Two series of allyl sulfonamides, prepared from Morita-Baylis-Hillman adducts and primary aromatic sulfonamides, were fully characterized. The Z configuration for the products derived from 2-[hydroxy(phenyl)methyl]acrylonitrile (1) and E configuration for those derived from methyl 2-[hydroxy(phenyl)methyl]acrylate (2) were confirmed by X-ray diffraction for one compound of each series (1e, 2f). Density functional theory calculations for all allyl sulfonamides agreed with the X-ray crystallographic data. X-ray diffraction studies indicate that these compounds form dimers in their crystal structures. Fingerprint plots show that compound 1e is stabilized by H⋯H, C⋯H/H⋯C, O⋯H/H⋯O and N⋯H/H⋯N interactions, while the compound 2f has no N⋯H/H⋯N contacts. Hirshfeld surface analyses were performed to gain insight into the behavior of these interactions. Calculated frontier orbitals showed that their highest occupied and lowest unoccupied molecular orbitals are antibonding orbitals. The allyl sulfonamides 1e and 2f are among the most active compounds in each series, inhibiting approximately 60% of the mycelial growth of Botrytiscinerea at 3 mmol L-1.

ABSTRACT: The biotrophic fungus Hemileia vastatrix causes coffee leaf rust (CLR), one of the most devastating diseases in Coffea arabica . Coffee, like other plants, has developed effective mechanisms to recognize and respond to infections caused by pathogens. Plant resistance gene analogs (RGAs) have been identified in certain plants as candidates for resistance ( R ) genes or membrane receptors that activate the R genes. The RGAs identified in different plants possess conserved domains that play specific roles in the fight against pathogens. Despite the importance of RGAs, in coffee plants these genes and other molecular mechanisms of disease resistance are still unknown. This study aimed to sequence and characterize candidate genes from coffee plants with the potential for involvement in resistance to H. vastatrix . Sequencing was performed based on a library of bacterial artificial chromosomes (BAC) of the coffee clone ‘Híbrido de Timor’ (HdT) CIFC 832/2 and screened using a functional marker. Two RGAs, HdT_LRR_RLK1 and HdT_LRR_RLK2, containing the motif of leucine-rich repeat-like kinase (LRR-RLK) were identified. Based on the presence or absence of the HdT_LRR_RLK2 RGA in a number of differential coffee clones containing different combinations of the rust resistance gene, these RGAs did not correspond to any resistance gene already characterized (SH1-9). These genes were also analyzed using qPCR and demonstrated a major expression peak at 24 h after inoculation in both the compatible and incompatible interactions between coffee and H. vastatrix . These results are valuable information for breeding programs aimed at developing CLR-resistant cultivars, in addition to enabling a better understanding of the interactions between coffee and H. vastatrix .

ABSTRACT This study investigated the effect of different phosphites on the control of coffee leaf rust (CLR) caused by Hemileia vastatrix, considered the major disease affecting coffee yield worldwide. Three-month-old coffee plants were sprayed with two doses each of the phosphite solutions (standar., and double), as follows: K (40% P2O5; 1.., and 3 mL∙L-1), K (30% P2O5; ., and 6 mL∙L-1), Cu (2.., and 5 mL∙L-1), Mn+Zn (., and 6 mL∙L-1., and Na (., and 6 mL∙L-1) 24 h before being inoculated with H. vastatrix. Leaves were not washed or washed with deionized water after the foliar phosphites spray. Plants sprayed with water served as the control treatment. Inoculation was performed on the abaxial side of the first pair of expanded leaves using a camel hairbrush with a suspension of urediniospores (1 mg per leaf). All phosphites applied at the standard doses (from 1.5 to 3 mL∙L-1) reduced the total number of pustules (TNP) per leaf by 28-69% regardless of washing treatment. The biggest reductions were observed for Cu phosphite, which decreased the TNP per leaf by 6., and 69% withou., and with leaf washing, respectively. A similar trend was observed when the double doses of phosphites (from 3 to 6 mL∙L-1) were used, though Na phosphite without leaf washin., and Mn/Zn phosphite withou., and with leaf washing were not efficient to reduce the TNP per leaf. Without leaf washing, only C., and Na phosphites decreased CLR severity at the standard doses (53-61%), whereas all phosphites, except the Mn/Zn phosphite, reduced CLR severity at the double dose. The CLR severity was decreased using K 30%, K 40., and Cu phosphites when applied at the standard doses with leaf washing (41-59%). With double doses, only C., and Na phosphites decreased CLR severity by 55% for both treatments. In conclusion, the efficiency of the phosphites for CLR control varied according to the accompanying cation, dos., and washing conditions. The Cu phosphite resulted in the best CLR control regardless of the dose use., and the washing conditions.

