Weed control in young coffee plantations through post emergence herbicide application onto total area

This study was carried out to investigate the efficiency of several herbicides under field conditions, by post-emergence application onto the entire area, their effect on the control of weeds in young coffee plantations and commercial coffee and bean intercropping system, as well as on both crops. Seedlings of Coffea arabica cv. Red Catuaí with four to six leaf pairs were transplanted to the field and treated according to conventional agronomic practices. A bean and coffee intercropping system was established by sowing three lines of beans in the coffee inter-rows. At the time the herbicides were sprayed, the coffee plants had six to ten leaf pairs; the bean plants, three leaflets; and the weeds were at an early development stage. Fluazifop-p-butyl and clethodim were selective for coffee plants and controlled only Brachiaria plantaginea and Digitaria horizontalis efficiently. Broad-leaved weeds (Amaranthus retroflexus, Bidens pilosa, Coronopus didymus, Emilia sonchifolia, Galinsoga parviflora, Ipomoea grandifolia, Lepidium virginicum, and Raphanus raphanistrum) were controlled with high efficiency by sole applications of fomesafen, flazasulfuron, and oxyfluorfen, except B. pilosa, C. didymus, and R. raphanistrum for oxyfluorfen. Sequential applications in seven-day intervals of fomesafen + fluazifop-p-butyl, or clethodim, and two commercial mixtures of fomesafen + fluazifop-p-butyl simultaneously controlled both types of weed. Cyperus rotundus was only controlled by flazasulfuron. Except for fluazifop-p-butyl and clethodim, all herbicide treatments caused only slight injuries on younger coffee leaves. However, further plant growth was not impaired and coffee plant height and stem diameter were therefore similar in the treatments, as evaluated four months later. Fomesafen, fluazifop-p-butyl, and clethodim, at sole or sequential application, and the commercial mixtures of fomesafen + fluazifop-p-butyl were also highly selective for bean crop; thus at doses recommended for bean crop, these herbicides may be applied to control weeds in coffee and bean intercropping systems by spraying the entire area.

Rice seedling and plant development as affected by increasing rates of penoxsulam under controlled environments

Rice is a major staple in many countries. Weed control is one of the factors limiting higher rice yield. ALS (acetolactate synthase)-inhibiting herbicides are desirable weed control herbicides because of their high efficacy, low toxicity to mammalians, and low rates used. An important herbicide characteristic is high selectivity to the crop, since it facilitates fast crop establishment and greater crop advantage over the weeds. The objectives of this work were to study the effects of increasing rates of the ALS-inhibiting herbicide penoxsulam on seed integrity and germination, and seedling and plant development of rice cv. BRS Pelota under controlled laboratory and greenhouse conditions. The results showed that penoxsulam affected rice germination and seedling and plant growth at rates above 54 g a.i. ha-1, and that penoxsulam is safe for rice seedling development at the currently recommended rates.

