RESUMOO presente estudo foi realizado a partir de amostras de um Cambissolo Háplico Ta Eutrófico vértico, localizado em Campos dos Goytacazes, norte do estado do Rio de Janeiro, e submetido ao cultivo por longo tempo com cana-deaçúcar. Em uma das áreas de coleta, a cana foi cultivada, por 55 anos, sem a queima por ocasião da colheita. Na outra, por 35 anos, houve a adição anual de cerca de 120 m 3 ha -1 de vinhaça, por meio de irrigação por aspersão e colheita com a cana queimada. Outras duas áreas, respectivamente adjacentes a essas, onde se realizou a queima por ocasião da colheita durante 55 anos e não se procedeu à adição de vinhaça por 35 anos e colhida com queima do canavial, foram utilizadas para coleta

Resumo -A bioatividade de ácidos húmicos (AH) isolados de lodo da estação de tratamento de esgoto (AHL) e de vermicomposto (AHV) foi avaliada pela ação dessas substâncias sobre o transporte de prótons através da membrana plasmática de células de raízes de café e milho e sua relação com o desenvolvimento dessas espécies. Houve estímulo da área superficial radicular em ambas as espécies cultivadas com ambos AH, mostrando uma concentração ótima em torno de 40 mg L -1 . Nessa condição, os tratamentos com AHL e AHV estimularam a H + -ATPase de membrana plasmática em plântulas de café e milho. Os AHL foram mais efetivos na promoção desses efeitos do que os AHV. A modificação do perfil cromatográfico dos AH em solução antes e após o cultivo das plântulas revelou que a interação planta-AH promoveu uma redistribuição das massas moleculares dessas substâncias, sugerindo uma dinâmica de mobilização de subunidades funcionais dos AH por exsudatos das raízes. A análise estrutural dos AH detectou a presença de grupamentos de auxina. A análise comparativa da ação desses dois AH sobre as espécies representantes de plantas monocotiledôneas (milho) e dicotiledôneas (café) apontam para a ativação da H + -ATPase de plasmalema como possível marcador metabólico de bioatividade dos ácidos húmicos.Termos para indexação: Zea mays, Coffea arabica, lodo residual, ácidos orgânicos, vermicomposto. Humic acids bioactivity: effects on root development and on the plasma membrane proton pumpAbstract -The bioactivity of humic acids (HA) isolated from sludge of the station of sewer treatment (HAL) and from vermicompost (HAV) was evaluated through the action of those substances on primary transport of protons of the plasma membrane of coffee and corn root cells and its relationship with the development of those species. A stimulation in the superficial area of roots was observed for both species cultivated with both humic acids, exhibiting an optimum concentration, about 40 mg L -1 of HA. In this condition the treatment with HAL and HAV stimulated the plasma membrane H + -ATPase of corn and coffee roots. HAL were more effective to promote those effects than HAV. The modification of the chromatographic profile of the HA in solution before and after the cultivation of the seedlings revealed that the interaction plant-HA promoted a rearrangement of the average molecular weight of those substances suggesting a dynamic mobilization of bioactive subunits of the HA by plant exudates. The structural analysis of the HA has detected the presence of auxin groups. A comparative analysis of the action of those HA on the monocotyledonous (corn) and dicotyledonous (coffee) plants indicates to the activation of plasmallema H + -ATPase as a possible metabolic marker for bioactivity of humic acids.

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Herein we describe NMR experiments and structural modifications of 4-methyl-2-phenylpyrimidine-N-acylhydrazone compounds (aryl-NAH) in order to discover if duplication of some signals in their 1 H-and 13 C-NMR spectra was related to a mixture of imine double bond stereoisomers (E/Z) or CO-NH bond conformers (syn and anti-periplanar). NMR data from NOEdiff, 2D-NOESY and 1 H-NMR spectra at different temperatures, and also the synthesis of isopropylidene hydrazone revealed the nature of duplicated signals of a 4-methyl-2-phenylpyrimidine-N-acylhydrazone derivative as a mixture of two conformers in solution. Further we investigated the stereoelectronic influence of substituents at the ortho position on the pyrimidine ring with respect to the carbonyl group, as well as the OPEN ACCESSMolecules 2013, 18 11684 electronic effects of pyrimidine by changing it to phenyl. The conformer equilibrium was attributed to the decoplanarization of the aromatic ring and carbonyl group (generated by an ortho-alkyl group) and/or the electron withdrawing character of the pyrimidine ring. Both effects increased the rotational barrier of the C-N amide bond, as verified by the ΔG ≠ values calculated from dynamic NMR. As far as we know, it is the first description of aryl-NAH compounds presenting two CO-NH bond-related conformations.

A series of humic matter samples isolated from a soil sequence, different oxisols, size‐fractionated from a vermicompost humic acid and subjected to chemical modifications, were characterized by CPMAS 13C‐NMR spectroscopy. The relative signal areas in chemical shift regions of NMR spectra of the four sets of samples were analysed by principal component analysis (PCA). Hierarchical cluster analysis (HCA) was applied to build a classification model, which allowed the recognition of humic matter according to its origin. The relationship between carbon species and biological activity of humic acids, as promoters of lateral root emergence, was obtained by applying PLS multivariate analysis. This showed that lateral root emergence was mostly related to NMR parameters such as the hydrophobicity index (HB/HI) and the 40–110 and 160–200 ppm chemical shift regions (hydrophilic carbon HI), while the content of hydrophobic (HB) carbon in humic samples was negatively correlated with induction of lateral root hair. Our results represent a step further in the structure‐bioactivity relationship of natural humic substances and confirm their role as plant root growth promoters.