ABSTRACT Genomic selection (GS) emphasizes the simultaneous prediction of the genetic effects of thousands of scattered markers over the genome. Several statistical methodologies have been used in GS for the prediction of genetic merit. In general, such methodologies require certain assumptions about the data, such as the normality of the distribution of phenotypic values. To circumvent the non-normality of phenotypic values, the literature suggests the use of Bayesian Generalized Linear Regression (GBLASSO). Another alternative is the models based on machine learning, represented by methodologies such as Artificial Neural Networks (ANN), Decision Trees (DT) and related possible refinements such as Bagging, Random Forest and Boosting. This study aimed to use DT and its refinements for predicting resistance to orange rust in Arabica coffee. Additionally, DT and its refinements were used to identify the importance of markers related to the characteristic of interest. The results were compared with those from GBLASSO and ANN. Data on coffee rust resistance of 245 Arabica coffee plants genotyped for 137 markers were used. The DT refinements presented equal or inferior values of Apparent Error Rate compared to those obtained by DT, GBLASSO, and ANN. Moreover, DT refinements were able to identify important markers for the characteristic of interest. Out of 14 of the most important markers analyzed in each methodology, 9.3 markers on average were in regions of quantitative trait loci (QTLs) related to resistance to disease listed in the literature.

Twelve tetraphenylphosphonium allyldithiocarbimates were synthesized and fully characterized by high-resolution electrospray ionization mass spectrometry (HR-ESI-MS), infrared and nuclear magnetic resonance (NMR) spectroscopies. The spectroscopic data indicated that the allyldithiocarbimate anions present Z configuration, as confirmed by X-ray crystallography. These new compounds inhibited the germination of Phakopsora pachyrhizi and Hemileia vastatrix at very low doses, with IC50 (concentration to achieve 50% of inhibition of spore germination) values ranging from 0.028 to 0.166 mmol L-1, and IC90 (concentration to achieve 90% of inhibition of spore germination) values varying from 0.156 to 0.528 mmol L-1. Allyldithiocarbimate salts are lead compounds for the development of new antifungals for coffee leaf rust and Asian soybean rust, devastating plant diseases with limited control options.

RESUMO A hérnia das crucíferas é uma doença radicular causada pelo fungo Plasmodiophora brassicae, responsável por danos econômicos no cultivo de brássicas que podem ultrapassar 40%. Devido a doença vem gradativamente ocorrendo declínio produtivo de brássicas em diversos países e no Brasil com volume aproximado de 50 mil toneladas comercializadas no país por ano. Existem poucos estudos envolvendo o controle desta doença, devido a isto foi elaborado um experimento com quatro tratamentos: T1.controle negativo , T2.bioestimulantes (fósforo + auxina + ácido fúlvico), T3.bioestimulante + fungicida (fósforo + auxina + ácido fúlvico + ciazofamida) e T4. fungicida (ciazofamida). A menor incidência obtida na última avaliação foi de 21% (79% de controle) com a mistura bioestimulante e fungicida; o bioestimulante sozinho não diferiu do controle negativo, considerando a condição de alta pressão de inóculo, servindo de base para trabalhos futuros com a mistura de novos compostos e agentes de biocontrole compatíveis com o fungicida.

