Two-part fractional regression model with conditional FDH responses: an application to Brazilian agriculture

We extend the notion of a two-part fractional regression model with conditional free disposal hull efficiency responses to accommodate two-stage regression analysis. The two-part regression model includes the binomial model with a nonlinear specification for the expected response in (0,1] and is a more general formulation in the context of fractional regressions. We use nonlinear least squares to assess the effect of covariates in the conditional efficiency response. The approach is applied to Brazilian agricultural county data, as reported in the Brazilian agricultural census of 2006. The efficiency measure is output oriented and assumes variable returns to scale. Output is rural gross income and inputs are land expenses, labor expenses and expenses on other technological inputs. The covariates affecting production are credit, technical assistance, a rural development index, income concentration, measured by the Gini index, and regional dummies. Overall Brazilian rural production performance responds positively to all covariates.

     

The Synthesis and Photoisomerization of 5-Methyl-5-Vinyl-1,3-Cyclopentadiene

A versatile scheme for the synthesis of geminally disubstituted cyclopentadienes is used to prepare the title compound 4 . This remarkably stable vinyl-cyclopentadiene, distinguished by its C_s symmetry, undergoes exclusively electrocyclic ring closure upon direct π–π* excitation at 254 nm. The epimeric vinyl-housenes 11 and 12 , which, for geometric reasons, are insensitive to the walk rearrangement, are suggested to be the primary photo-products. One of them, 12 , due to its syn-oriented vinyl group, undergoes spontaneous copy rearrangement to give 2-methylbicyclo[3.2.1]hepta-2,6-diene ( 13 ). The other, 11 , having an anti-oriented vinyl group, can only undergo thermal return to the starting material 4 . Whereas no leakage to a 1,5-vinyl migration is discernible for the S₁ state of 4 , the benzophenone-sensitized photolysis at 350 nm is shown to be governed by this rearrangement. 1-Methyl-5-vinylcyclopenta-1,3-diene ( 14 ), the unstable primary product of the sensitized photoreaction, is trapped by 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione (PTAD).     

Effets de substituant,d'hétéroatome et de solvant sur les cinétiques de décoloration thermique et les spectres d'absorption de photomérocyanines en série spiro[indoline-oxazine]

Substituent, Heteroatom, and Solvent Effects on the Thermal-Bleaching Kinetics and Absorption Spectra of Photomerocyanines Issued from Spiro[indoline-oxazines] Quantitative information useful for the development of new photochromic systems is obtained from the study of heteroatom and substituent effects on the thermal-bleaching kinetics and the absorption spectra of the photomerocyanines issued from spiro[indoline-oxazines]. The effect on photochromic properties of the presence of N-atoms either in the dimethine bridge or in the aromatic rings has been investigated through the comparison of spiro[indoline-naphthopyrans] C with spiro[indoline-naphthoxazines] A and with spiro[indoline-quinolinoxazines] B . Besides the occurrence of biexponential thermal-bleaching kinetics in non-polar solvents is observed: a tentative explanation for this observation is given which involves the formation, in either sequential or parallel steps, of energetically distinct stereoisomers of the opened form.     

A New System of Multiple Emulsions with Lamellar Gel Phases from Vegetable Oil

Emulsions are excellent pharmaceutical vehicles used in both the pharmacy and cosmetic industries. Vegetable oils have several effects/benefits on skin and can be used in emulsions to release principal active components for cosmetic purposes. Herein, multiple W/O/W emulsions were formulated in a one-step emulsification method, and the resulting anisotropic structures were characterized by x-ray diffraction measurements. The multiple emulsions obtained were stable and maintained their anisotropic structures over 2 years. WAXS (wide-angle x-ray scattering) measurements of these emulsions suggested that the carbon chains of the surfactant around the globules are disposed in a gel network phase. Furthermore, SAXS (small-angle x-ray scattering) measurements indicated that the surfactant is organized in lamellar layers around the globules. Thus, for the first time, we demonstrated that stable lamellar gel phase multiple emulsions can be made from vegetable oils. In addition to having the advantage of being prepared in one step, these emulsions have desirable characteristics that can be used in the cosmetic industry as natural active principles with low surfactant concentration and the unique features of multiple emulsions with gel phases.     

