Photoinduced Degradation of the Herbicide Clomazone Model Reactions for Natural and Technical Systems

The photodegradation of the herbicide clomazone in the presence of S(2)O(8)(2-) or of humic substances of different origin was investigated. A value of (9.4 +/- 0.4) x 10(8) m(-1) s(-1) was measured for the bimolecular rate constant for the reaction of sulfate radicals with clomazone in flash-photolysis experiments. Steady state photolysis of peroxydisulfate, leading to the formation of the sulfate radicals, in the presence of clomazone was shown to be an efficient photodegradation method of the herbicide. This is a relevant result regarding the in situ chemical oxidation procedures involving peroxydisulfate as the oxidant. The main reaction products are 2-chlorobenzylalcohol and 2-chlorobenzaldehyde. The degradation kinetics of clomazone was also studied under steady state conditions induced by photolysis of Aldrich humic acid or a vermicompost extract (VCE). The results indicate that singlet oxygen is the main species responsible for clomazone degradation. The quantum yield of O(2)(a(1)Delta(g)) generation (lambda = 400 nm) for the VCE in D(2)O, Phi(Delta) = (1.3 +/- 0.1) x 10(-3), was determined by measuring the O(2)(a(1)Delta(g)) phosphorescence at 1270 nm. The value of the overall quenching constant of O(2)(a(1)Delta(g)) by clomazone was found to be (5.7 +/- 0.3) x 10(7) m(-1) s(-1) in D(2)O. The bimolecular rate constant for the reaction of clomazone with singlet oxygen was k(r) = (5.4 +/- 0.1) x 10(7) m(-1) s(-1), which means that the quenching process is mainly reactive.

New Analytic Solution of Boltzmann Transform for Horizontal Water Infiltration into Sand

The use of the Boltzmann transform function, lambda(theta), to solve the Richards equation when the diffusivity, D, is a function of only soil water content,., is now commonplace in the literature. Nevertheless, a new analytic solution of the Boltzmann transform lambda(h) as a function of matric potential for horizontal water infiltration into a sand was derived without invoking the concept or use of D(theta). The derivation assumes that a similarity exists between the soil water retention function and the Boltzmann transform lambda(theta). The solution successfully described soil water content profiles experimentally measured for different infiltration times into a homogeneous sand and agrees with those presented by Philip in 1955 and 1957. The applicability of this solution for all soils remains open, but it is anticipated to hold for soils whose air-filled pore-size distribution before wetting is sufficiently narrow to yield a sharp increase of water content at the wetting front during infiltration. It also improves and provides a versatile alternative to the well-known analysis pioneered by Green and Ampt in 1911.

Predation potential and biology of Protogamasellopsis posnaniensis Wisniewski & Hirschmann (Acari: Rhodacaridae)

Rhodacaridae are cosmopolitan mites mentioned as predators, although nothing is known about their potential as biological control agents. One of the objectives of the work reported in this paper was to evaluate the potential of Protogamasellopsis posnaniensis (Acari: Rhodacaridae) as predator of representative species of insects of the families Sciaridae (Bradysia matogrossensis (Lane)) and Thripidae (Frankliniella occidentalis (Pergande)), of mites of the family Acaridae (Tyrophagus putrescentiae (Schrank) and Rhizoglyphus echinopus (Fumouze & Robin) and of nematodes of the family Rhabditidae (Protorhabditis sp.). Another objective was to determine the biological cycle of P. posnaniensis when fed the prey on which it performed best in the preceding predation test. The study was conducted in a laboratory where the experimental units were maintained at 25 +/- 1 degrees C, 97 +/- 3% RH and in the dark. Although the predator was able to kill all prey species considered in this study, the most favorable prey were T. putrescentiae, F. occidentalis and Protorhabditis sp. Survivorship of the predator in predation tests was always 98% or higher. Life table biological parameters when the predator was fed T. putrescentiae were: R(o) = 109.29; T = 19.06 days; lambda = 1.28 e r(m) = 0.32 female/female/day. Despite preying upon larvae of B. matogrossensis, eggs of the former can also be killed by the latter. The results indicated that A posnaniensis is a promising biological control agent, deserving additional studies on its possible use for the control of soil pests. (C) 2008 Elsevier Inc. All rights reserved.