ABSTRACT Clubroot of crucifers is a root disease caused by the fungus Plasmodiophora brassicae, responsible for causing more than 40% economic damage to brassica crops. This disease has led to a gradual decline in brassica production in several countries, including Brazil, where an approximate volume of 50 thousand tons are marketed every year. There are few studies involving the control of this disease, which led to the development of an experiment with four treatments: T1. negative control, T2. biostimulant (phosphorus + auxin + fulvic acid), T3. biostimulant + fungicide (phosphorus + auxin + fulvic acid + cyazofamid) and T4. fungicide (cyazofamid). The lowest incidence value obtained in the last evaluation was 21% (79% control) with the mixture of biostimulant and fungicide; the biostimulant alone did not significantly differ from the negative control, considering the condition of high inoculum density, which serves as a basis for future studies with a mixture of new compounds and biocontrol agents compatible with the fungicide.

Abstract Coffee tree is a shrub with dimorphic branches. The orthotropic stem grows vertically with two near-horizontal plagiotropic branches, per node, in opposite phyllotaxy. The consecutive nodes of the orthotropic stem are organized in parastichies. We report here mutant plants of Coffea arabica with triple plagiotropic branch, resulted from the whorled phyllotaxy of the orthotropic stem. In mutant plants three plagiotropic branches in the same node are separated by angles of approximately 120o, while in normal plants two plagiotropic branches in the same node are separated by angles of approximately 180o. In mutant plants the angles of the parastichies increase approximately 50o clockwise between consecutive nodes, while in normal plants the angles increase approximately 87o. The plant architecture is changed. The triple plagiotropic branch is a putative mutant with potential to be explored in coffee breeding programs. The hypotheses for the origin of the mutation and the research perspectives are discussed.

ABSTRACT The aim of this study was to evaluate the resistance of Botrytis cinerea to the fungicides currently used for its control in Brazil. Isolates of the fungus were collected from different strawberry-producing fields in the states of Espírito Santo, Minas Gerais, and São Paulo, Brazil. First, a total of 183 isolates were identified at the species level using specific primers for the glyceraldehyde-3-phosphate dehydrogenase (G3PDH) gene. The isolates were grown on potato dextrose agar (PDA) containing the fungicides procymidone, iprodione, and thiophanate-methyl in different concentrations: 0.0 (control), 0.1; 1.0; 10.0; 100.0 and 1,000.0 μg∙mL−1. The percentage of mycelial growth inhibition was used to determine the effective concentration of the fungicide that was able to inhibit colony growth by 50% (EC50). Approximately 25.7% of the isolates were resistant to iprodione, 53.0% were resistant to procymidone, and 93.0% were resistant to thiophanate-methyl. Moreover, crossresistance and multiple resistance were verified, with 19.7% of the isolates showing resistance to 3 fungicides simultaneously. This finding explains the ineffectiveness of fungicides application to control gray mold in strawberry fields in Brazil and highlights the need for new strategies to manage this disease in the culture.

RESUMO: O uso de cultivares resistentes é a principal medida para o manejo da antracnose do colmo em milho. Neste trabalho, objetivou-se identificar linhagens com níveis de resistência à antracnose do colmo, similar ao híbrido 2B710, considerado resistente. Dois experimentos foram conduzidos na Embrapa Milho e Sorgo. No primeiro experimento, foram avaliados 234 linhagens e os híbridos BRS1010 (suscetível) e 2B710 (resistente). Foi realizada inoculação artificial com um isolado de C. graminicola , na fase de pré-pendoamento e, após 30 dias, foi realizada a avaliação da severidade da antracnose no colmo. O segundo experimento foi conduzido com 48 linhagens e os híbridos inoculados com dois isolados de C. graminicola . No primeiro experimento, os genótipos formaram oito grupos com base na severidade da doença e as linhagens do último grupo foram consideradas as mais resistentes, incluindo o híbrido 2B710, em que os genótipos apresentaram valores de severidade entre 11,50 a 23%. No segundo experimento, houve interação entre os fatores linhagens e isolados e, de modo geral, as linhagens apresentaram a mesma tendência de reação obtida no primeiro experimento, no entanto, a severidade da doença foi maior para a maioria das linhagens, mesmo quando utilizado o outro isolado. Com isso, foi possível realizar a seleção de linhagens com bons níveis de resistência, as quais podem ser utilizadas em programas de melhoramento, em estudos de herança, desenvolvimento de híbridos e identificação de marcadores moleculares, associados com resistência à antracnose do colmo.