Comprehensive two-dimensional liquid chromatography-based quali-quantitative screening of aqueous phases from pyrolysis bio-oils

Pyrolysis processes are an alternative to minimize the environmental problem associated to agrifood industrial wastes. The main product resulting from these processes is a high-value liquid product, called bio-oil. Recently, the use of comprehensive two-dimensional liquid chromatography (LC × LC) has been demonstrated as a useful tool to improve the characterization of the water-soluble phases of bio-oils, considering their complexity and high water content. However, the precise composition of bio-oils from different agrifood byproducts is still unknown. In the present study, the qualitative and quantitative screening of eight aqueous phases from different biomasses, not yet reported in the literature, using LC × LC is presented. The two-dimensional approach was based on the use of two reverse phase separations. An amide column in the first dimension together with a C18 column in the second dimension were employed. Thanks to the use of diode array and mass spectrometry detection, 28 compounds were identified and quantified in the aqueous phase samples with good figures of merit. Samples showed a distinct quali-quantitative composition and a great predominance of compounds belonging to aldehydes, ketones and phenols, most of them with high polarity.     

Conley's spectral sequence via the sweeping algorithm

In this article we consider a spectral sequence (Er,dr) associated to a filtered Morse-Conley chain complex (C,Δ), where Δ is a connection matrix. The underlying motivation is to understand connection matrices under continuation. We show how the spectral sequence is completely determined by a family of connection matrices. This family is obtained by a sweeping algorithm for Δ over fields F as well as over Z. This algorithm constructs a sequence of similar matrices Δ⁰=Δ,Δ¹,… , where each matrix is related to the others via a change-of-basis matrix. Each matrix Δr over F (resp., over Z) determines the vector space (resp., Z-module) Er and the differential dr. We also prove the integrality of the final matrix ΔR produced by the sweeping algorithm over Z which is quite surprising, mainly because the intermediate matrices in the process may not have this property. Several other properties of the change-of-basis matrices as well as the intermediate matrices Δr are obtained.     

Analytical characterization of mannosylerythritol lipid biosurfactants produced by biosynthesis based on feedstock sources from the agrofood industry

Mannosylerythritol lipids (MELs) are currently one of the most promising biosurfactants because of their multifunctional applications and good biodegradability. Depending on the yeast strain and the feedstock used for the fermentation process, structural variations in the MELs obtained occur. Therefore, MELs produced by Pseudozyma aphidis DSMZ 70725 with a soybean oil feedstock were characterized by chromatography and mass spectrometry (MS). Column chromatography with silica provided fractionation of the different types of MEL. High-performance liquid chromatography combined with MS was employed for the analysis of the MEL fractions and crude mixtures. A characteristic MS pattern for the MELs was obtained and indications of the presence of new MEL homologues, showing the incorporation of longer and more unsaturated fatty acid chains than previously reported, were given. Gas chromatography?CMS analysis confirmed the presence of such unsaturated fatty acid chains in the MELs, demonstrating the incorporation of fatty acids with lengths ranging from C₈ to C₁₄ and with up to two unsaturations per chain. The incorporation of C₁₆ and C₁₈ fatty acid chains requires further investigation. MS/MS data allowed the unambiguous identification of the fatty acids present in the MELs. The product ion spectra also revealed the presence of a new isomeric class of MELs, bearing an acetyl group on the erythritol moiety.     

On an evolution equation with acoustic boundary conditions

In this paper, we analyze from the mathematical point of view a model for small vertical vibrations of an elastic string with weak internal damping and quadratic term, coupled with mixed boundary conditions of Dirichlet type and acoustic type. Our goal is to extend some of the results of Frota‐Goldstein work in the sense of considering a weaker internal damping and one more quadratic nonlinearity in the elastic string equation. Copyright © 2011 John Wiley & Sons, Ltd.     

Carboxylic Acids Supported on Silica: A Smooth Acylating Agent for Alcohols

An alternative procedure for the esterification of alcohols by short-chain carboxylic acids supported on silica is presented.     

Synthesis of Homo- and Heterofunctionalized Glycoclusters and Binding to Pseudomonas aeruginosa Lectins PA-IL and PA-IIL

Homo- and heterofunctionalized glycoclusters with galactose and/or fucose residues targeting both PA-IL and PA-IIL lectins of Pseudomonas aeruginosa were synthesized using "Click" chemistry and DNA chemistry. Their binding to lectins (separately or in a mixture) was studied using a DNA Directed Immobilization carbohydrate microarray. Homoglycoclusters bind selectively to their lectin while the heteroglycocluster binds simultaneously both lectins with a slight lower affinity.