Life history of the predatory mite Phytoseiulus fragariae on Tetranychus evansi and Tetranychus urticae (Acari : Phytoseiidae, Tetranychidae) at five temperatures

Tetranychus evansi Baker and Pritchard and Tetranychus urticae Koch (Acari: Tetranychidae) are important pests of Solanaceae in many countries. Several studies have demonstrated that T. urticae is an acceptable prey to many predatory mites, although the suitability of this prey depends on the host plant. T. evansi, has been shown to be an unfavorable prey to most predatory mites that have been tested against it. The predator Phytoseiulus fragariae Denmark and Schicha (Acari: Phytoseiidae) has been found in association with the two species in Brazil. The objective of this work was to compare biological parameters of P. fragariae on T. evansi and on T. urticae as prey. The study was conducted under laboratory conditions at 10, 15, 20, 25 and 30 degrees C. At all temperatures, survivorship was lower on T. evansi than on T. urticae. No predator reached adulthood at 10 degrees C on the former species; even on the latter species, only about 36% of the predators reached adulthood at 10 degrees C. For both prey, in general, duration of each life stage was shorter, total fecundity was lower and intrinsic rate of population increase (r(m) ) was higher with increasing temperatures. The slower rate of development of P. fragariae on T. evansi resulted in a slightly higher thermal requirement (103.9 degree-days) on that prey than on T. urticae (97.1 degree-days). The values of net reproduction rate (R-0), intrinsic rate of increase (r (m) ) and finite rate of increase (lambda) were significantly higher on T. urticae, indicating faster population increase of the predator on this prey species. The highest value of r (m) of the predator was 0.154 and 0.337 female per female per day on T. evansi and on T. urticae, respectively. The results suggested that P. fragariae cannot be considered a good predator of T. evansi.

Biomarkers of metabolic syndrome and its relationship with the zinc nutritional status in obese women

Introduction: Obesity is a chronic disease that induces risk factors for metabolic syndrome and, is associated with disturbances in the metabolism of the zinc. Therefore, the aim of this study was to investigate the existence of relationship between the biomarkers of metabolic syndrome and the zinc nutricional status in obese women. Method: Seventy-three premenopausal women, aged between 20 and 50 years, were divided into two groups: case group, composed of obese (n = 37) and control group, composed of no obese (n = 36). The assessment of the body mass index and waist circumference were carried out using anthropometric measurements. The plasmatic and erythrocytary zinc were analyzed by method atomic absorption spectrophotometry (lambda=213.9 nm). Results: In the study, body mass index and waist circumference were higher in obese women than control group (p < 0.05). The mean plasmatic zinc was 72.2 +/- 9.0 mu g/dl in obese women and 73.4 +/- 8.5 mu g/dl in control group (p > 0.05). The mean erythrocytary zinc was 36.4 +/- 15.0 mu g/gHb and 45.4 +/- 14.3 mu g/gHb in the obese and controls, respectively (p < 0.05). Regression analysis showed that the body mass index (t=-2.85) and waist circumference (t=-2.37) have a negative relationship only with the erythrocytary zinc (R(2)=0.32, p < 0.05). Conclusions: The study shows that there are alterations in biochemical parameters of zinc in obese women, with low zinc concentrations in erythrocytes. Regression analysis demonstrates that the erythrocytary zinc is influenced by biomarkers of the metabolic syndrome, presenting an inverse relationship with the waist circumference and body mass index.