Selective inhibition of human tankyrases

Tankyrases belong to the Diphtheria toxin-like ADP-ribosyltransferase (ARTD) enzyme superfamily, also known as poly(ADP-ribose) polymerases (PARPs). They catalyze a covalent post-translational modification reaction where they transfer ADP-ribose units from NAD+ to target proteins. Tankyrases are involved in many cellular processes and their roles in telomere homeostasis, Wnt signaling and in several diseases including cancers have made them interesting drug targets. In this thesis project, selective inhibition of human tankyrases was studied. A homogeneous fluorescence-based assay was developed to screen the compound libraries. The assay is inexpensive, operationally easy, and performs well according to the statistical analysis. Assay suitability was confirmed by screening a natural product library. Flavone was identified as the most potent inhibitor in the library and this motivated us to screen a larger flavonoid library. Results showed that flavones were indeed the best inhibitor of tankyrases among flavonoids. To further study the structure-activity relationship, a small library of flavones containing single substitution was screened and potency measurements allowed us to generate structure-activity relationship. Compounds containing substitutions at 4´-position were more potent in comparison to other substitutions, and importantly, hydrophobic groups improved isoenzyme selectivity as well as the potency. A flavone derivative containing a hydrophobic isopropyl group (compound 22), displayed 6 nM potency against TNKS1, excellent isoenzyme selectivity and Wnt signaling inhibition. Protein interactions with compounds were studied by solving complex crystal structures of the compounds with TNKS2 catalytic domain. A novel tankyrase inhibitor (IWR-1) was also crystallized in complex with TNKS2 catalytic domain. The crystal structure of TNKS2 in complex with IWR-1 showed that the compound binds to adenosine site and it was the first known ARTD inhibitor of this kind. To date, there is no structural information available about the substrate binding with any of the ARTD family members; therefore NAD+ was soaked with TNKS2 catalytic domain crystals. However, analysis of crystal structure showed that NAD+ was hydrolyzed to nicotinamide. Also, a co-crystal structure of NAD+ mimic compound, EB-47, was solved which was used to deduce some insights about the substrate interactions with the enzyme. Like EB-47, other ARTD1 inhibitors were also shown to inhibit tankyrases. It indicated that selectivity of the ARTD1 inhibitors should be considered as some of the effects in cells could come from tankyrase inhibition. In conclusion, the study provides novel information on tankyrase inhibition and presents new insight into the selectivity and potency of compounds.

Optimization and validation of the solid-liquid extraction technique for determination of picloram in soils by high performance liquid chromatography

The objective of this study was to optimize and validate the solid-liquid extraction (ESL) technique for determination of picloram residues in soil samples. At the optimization stage, the optimal conditions for extraction of soil samples were determined using univariate analysis. Ratio soil/solution extraction, type and time of agitation, ionic strength and pH of extraction solution were evaluated. Based on the optimized parameters, the following method of extraction and analysis of picloram was developed: weigh 2.00 g of soil dried and sieved through a sieve mesh of 2.0 mm pore, add 20.0 mL of KCl concentration of 0.5 mol L-1, shake the bottle in the vortex for 10 seconds to form suspension and adjust to pH 7.00, with alkaline KOH 0.1 mol L-1. Homogenate the system in a shaker system for 60 minutes and then let it stand for 10 minutes. The bottles are centrifuged for 10 minutes at 3,500 rpm. After the settlement of the soil particles and cleaning of the supernatant extract, an aliquot is withdrawn and analyzed by high performance liquid chromatography. The optimized method was validated by determining the selectivity, linearity, detection and quantification limits, precision and accuracy. The ESL methodology was efficient for analysis of residues of the pesticides studied, with percentages of recovery above 90%. The limits of detection and quantification were 20.0 and 66.0 mg kg-1 soil for the PVA, and 40.0 and 132.0 mg kg-1 soil for the VLA. The coefficients of variation (CV) were equal to 2.32 and 2.69 for PVA and TH soils, respectively. The methodology resulted in low organic solvent consumption and cleaner extracts, as well as no purification steps for chromatographic analysis were required. The parameters evaluated in the validation process indicated that the ESL methodology is efficient for the extraction of picloram residues in soils, with low limits of detection and quantification.

Mefenpyr-diethyl action on fenoxaprop-p-ethyl detoxification in wheat varieties

Safeners protect crops against herbicide injury. The aim of this study was to examine the differential susceptibility of five wheat (Triticum aestivum) varieties to the herbicide fenoxaprop-p-ethyl, as well as the performance of mefenpyr-diethyl on minimizing herbicide injury and on lipid contents. Varieties BRS 49, CD 104, CEP 24, IAPAR 78 and Rubi were sprayed with fenoxaprop-p-ethyl (69 g ha¹), fenoxaprop-p-ethyl + mefenpyr-diethyl (69 g + 18.75 g ha-1), or mefenpyr-diethyl (18.75 g ha-1). Plants were evaluated visually for injury at 7 and 14 days after treatment (DAT). Glutathione S-transferase (GST) activity was assayed in aerial parts at 7 DAT, and lipid content was measured at 14 DAT. Varieties CEP 24, IAPAR 78 and Rubi were more tolerant to fenoxaprop-p-ethyl than BRS 49, and CD 104 rapidly recovering from the slight phytotoxicity symptoms produced by the herbicide. Mefenpyr-diethyl prevented crop injury associated with the herbicide. GST activity did not correlate directly with fenoxaprop-p-ethyl detoxification. However, lipid content was related to the susceptibility of wheat to fenoxaprop-p-ethyl treatment.

