Triplet carbonyls: from photophysics to biochemistry

Triplet carbonyls can be generated not only from the thermal cleavage of dioxetanes, but also enzymatically from appropriate substrates. The excited species can phosphoresce with an intensity depending upon the extent of shielding from deactivating oxygen collisions, react and also transfer energy, thus promoting sensitized emission and sensitized photochemistry. © 1994.

Model to design drip hose lateral line using two spacing between emitters

The use of non-pressure compensating drip hose in horticultural and annual cycle fruits is growing in Brazil. In this case, the challenge for designers is getting longer lateral lines with high values of uniformity. The objective of this study was to develop a model to design longer lateral lines using non-pressure compensating drip hose. Using the developed model, the hypotheses to be evaluated were: a) the use of two different spacing between emitters in the same lateral line allows longer length; b) it is possible to get longer lateral lines using high values of pressure variation in the lateral lines since the distribution uniformity stays below allowable limits. A computer program was developed in Delphi based on the model developed and it is able to design lateral lines in level using non-pressure compensating drip hose. The input data are: desired distribution uniformity (DU); initial and final pressure in the lateral line; coefficients of relationship between emitter discharge and pressure head; hose internal diameter; pipe cross-sectional area with the dripper; and roughness coefficient for the Hazen-Williams equation. The program allows calculate the lateral line length with three possibilities: selecting two spacing between emitters and defining the exchange point; using two pre-established spacing between emitters and calculating the length of each section with different spacing; using one emitter spacing. Results showed that the use of two sections with different spacing between drippers in the lateral line didn't allow longer length but got better uniformity when compared with lateral line with one spacing between emitters. The adoption of two spacing increased the flow rate per meter in the final section which represented approximately 80% of the lateral line total length and this justifies their use. The software allowed DU above 90% with pressure head variation of 40% and the use of two spacing between emitters. The developed model/software showed to be accurate, easy to handle and useful for lateral line design using non-pressure compensating drip hose.

Triplet entropy analysis of hemagglutinin and neuraminidase sequences measures influenza virus phylodynamics

The influenza virus has been a challenge to science due to its ability to withstand new environmental conditions. Taking into account the development of virus sequence databases, computational approaches can be helpful to understand virus behavior over time. Furthermore, they can suggest new directions to deal with influenza. This work presents triplet entropy analysis as a potential phylodynamic tool to quantify nucleotide organization of viral sequences. The application of this measure to segments of hemagglutinin (HA) and neuraminidase (NA) of H1N1 and H3N2 virus subtypes has shown some variability effects along timeline, inferring about virus evolution. Sequences were divided by year and compared for virus subtype (H1N1 and H3N2). The nonparametric Mann-Whitney test was used for comparison between groups. Results show that differentiation in entropy precedes differentiation in GC content for both groups. Considering the HA fragment, both triplet entropy as well as GC concentration show intersection in 2009, year of the recent pandemic. Some conclusions about possible flu evolutionary lines were drawn. © 2013 Elsevier B.V.

Taxa de emissão de CO2 de um latossolo fertirrigado com ácido fosfórico por gotejamento

A aplicação de fertilizantes fosfatados por meio de fertirrigação com sistemas de irrigação localizada pode causar obstrução de emissores. Para evitar esse problema, pode ser utilizado o ácido fosfórico como fonte de fósforo às plantas. Porém, têm sido pouco investigados os efeitos da irrigação relacionados às perdas de CO2 do solo para a atmosfera, em conseqüência da decomposição do carbono orgânico e da infiltração de água no solo. Neste trabalho, investigou-se, no período de um mês, o efeito da fertirrigação com ácido fosfórico nas taxas de emissão de CO2 de um latossolo desprovido de vegetação, na Área Experimental de Irrigação da UNESP, Câmpus de Jaboticabal - SP. Utilizou-se de um sistema de irrigação por gotejamento, com delineamento experimental em blocos casualizados, constando de cinco repetições e cinco tratamentos (0; 30; 60; 90 e 120 kg ha-1de P2O5), aplicados via fertirrigação com ácido fosfórico. Verificou-se que as taxas de emissão de CO2 aumentaram significativamente após as fertirrigações, porém não houve efeito da dose do ácido fosfórico sobre as taxas. A umidade do solo mostrou-se um fator importante na relação entre as variações das taxas de emissão e a temperatura do solo ao longo do período estudado.