Broad spectrum bioactive sunscreens

The development of sunscreens containing reduced concentration of chemical UV filters, even though, possessing broad spectrum effectiveness with the use of natural raw materials that improve and infer UV absorption is of great interest. Due to the structural similarities between polyphenolic compounds and organic UV filters, they might exert photoprotection activity. The objective of the present research work was to develop bioactive sunscreen delivery systems containing rutin, Passiflora incarnata L. and Plantago lanceolata extracts associated or not with organic and inorganic UV filters. UV transmission of the sunscreen delivery system films was performed by using diffuse transmittance measurements coupling to an integrating sphere. In vitro photoprotection efficacy was evaluated according to the following parameters: estimated sun protection factor (SPF); Boot`s Star Rating category; UVA/UVB ratio; and critical wavelength (lambda(c)). Sunscreen delivery systems obtained SPF values ranging from 0.972 +/- 0.004 to 28.064 +/- 2.429 and bioactive compounds interacted with the UV filters positive and negatively. This behavior may be attributed to: the composition of the delivery system: the presence of inorganic UV filter and quantitative composition of the organic UV filters; and the phytochemical composition of the P. incarnate L and P. lanceolato extracts. Among all associations of bioactive compounds and UV filters, we found that the broad spectrum sunscreen was accomplished when 1.68% (w/w) P incarnata L. dry extract was in the presence of 7.0% (w/w) ethylhexyl methoxycinnamate, 2.0% (w/w) benzophenone-3 and 2.0% (w/w) TiO(2). It was demonstrated that this association generated estimated SPF of 20.072 +/- 0.906 and it has improved the protective defense against UVA radiation accompanying augmentation of the UVA/UVB ratio from 0.49 to 0.52 and lambda(c) from 364 to 368.6 nm. (c) 2008 Elsevier B.V. All rights reserved.

Photochemical production of nitric oxide from a nitrosyl phthalocyanine ruthenium complex by irradiation with light in the phototherapeutic window

The photochemical behavior of [Ru(NO)(NO)(2)pc] (pc = phthalocyanine) is reported in this paper. In addition to ligand localized absorption bands (lambda < 300 nm), the electronic spectrum of this complex in dichloromethane solution was dominated by an intense absorption at 640 nm characterized as Q-bands. Irradiation of [Ru(NO)(NO)(2)pc] at 366 and 660 nm led to the production of nitric oxide (NO) as detected by a NO-sensor. NO production by light irradiation at high energy involved excitation of d(pi)-pi* transition, while a photoinduced electron transfer occurred at long wavelength irradiation. The NO quantum yields varied from 1.4 x 10(-3) to 2.3 x 10(-2) mol einstein(-1), depending on oxygen concentration. (c) 2008 Elsevier B.V. All rights reserved.

The bimolecular sensitization of nitric oxide release from weak interacting ruthenium units

This work reports on the bimolecular sensitization of nitric oxide release from cis-[Ru(bpy)(2)(iso)-NO](PF(6))(3) (1) (iso = isoquinoline and bpy = 2,2`- bipyridine) by irradiating the MLCT transition of the chloro analog cis-[Ru(bpy) 2(iso) Cl] PF6 (2). The compounds displayed peaks in the ESI-MS spectra at m/z 749.1 and m/z 578.1 ascribed, respectively, to ([1(NO(o))-2PF(6)center dot CH(3)OH](2+)) and ([2-PF(6)](+)). In the cyclic voltammograms, the nitrosyl complex presented two redox waves related to the NO ligand at 0.48 and -0.37 V (versus Ag/AgCl, NO(+/0/-1) processes), while the sensitizer showed two reversible waves at 0.79 and -1.46 V (versus Ag/AgCl, Ru(2+/3+) and bpy(0/-1), respectively). The most important feature of this system is that the nitrosyl compound does not have significant absorption in the visible region, while the sensitizer has an intense band centered at 496 nm. The irradiation of an equimolar mixture of the two compounds in an ethanol: water solution (v: v) with light of lambda > 500 nm leads to NO release, as probed by amperometric measurements. The variational method was applied, showing that the two compounds self-assembly in solution with a 1: 1 stoichiometry. Fluorescence spectra acquired at 77 K provided the E(0-0) for the system and, from the thermodynamic cycle it was estimated that the photoinduced electron transfer between the species has a Delta G value of -1.59 eV. (C) 2011 Elsevier B. V. All rights reserved.

Exploring weak interactions to assemble a nitrosyl-ruthenium compound able to release NO under visible light irradiation

This work reports oil a novel nitrosyl-ruthenium complex hearing the azanaphthalene ligand quinazoline (qui) ill its coordination sphere. The product crystallizes with ail additional quinazoline molecule, yielding the compound cis-[Ru(bpy)(2)(qui)NO](PF(6))(3).(qui). This feature leads to all absorption band at lambda(max) = 430 nm in CH(3)CN and lambda(max) = 420 nm in phosphate buffer, which promotes the photorelease of nitric oxide under visible light irradiation (lambda > 400 nm), in 1 ethanol: 1 water (v/v) mixture or under physiological pH. Both the intensity and energy of this transition are dependent on solvent and solution pH, suggesting that the transition has a charge transfer nature, and that the association of the second quinazoline molecule with the complex is driven by weak interactions, possibly of the pi-stacking type. (C) 2009 Elsevier Ltd. All rights reserved.