ABSTRACT: Adoption of resistant cultivars is the primary measure used to control anthracnose stalk rot. The goal of this study was to identify maize-resistant genotypes to anthracnose stalk rot, which are similar to the hybrid 2B710. Experiments were performed at Embrapa Maize and Sorghum experimental fields in Brazil. The first experimental trial evaluated 234 maize lines as well as two commercials hybrids, BRS1010 (susceptible) and 2B710 (resistant). Artificial inoculations were performed with a strain at the blister (R2) phase, and evaluation of disease severity was performed after 30 days. The second experimental trial evaluated 48 maize lines and hybrids, inoculated with two Colletotrichum graminicola strains. In the first trial, eight resistance groups were formed, and the last lines were more resistant, as was the hybrid 2B710, with values between 11.50% and 23.0% of severity. In the second trial, there was an interaction between the two factors, lines and isolates, and the lines often showed the same reaction features as those obtained in the first trial. However, the disease severity was higher for most lines, even when using other isolates. These lines with effective levels of resistance could be used in future studies of inheritance, in programs to develop hybrids, and to identify molecular markers associated with resistance to anthracnose stalk rot in maize.

Six new salts of organometallic complexes of tin(IV) with the general formulae: (Ph4P)2[Sn(Bu)2(RSO2N=CS2)2] and [Fe(phen)3][Sn(Bu)2(RSO2N=CS2)2] [Ph4P = tetraphenylphosphonium, R = CH3 (1), C2H5 (2) and C4H9 (3); Fe(phen)3 = tris(1,10-phenanthroline)iron(II), R = CH3 (4), C2H5 (5) and C4H9 (6)] were synthetized from potassium dithiocarbimates (RSO2N=CS2K2.H2O) in reaction with dichlorobis-n-butyltin(IV) and tetraphenylphosphonium chloride (1-3) in N,N-dimethylformamide or tris(1,10-phenanthroline)iron(II) (4-6) in methanol. The new compounds were characterized by elemental analysis of Fe and Sn, and by vibrational, Mössbauer and nuclear magnetic resonance of 1H, 13C and 119Sn spectroscopies. High-resolution mass spectra in the negative and positive modes were also obtained. The elemental analyses and the exact masses obtained for the cations and the complex anions were consistent with the proposed formulae. The Mössbauer spectroscopic data were consistent with the presence of tin(IV) with coordination numbers between 4 and 5 (compounds 1-6), and of hexacoordinated iron(II) (compounds 4-6). The 1H and 13C NMR spectra presented all the expected signals for the cations and anions, and the signals observed in the 119Sn NMR spectra indicated an equilibrium between tetra- and pentacoordination around the tin atoms in solution. The in vitro activity of the new compounds was evaluated against Botrytis cinerea and Colletotrichum acutatum.