Changes on emitter discharge under different water temperature and pressure

The study was conducted at the Research Laboratory of Hydraulic and Irrigation Group in the Rural Engineering Department, Technical University of Madrid (Universidad Politecnica de Madrid), Madrid, Spain. Water temperatures of 20, 30, 40 degrees C and system pressures often encountered in irrigation practices of 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 and 200 k Pa were applied to determine the effects of different water temperatures and pressures on emitter discharge. Non-pressure compensating in-line emitter which has turbulent flow regime with a long-path (labyrinth), emitter discharge was 4 L h(-1) at system pressure of 100 kPa according to the manufacturer recommended, was used. Emitters were spaced 20 cm along the drip laterals with 16 mm diameter. Discharge equations and coefficients of variation related to temperatures of 20, 30 and 40 degrees C were obtained as q = 0.375H(0.51), q = 0.358H(0.52), q = 0.346H(0.53) and 2.68, 2.09, 3.65, respectively. Discharge of the emitter was affected by different system pressures and increased as potentially (R = 0993-0996). In general. the emitter discharge increased with increasing temperature. However, especially in the common system pressures of 90-120 k Pa, differences of obtained emitter discharges between the different water temperatures were not significant (1%).

Theoretical study on the molecular mechanism for the reaction of VO2+ with C2H4

The complex reaction between VO2+ ((1)A(1)/(3)A) and C2H4 (Ag-1(g)/(3)A(1)) to yield VO+ ((1)Delta/(3)Sigma) and CH3CHO ('A'/(3)A) has been studied by means of B3LYP/6-31G* and B3LYP/6-311G(2d,p) calculations. The structures of all reactants, products, intermediates, and transition structures of this reaction have been optimized and characterized at the fundamental singlet and first excited triplet electronic states. Crossing points are localized, and possible spin inversion processes are discussed by means of the intrinsic reaction coordinate approach. Relevant stationary points along the most favorable reaction pathways have been studied at the CCSD/6-311G(2d,p)//B3LYP/6-311G(2d,p) calculation level. The theoretical results allow the development of thermodynamic and kinetic arguments about the reaction pathways of the title process. In the singlet state, the first step is the barrierless obtention of a reactant complex associated with the formation of a V-C bond, while in the triplet state a three-membered ring addition complex with the V bonded to the two C atoms is obtained. Similar behavior is found in the exit channels: the product complexes can be formed from isolated products without barriers. The reactant and product complexes are the most stable stationary points in the singlet and triplet electronic states. From the singlet state reactant complex, two reaction pathways are posssible to reach the triplet state product complex. (i) A mechanism in which a hydrogen transfer process is the first and rate limiting step and the second step is an oxygen transfer between vanadium and carbon atoms with a concomitant change in the spin state. The crossing point between singlet and triplet spin states is not kinetically relevant because it takes place at a later stage occurring in the exit channel. (ii) A mechanism in which the first stage renders a four-membered ring between vanadyl cation and the ethylene fragment and an oxygencarbon bond is formed; on going from this minimum to the second transition structure, associated with a carbon-vanadium bond breaking process, the crossing point between singlet and triplet spin states is reached. The final step is the hydrogen transfer between both carbon atoms to yield the product complex. In this case the spin change opens a lower barrier pathway. The transition structures with larger values of relative energies for both reactive channels of VO2+ ((1)A(1)) + C2H4 (Ag-1) --> VO+ ((3)Sigma) + CH3CHO ((1)A') present similar energies, and the two reaction pathways can be considered as competitive.