Half-Filled Layered Organic Superconductors and the Resonating-Valence-Bond Theory of the Hubbard-Heisenberg Model

We present a resonating-valence-bond theory of superconductivity for the Hubbard-Heisenberg model on an anisotropic triangular lattice. Our calculations are consistent with the observed phase diagram of the half-filled layered organic superconductors, such as the beta, beta('), kappa, and lambda phases of (BEDT-TTF)(2)X [bis(ethylenedithio)tetrathiafulvalene] and (BETS)(2)X [bis(ethylenedithio)tetraselenafulvalene]. We find a first order transition from a Mott insulator to a d(x)(2)-y(2) superconductor with a small superfluid stiffness and a pseudogap with d(x)(2)-y(2) symmetry.

On the nonlinear Neumann problem with critical and supercritical nonlinearities

We investigate the solvability of the Neumann problem (1.1) involving a critical Sobolev exponent. In the first part of this work it is assumed that the coeffcients Q and h are at least continuous. Moreover Q is positive on overline Omega and lambda > 0 is a parameter. We examine the common effect of the mean curvature and the shape of the graphs of the coeffcients Q and h on the existence of low energy solutions. In the second part of this work we consider the same problem with Q replaced by - Q. In this case the problem can be supercritical and the existence results depend on integrability conditions on Q and h.

Bifurcation in growth patterns for arrays of parallel Griffith, edge and sliding cracks

This paper presents the recent finding by Muhlhaus et al [1] that bifurcation of crack growth patterns exists for arrays of two-dimensional cracks. This bifurcation is a result of the nonlinear effect due to crack interaction, which is, in the present analysis, approximated by the dipole asymptotic or pseudo-traction method. The nonlinear parameter for the problem is the crack length/ spacing ratio lambda = a/h. For parallel and edge crack arrays under far field tension, uniform crack growth patterns (all cracks having same size) yield to nonuniform crack growth patterns (i.e. bifurcation) if lambda is larger than a critical value lambda(cr) (note that such bifurcation is not found for collinear crack arrays). For parallel and edge crack arrays respectively, the value of lambda(cr) decreases monotonically from (2/9)(1/2) and (2/15.096)(1/2) for arrays of 2 cracks, to (2/3)(1/2)/pi and (2/5.032)(1/2)/pi for infinite arrays of cracks. The critical parameter lambda(cr) is calculated numerically for arrays of up to 100 cracks, whilst discrete Fourier transform is used to obtain the exact solution of lambda(cr) for infinite crack arrays. For geomaterials, bifurcation can also occurs when array of sliding cracks are under compression.

Iron(III) and iron(II) complexes of 1-thia-4,7-diazacyclononane ([9]aneN(2)S) and 1,4-dithia-7-azacyclononane ([9]aneNS(2)). X-Ray structural analyses, magnetic susceptibility, Mossbauer, EPR and electronic spectroscopy