Use of herbicides on turfgrass

In crop production, weeds must be controlled so as not to adversely affect crop yield and crop quality. Thus, a low level of weeds infesting a field, in most instances, is not a problem. Except in sod or seed production, turfgrass does not have a yield component. The value of turfgrass is its inherent aesthetic quality and usability. Aesthetic quality is the beauty and value that turfgrass adds to a managed landscape. Usability can be the durability of a sport field, trueness of golf putting green roll, or reduction in soil loss from water runoff or wind. Any weed presence in turfgrass can decrease the aesthetic quality and usability of turfgrass. Utilizing herbicides is the only way to completely control weeds in a turfgrass stand. While it is possible to reduce weed populations using cultural or mechanical management practices, it is impossible to completely eliminate weeds as can be accomplished with herbicides. This manuscript will review the major herbicides used in turfgrass in the United States with respect to their modes of action, herbicide family, and primary use in turfgrass.

Growth inhibitors in turfgrass

Well-maintained lawns are comfortable and safe places for leisure activities and sports practice, and they also bring environmental benefits; for example, they reduce soil exposure to erosion and releases atmospheric CO2, thus reducing the greenhouse effect. However, regardless of the purpose of use or the choice of the plant species to form the lawn, the highest costs involve cutting that is needed to keep the turfgrass at its appropriate height. Successive lawn cutting operations are necessary basically because of the vegetative and reproductive growth of turfgrass which, in Brazil, occurs mainly from October to March. Expenditures with successive mechanical cuttings have fostered the search of alternative procedures to keep lawn plants at appropriate height, such as the use of plant growth inhibitors, an increasingly interesting procedure. Since the use of this technology in Brazil is still at its early stage, the aim of this literature review is to examine aspects associated with lawn management by using growth inhibitors. Another alternative is to increase the knowledge of the classification and rational application of the different compounds currently available in the market.

Sorption of fomesafen in Brazilian soils

The study of the dynamics of a herbicide in the soil focus on the interactions with environmental components to obtain agronomic efficiency, ensuring selectivity to the culture and risk reduction of environmental impact. This study evaluated the sorption process of fomesafen in the Brazilian soils Ultisol, Cambisol, and Organosol. Besides soil, washed sand was used as an inert material for determination of the sorption ratio of fomesafen in the soil. The bioassay method was applied, using Sorghum vulgare plants as bio-indicator of herbicide presence. Plant poisoning evaluation and harvest for dry matter determination were carried out 21 days after sorghum sowing. To calculate C50, the nonlinear log-logistic model was applied and sorption ratios of the herbicide were obtained in different soils. The decreasing sorption ratio of formesafen in the soils was: Organosol > Ultisol > Cambisol. It was concluded that the contents of organic matter and clay in the soils were the attributes that most influenced fomesafen sorption.

Directed-spray application of paraquat and diuron in physic nut plants

There is little information about the selectivity of herbicides in physic nut (Jatropha curcas) in Brazil. Therefore, this study aimed to evaluate the selectivity of different doses and mixtures of paraquat and diuron in direted-spray applications in physic nut plants in greenhouse conditions. The study used a randomized block design, with five replicates. The treatments were: paraquat (200 and 600 g ha-1), diuron (1,000 and 2,000 g ha-1), paraquat + diuron (200 + 1,000 g ha-1), paraquat + diuron (200 + 2,000 g ha-1), paraquat + diuron (600 + 1,000 g ha-1), paraquat + diuron (600 + 2,000 g ha-1) and a control (no application). Directed-spray application was performed at 70 days after sowing by the lower third of the plants. The treatments of diuron and paraquat + diuron mixtures affected the growth and photosynthetic activity of physic nut plants, injuries being more pronounced at doses of diuron of 2,000 g ha‑1, while the isolated application of paraquat at doses of 200 and 600 g ha-1 showed good selectivity potential for physic nut plants.