A theoretical study on the gas phase reactions of the anions NbO3-, NbO5-, and NbO2(0H)(2)(-) with H2O and O-2

The potential energy surfaces at the singlet (s) and the triplet (t) electronic states associated with the gas-phase ion/molecule reactions of NbO3-, NbO5-, and NbO2(OH)(2)(-) with H2O and O-2 have been investigated by means of DFT calculations at the B3LYP level. An analysis of the results points out that the most favorable reactive channel comprises s-NbO3- reacting with H2O to give an ion-molecule complex s-NbO3(H2O)without a barrier. From this minima, an intramolecular hydrogen transfer takes place between the incoming water molecule and an oxygen atom of the NbO3- fragment to render the most stable minimum, s-NbO2(OH)(2)(-). This oxyhydroxide system reacts with O-2 along a barrierless process to obtain the triplet t-NbO4(OH)(2)(-)-A intermediate, and the crossing point, CP1, between s and t electronic states has been characterized. The next step is the hydrogen-transfer process between the oxygen atom of a hydroxyl group and the one adjacent oxygen atom to render a minimum with the two OH groups near each other, t-NbO4(OH)(2)(-)-B. From this point, the last hydrogen migration takes place, to obtain the product complex, t-NbO5(H2O)(-), that can be connected with the singlet separated products, s-NbO5- and H2O. Therefore, a second crossing point, CP2, has been localized. The nature of the chemical bonding of the key minima (NbO3-, NbO2(OH)(2)(-), NbO4(OH)(2)(-)-B, and NbO5-) in both electronic states of the reaction and an interaction with O-2 has been studied by topological analysis of Becke-Edgecombe electron-localization function (ELF) and atoms-in-molecules (AIM) methodology. The niobium-oxygen interactions are characterized as unshared-electron (ionic) interactions and some oxygen-oxygen interactions as protocovalent bonds.

Convergent variational calculation of positronium-hydrogen-atom scattering lengths

We present a convergent variational basis-set calculational scheme for elastic scattering of the positronium atom by the hydrogen atom in S wave. Highly correlated trial functions with appropriate symmetry are needed to achieve convergence. We report convergent results for scattering lengths in atomic units for both singlet (= 3.49 +/-0.20) and triplet (= 2.46 +/-0.10) states.

Spontaneous breaking of the lepton number and invisible majoron in a 3-3-1 model

In this work we implement the spontaneous breaking of lepton number in version II of the 3-3-1 models and study their phenomenological consequences. The main result of this work is that our majoron is invisible even though it belongs to a triplet representation by the 3-3-1 symmetry.

Search for heavy lepton partners of neutrinos in proton-proton collisions in the context of the type III seesaw mechanism

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Decay properties of a class of doubly charged Higgs bosons

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Cubic interactions and quantum criticality in dimerized antiferromagnets

In certain Mott-insulating dimerized antiferromagnets, triplet excitations of the paramagnetic phase display both three-particle and four-particle interactions. When such a magnet undergoes a quantum phase transition into a magnetically ordered state, the three-particle interaction becomes part of the critical theory provided that the lattice ordering wave vector is zero. One microscopic example is the staggered-dimer antiferromagnet on the square lattice, for which deviations from O(3) universality have been reported in numerical studies. Using both symmetry arguments and microscopic calculations, we show that a nontrivial cubic term arises in the relevant order-parameter quantum field theory, and we assess its consequences using a combination of analytical and numerical methods. We also present finite-temperature quantum Monte Carlo data for the staggered-dimer antiferromagnet which complement recently published results. The data can be consistently interpreted in terms of critical exponents identical to that of the standard O(3) universality class, but with anomalously large corrections to scaling. We argue that the cubic interaction of critical triplons, although irrelevant in two spatial dimensions, is responsible for the leading corrections to scaling due to its small scaling dimension.

Natural Peccei-Quinn symmetry in the 3-3-1 model with a minimal scalar sector

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Triangular-lattice anisotropic dimerized Heisenberg antiferromagnet: Stability and excitations of the quantum paramagnetic phase

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)