The complexes [Fe([9]aneN(2)S)(2)][ClO4](2), [Fe([9]aneN(2)S)(2)][ClO4](3) and [Fe([9]aneNS(2))(2)][ClO4](2) ([9]aneN(2)S = 1-thia-4. 7-diazacyclononane and [9]aneNS(2) = 1,4-dithia-7-azacyclononane) have been prepared and the latter two characterised by X-ray crystallography. The Mossbauer spectra (isomer shift/mm s(-1), quadrupole splitting/mm s(-1), 4.2 K) for [Fe([9]aneN(2)S)(2)][ClO4](2) (0.52, 0.57), [Fe([9]aneN(2)S)(2)][ClO4](3) (0.25, 2.72) and [Fe([9]aneNS(2))(2)][ClO4](2) (0.43, 0.28) are typical for iron(II) and iron(III) complexes. Variable-temperature susceptibility measurements for [Fe([9]aneN(2)S)(2)][ClO4](2) (2-300 K) revealed temperature-dependent behaviour in both the solid state [2.95 mu(B) (300 K)-0.5 mu(B) (4.2 K)] and solution (Delta H degrees 20-22 kJ mol(-1), Delta S degrees 53-60 J mol(-1) K-1). For [Fe([9]aneN(2)S)(2)][ClO4](3) in the solid state [2.3 mu(B) (300 K)-1.9 mu(B) (4.2 K)] the magnetic data were fit to a simple model (H = -lambda L . S + mu L-z) to give the spin-orbit coupling constant (lambda) of -260 +/- 10 cm(-1). The solid-state X-band EPR spectrum of [Fe([9]aneN(2)S)(2)][ClO4](3) revealed axial symmetry (g(perpendicular to) = 2.607, g(parallel to) = 1.599). Resolution of g(perpendicular to) into two components at Q-band frequencies indicated a rhombic distortion. The low-temperature single-crystal absorption spectra of [Fe([9]aneN(2)S)(2)][ClO4](2) and [Fe([9]aneNS(2))(2)][ClO4](2) exhibited additional bands which resembled pseudotetragonal low-symmetry splitting of the parent octahedral (1)A(1g) --> T-1(2g) and (1)A(1g) ---> T-1(1g) transitions. However, the magnitude of these splittings was too large, requiring 10Dq for the thioether donors to be significantly larger than for the amine donors. Instead, these bands were tentatively assigned to weak, low-energy S --> Fe-II charge-transfer transitions. Above 200 K, thermal occupation of the high-spin T-5(2g) ground state resulted in observation of the T-5(2g) --> E-5(g) transition in the crystal spectrum of [Fe([9]aneN(2)S)(2)][ClO4](2). From a temperature-dependence study, the separation of the low-spin (1)A(1g) and high-spin T-5(2g) ground states was approximately 1700 cm(-1). The spectrum of the iron(III) complex [Fe([9]aneN(2)S)(2)][ClO4](3) is consistent with a low-spin d(5) configuration.

Determination of pindolol enantiomers in human plasma and urine by simple liquid-liquid extraction and high-performance liquid chromatography

A simple method for the measurement of pindolol enantiomers by HPLC is presented. Alkalinized serum or urine is extracted with ethyl acetate and the residue remaining after evaporation of the organic layer is then derivatised with (S)-(-)-alpha-methylbenzyl isocyanate. The diastereoisomers of derivatised pindolol and metoprolol (internal standard) are separated by high-performance liquid chromatography (HPLC) using a C-18 silica column and detected using fluorescence (excitation lambda: 215 nm, emission lambda: 320 nm). The assay displays reproducible linearity for pindolol enantiomers with a correlation coefficient of r(2) greater than or equal to 0.998 over the concentration range 8-100 ng ml(-1) for plasma and 0.1-2.5 mu g ml(-1) for urine. The coefficient of variation for accuracy and precision of the quality control samples for both plasma and urine are consistently

Decoherence and coherent population transfer between two coupled systems

We show that an arbitrary system described by two dipole moments exhibits coherent superpositions of internal states that can be completely decoupled fi om the dissipative interactions (responsible for decoherence) and an external driving laser field. These superpositions, known as dark or trapping states, can he completely stable or can coherently interact with the remaining states. We examine the master equation describing the dissipative evolution of the system and identify conditions for population trapping and also classify processes that can transfer the population to these undriven and nondecaying states. It is shown that coherent transfers are possible only if the two systems are nonidentical, that is the transitions have different frequencies and/or decay rates. in particular, we find that the trapping conditions can involve both coherent and dissipative interactions, and depending on the energy level structure of the system, the population can be trapped in a linear superposition of two or more bare states, a dressed state corresponding to an eigenstate of the system plus external fields or, in some cases. in one of the excited states of the system. A comprehensive analysis is presented of the different processes that are responsible for population trapping, and we illustrate these ideas with three examples of two coupled systems: single V- and Lambda-type three-level atoms and two nonidentical tao-level atoms, which are known to exhibit dark states. We show that the effect of population trapping does not necessarily require decoupling of the antisymmetric superposition from the dissipative interactions. We also find that the vacuum-induced coherent coupling between the systems could be easily observed in Lambda-type atoms. Our analysis of the population trapping in two nonidentical atoms shows that the atoms can be driven into a maximally entangled state which is completely decoupled from the dissipative interaction.