Chemical control of Pileamicrophylla in cattleya seedlings (Cattleyatenebrosa x Cattleyaleopoldy)

Species of the orchidaceae family are grown for marketing flowers and among them the genus Cattleya stands out. However, due to its slow growth, the substrate is subjected to weed infestation. Therefore, this study aims to evaluate the selectivity and efficiency of herbicides in controlling Pilea microphylla in Cattleya orchid seedlings (Cattleya tenebrosa x Cattleya leopoldy). We used a completely randomized design with four replications. The evaluated herbicides were oxyfluorfen (0, 120, 240 and 480 g ha-1), flumioxazin (0, 12.5, 25 and 40 g ha-1), nicosulfuron (0, 20, 40 and 80 g ha-1) mesotrione (0, 96, 144 and 192 g ha-1), clethodim (0, 60, 84 and 108 g ha-1) and metsulfuron-methyl (0, 1.2, 1.8 and 2.4 g ha-1). At post-emergence applying time, the Cattleya plants had three bulb sand were 10 cm tall, while P. microphylla, where 5 cm tall. Nicosulfuron, mesotrione and clethodim herbicides did not control P. microphylla, while oxyfluorfen and flumioxazin showed over 90% efficiency level sin controlling P. microphyllafrom 14 days after application (DAA). As to metsulfuron-methyl, it showed efficiency superior to 90% from the control dose of 1.8 g ha-1 at 28 DAA. All herbicides were selective plants of Cattleya, however, only oxyfluorfen, flumioxazin and metsulfuron-methyl were effective in controlling P. microphylla.

How glyphosate may affect transgenic soybean in different soil and phosphorus levels

The technology that employs genetic modifications brought a significant increase in the utilization of glyphosate. Transgenic soybean has been suffering injury, even though it possesses a resistance mechanism to glyphosate. Currently, there are only a few studies on the dynamics of glyphosate in transgenic soybean planted in soils with different textures interacting with phosphorus concentrations. This study focused on assessing the effects of glyphosate in transgenic soybean plants on different types of soil and at different phosphorus levels. The experimental design was completely randomized, in factorial design: 2 x 6 x 3, that being 2 soil types, 6 doses of glyphosate and 3 levels of phosphorus, and four replications. Plants were cultivated for thirty days in pots with two types of soil, one being clayey (Red-Yellow Latosol) and the other sandy (Quartzarenic Neosol). They received one, two, and three times the maintenance dose of fertilization of phosphorus, corresponding to: 170, 250 and 330 kg of P2O5 ha-1 to QN, and 380, 460 and 540 kg P2O5 ha-1 to RYL, respectively. Glyphosate was applied at six different doses: 0, 1,200, 2,400, 12,000, 60,000 and 120,000 g ha-1 of active ingredient. Plant height, a and b chlorophyll, and shoot were lower for the plants that received lower doses of glyphosate, regardless of the type of soil. Greater availability of phosphorus and lower amount of glyphosate used in Quartzarenic Neosol soil provided for less phytointoxication symptoms in transgenic soybean.

Application of Sulfentrazone in Stages of Germination of IAC 90 Cassava Cuttings in Clay Soils and Sandy