Resumo: O objetivo deste trabalho foi avaliar a eficiência da aplicação foliar de fungicidas na redução da incidência de patógenos fúngicos, de grãos ardidos e de fumonisinas totais em grãos de milho (Zea mays). Foram conduzidos três ensaios: um no município de Luís Eduardo Magalhães, na Bahia, e dois em Sete Lagoas, em Minas Gerais, nas safras 2010/2011 e 2011/2012, com cultivo de diferentes híbridos comerciais. Os seguintes fungicidas foram aplicados zero, uma e duas vezes: picoxistrobina + ciproconazol, piraclostrobina + epoxiconazole, trifloxistrobina + tebuconazole, azoxistrobina + ciproconazol e tiofanato metílico. Em todos os ensaios, foram realizados a quantificação da incidência de grãos ardidos, o teste de patologia de sementes e a quantificação dos teores de fumonisinas totais. Não foi observada diferença significativa para os fatores fungicida e número de aplicações, exceto para rendimento de grãos, em todos os ensaios. Esses resultados são indicativos da ineficiência da aplicação de fungicidas na redução da incidência de patógenos fúngicos, de grãos ardidos e dos teores de fumonisinas totais em grãos de milho.

Abstract: The objective of this work was to evaluate fungicide leaf application on the reduction of fungal pathogen incidence, kernel rot, and total fumonisins in corn (Zea mays) kernels. Three experiments were performed: one in the municipality of Luís Eduardo Magalhães, in the state of Bahia, and two in the municipality of Sete Lagoas, in the state of Minas Gerais, Brazil, during the 2010/2011 and 2011/2012 crop seasons, with planting of different commercial hybrids. The following fungicides were applied zero, one, and two times: picoxystrobin + cyproconazole, pyraclostrobin + epoxiconazole, trifloxystrobin + tebuconazole, azoxystrobin + cyproconazole, and thiophanate-methyl. For all trials, the quantification of kernel rot incidence, the grain pathology test, and the quantification of total fumonisins were performed. No significant difference was observed for the factors fungicide and number of applications, except for grain yield, in all trials. These results show the ineffectiveness of fungicide applications in reducing fungi incidence, kernel rot, and levels of total fumonisins in corn kernels.

Objetivou-se propor e validar uma escala diagramática para quantificar a antracnose do colmo em milho. A severidade da antracnose foi estimada por dez avaliadores sem o uso de escala em 139 entrenós, e os mesmos avaliadores avaliaram os entrenós usando uma escala publicada anteriormente na literatura (primeira escala) e uma nova escala proposta. Com o uso da escala proposta, todas as variáveis foram significativamente diferentes em relação à primeira escala, e os valores foram mais próximos de uma medição acurada (r=0,97, Cb=0.98, u=0.09, υ=1.06, ρc=0.96). Os maiores desvios do erro foram observados quando os avaliadores atribuíram notas sem o uso de escalas e com a primeira escala, com vários exemplos de erros maiores do que 30% do valor real. Com a escala proposta, poucos erros acima de 15% do valor real foram encontrados, e a maioria das notas dos avaliadores não ultrapassou, para mais ou para menos, 10% do valor real. Uma maior confiabilidade na estimativa da severidade da doença foi obtida com o uso da escala proposta, com a qual 100% das comparações resultaram em um R2>0,90. A nova escala diagramática proposta no presente trabalho melhorou a acurácia, precisão e confiabilidade das estimativas da severidade da antracnose do colmo em milho

This study aimed to validate a new diagrammatic scale to anthracnose stalk in corn. Anthracnose severity was estimated by ten raters without and with use of new scale on 139 internodes with different severity degrees and all evaluators rated the same internodes using the old scale published in the literature and a new proposed scale. All variables of the propose scale, were significantly different than those of old scale, and the values were closer to an accurate measurement (r=0.97, Cb=0.98, u=0:09, υ=1:06, ρc=0.96). The large error deviations were observed when evaluators given notes without the use of scales and also with the old scale, for examples with errors up to 30%. On the other hand the majority errors with the use the new scale were lower than 10%. Higher reliability was achieved with the use of the proposed scale, where 100% of the comparisons were achieved R2>0.90. According to the results the diagrammatic scale proposed in this study improves accuracy, precision and reliability of the evaluators to estimates the anthracnose stalk severity in corn