, as a function of the level of uniaxial pre-stretching and as function of the temperature profile.     

Driving in fog: The effects of driving experience and visibility on speed compensation and hazard avoidance

Inexperience is one of the strongest predictors for collisions, but it remains unclear how novice drivers differ from experienced drivers in terms of safety-related behavioural adaptations such as speed reduction in the presence of reduced visibility. To investigate the influence of driving experience on behavioural compensations to fog, average speed, speed variability, steering variability, collision rate, and hazard response time were measured in a driving simulator. Experienced drivers drove faster in clear visibility than novice drivers, yet they reduced their speed more in reduced visibility so that both groups drove at the same speed in simulated fog. Compared to experienced drivers, novice drivers had higher hazard response times, greater speed and steering variability, and were the only drivers to have collisions.     

Analysis of soluble lignin in sugarcane by ultrahigh performance liquid chromatography-tandem mass spectrometry with a do-it-yourself oligomer database

Lignin is a polymer found in the cell wall of plants and is one of the main obstacles to the implementation of second-generation ethanol production because it confers the recalcitrance of the lignocellulosic material. The recalcitrance of biomass is affected by the amount of lignin, by its monomer composition, and the way the monomers are arranged in the plant cell wall. Analysis of lignin structure demands mass spectrometry analysis, and identification of oligomers is usually based on libraries produced by laborious protocols. A robust method to build a do-it-yourself lignin oligomer library was tested. This library can be built using commercially available enzymes, standards, and reagents and is relatively easy to accomplish. An ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for the separation and characterization of monomers and oligomers was developed and was equally applicable to the synthetic lignin and to soluble lignin extracted from a sample of sugar cane.