Weeds interfere dramatically in the productive potential of cassava; however, information regarding herbicides that are selective to crops is still scarce. Thus, the aim in this study was to assess the initial growth of IAC 90 cassava plants after the application of sulfentrazone at different stages of germination of cassava in clayey and sandy soils. Three experiments were simultaneously deployed: the first experiment consisted in the application of sulfentrazone in the non-germinated stage of cassava cuttings; the second one in the stage of germinated cassavas cuttings (0.9 cm shoots); and the third one in applications in the stage of cassava cuttings with buds emerging (6.5 cm shoots and emerging from the soil). For each experiment the experimental design in randomized blocks was used in the 2 x 5 factorial arrangement with four replications. The factors were composed of two soils (sandy and clayey) and five doses of sulfentrazone (0, 250, 500, 750 and 1,000 g ha-1). It was found that depending on the herbicide dose, development stage of the buds of cassava cuttings and the type of soil, damage can occur in the initial development of the IAC 90 cassava plants. The greatest potential of sulfentrazone selectivity has occurred in applications in the non-germinated cassava cuttings stage and in doses lower than 500 g ha-1 in the clayey soil.

SELECTION OF HERBICIDES TARGETING THE USE IN CROP SYSTEMS CULTIVATED WITH SHOWY CROTALARIA

ABSTRACT The increase in the area planted with Crotalaria spectabilishas occurred by several factors, highlighting the potential to reduce the nematodes, nitrogen fixation and the high production of biomass. By becoming a species sown as a crop, it is necessary to control the weeds that coexist with showy crotalaria. This change in the use of this crop creates the possibility of this specie becoming a weed. The aim of this study was to assess the potential use of herbicides applied in preemergence and postemergence of C.spectabilisfor different purposes (control of volunteer and selectivity plants). Three experiments were installed in a greenhouse (two with herbicides applied in preemergence - in soils with distinct textural categories; and one experiment with herbicides applied in postemergence). The results of the experiments with herbicides applied in preemergence showed that: amicarbazone, atrazine, diuron, metribuzin, prometryn, fomesafen and sulfentrazone showed effectiveness for control of C.spectabilis in clayey soil. Besides these, flumioxazin and isoxaflutole also showed potential to be used in the control of showy crotalaria in soils with loam texture. In relation to the postemergence herbicides, atrazine, diuron, prometryn, flumioxazin, fomesafen, lactofen, saflufenacil, amonio-glufosinate and glyphosate can be used aiming the chemical control of C.spectabilis. Herbicides chlorimuron-ethyl, diclosulan, imazethapyr, pyrithiobac-sodium, trifloxysulfuron-sodium, clomazone, pendimethalin, S-metolachlor and trifluralin applied in preemergence, and imazethapyr, pyrithiobac-sodium, flumiclorac, bentazon and clethodim applied in postemergence caused low levels of injury to C.spectabilis plants, making necessary the development of new searches to ensure the selectivity of these products.

Changes in Photosynthesis and Oxidative Stress in Wheat Plants Submmited to Herbicides Application

The use of herbicides, even in tolerant crops, can cause stress evidenced by increase phytotoxicity affecting growth and development. The objectives of this study were to evaluate herbicides effect from different mechanisms of action in photosynthetic and oxidative stress parameters, as well visual phytotoxicity and wild radish control in wheat crop, cultivar Quartzo. Two trials were conducted where the first one evaluated the photosynthetic parameters on wheat plants in two seasons collection, following the application of herbicides bentazon, clodinafop, iodosulfuron, metribuzin, metsulfuron and 2,4-D; and the second one evaluated wild radish (Raphanus sativus) control, wheat phytotoxicity and yield due to bentazon, iodosulfuron, metribuzin, metsulfuron and 2,4-D herbicides application. Photosynthetic rate, stomatal conductance and transpiration were negatively affected by metribuzin, metsulfuron and 2,4-D herbicides at 24 and 120 HAS (hours after spraying) compared to control. Oxidative stress was similar or lower to control, when herbicide was applied and, in general, there was no difference between application times. Lipid peroxidation, catalase activity and phenols were higher in the first collection time. The application of herbicides iodosulfuron and 2,4-D reduces chlorophylls and carotenoids in wheat. Herbicides bentazon, iodosulfuron, metribuzin, metsulfuron and 2,4-D are selective to wheat, cultivar Quartzo and do not affect wheat yield. 2,4-D, metribuzin and iodosulfuron are more efficient for wild radish control.

Methyl and ethyl chloride synthesis in microreactors

Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.