Characterisation of Functional Brown Adipose Tissue In Adult Humans

The white adipose tissue mainly serves the purpose of energy storage, while brown adipose tissue (BAT) has the capacity to generate heat under cold conditions in mammals and in human infants. BAT is controlled by the central nervous system, and BAT function is accompanied by increased energy expenditure. However, it was not previously certain whether adult humans also have functional BAT. The aim of this doctoral work was to identify functional BAT in adult humans and to characterise its glucose uptake and blood flow under cold and insulin stimulation conditions in lean and in obese humans, by using positron emission tomography. Further, the impact of weight loss on BAT glucose uptake was assessed. Cerebral glucose uptake was also studied in relation to BAT function and cold exposure. The results showed that healthy adult humans have functional BAT, as assessed by the intense cold-induced glucose uptake and by biopsies. BAT was also found to be a highly insulinsensitive tissue in lean humans, but the effects of insulin and cold exposure were attenuated in obese humans, although the glucose uptake capacity of cold-activated BAT might be increased by weight loss. Blood flow in the BAT of lean humans was associated with whole-body energy expenditure. The presence of cold-activated BAT was related to lower body mass index and higher insulin sensitivity. Finally, BAT activation was linked to the activity of the cerebellum, the thalamus and certain neocortical regions. The cold-induced cerebral glucose uptake was also lower in obese than in lean adult humans.

Selectivity of glyphosate in tank mixtures for RR soybean in sequential applications with mixtures only in the first or second application

Tank mixtures among herbicides of different action mechanisms might increase weed control spectrum and may be an important strategy for preventing the development of resistance in RR soybean. However, little is known about the effects of these herbicide combinations on soybean plants. Hence, two experiments were carried out aiming at evaluating the selectivity of glyphosate mixtures with other active ingredients applied in postemergence to RR soybean. The first application was carried out at V1 to V2 soybean stage and the second at V3 to V4 (15 days after the first one). For experiment I, treatments (rates in g ha-1) evaluated were composed by two sequential applications: the first one with glyphosate (720) in tank mixtures with cloransulam (30.24), fomesafen (125), lactofen (72), chlorimuron (12.5), flumiclorac (30), bentazon (480) and imazethapyr (80); the second application consisted of isolated glyphosate (480). In experiment II, treatments also consisted of two sequential applications, but tank mixtures as described above were applied as the second application. The first one in this experiment consisted of isolated glyphosate (720). For both experiments, sequential applications of glyphosate alone at 720/480, 960/480, 1200/480 and 960/720 (Expt. I) or 720/480, 720/720, 720/960 and 720/1200 (Expt. II) were used as control treatments. Applications of glyphosate tank mixtures with other herbicides are more selective to RR soybean when applied at younger stages whereas applications at later stages might cause yield losses, especially when glyphosate is mixed with lactofen and bentazon.

Selectivity of glyphosate tank mixtures for RR soybean

An active ingredients mixture of different action mechanisms is an essential tool to prevent or manage areas with resistant weeds. However, it is important that such a mixture provides adequate selectivity to the crop. The aim of this work was to evaluate glyphosate selectivity to glyphosate-resistant (RR) soybean, and also verify if there is selectivity in mixtures with other active ingredients applied postemergence aimed at new control strategies, which might be used in RR soybean cultivation. The herbicides and respective rates (g ha-1) evaluated were: glyphosate (720, 960, 1,200, and 1,440), and the mixtures of glyphosate (960) with cloransulam-methyl (30.24), fomesafen (125), lactofen (72), chlorimuron-ethyl (12.5), flumiclorac-pentyl (30), bentazon (480), or imazethapyr (80). All treatments were applied in postemergence when the soybean crop was at V2 to V3 stage. Treatments with glyphosate or in mixtures with postemergent herbicides showed visual effects of phytotoxicity when applied to the glyphosate-resistant soybean. Effects such as reduction in plant height, crop closure, number of pods per plant, and hundred grain weight could be observed. However, the effects related to plant development were mostly transient and did not persist during the crop cycle. Among the studied treatments, only the mixture of glyphosate and lactofen was not selective to the crop, promoting negative effects on most characteristics analyzed and consequently reducing grain yield.

Herbicide selectivity in alfalfa crops

This study aimed to determine the selectivity of herbicides applied in pre- and post-emergence for alfalfa crops. Three separate experiments were carried out under greenhouse conditions. The first experiment was arranged in a completely randomized design with three replications in a 4 x 11 + 1 factorial scheme , with eleven herbicides (bentazon, chlorimuron-ethyl, fomesafen, fluazifop-p-butyl, saflufenacil, imazethapyr, clethodim, nicosulfuron, imazaquin, haloxyfop-methyl and MSMA), four doses of each herbicide (0.5 D, 0.75 D, 1.0 D and 1.25 D, where D = recommended dose), plus an untreated control. The products were applied to alfalfa plants at the stage of 4 to 5 leaf pairs. In the second experiment, the effect of pre-emergent herbicides on early alfalfa development was observed through a completely randomized design with five replications in a 3 x 4 x 2 factorial scheme, with three herbicides (hexazinone, atrazine + simazine, S-metolachlor), four doses (0.5 D, 0.75 D, 1.0 D and 1.25 D), and two types of soil texture (loamy and clay soil), plus an untreated control. The third experiment evaluated the action of atrazine, 2,550 g ha-1; clomazone - 600 g ha-1; diclosulam - 25 g ha-1; diuron+hexazinone - 936 + 264 g ha-1 and diuron+hexazinone +sulfometuron - 1,386 + 391 + 33.35 g ha-1 on alfalfa sown at different times after herbicide application. The effects of the treatments on alfalfa were evaluated according to visual phytotoxicity symptoms, plant height, and biomass of roots and shoots. Among the herbicides applied at post-emergence, imazethapyr, clethodim, haloxyfop-p-methyl and MSMA were selective for alfalfa, while among those applied at pre-emergence, none were selective, regardless of soil texture. The results of the third experiment showed that the herbicides diclosulam, hexazinone + diuron and atrazine caused less toxicity in alfalfa plants.

Selectivity of clomazone and S-metolachlor applied after cassava pruning

The objective of this work was to evaluate the selectivity of clomazone in two formulations and S-metolachlor applied on shoots of different sizes after pruning of 'Baianinha' cassava. The experiment was arranged in a randomized block design in a factorial 5 x 2 (5 treatments x 2 sizes of shoots after pruning - 10 and 33 cm) with four replications. The herbicides evaluated were: clomazone (encapsulated suspension - 900 g h-1), clomazone (encapsulated suspension - 1,080 g ha-1), clomazone (emulsifiable concentrate 900 g ha-1), S-metolachlor (1,920 g ha-1) and an untreated control. During the experiment, all plots were kept free of weed interference by hand weeding. It was concluded that both the formulations of clomazone and S-metolachlor were selective when applied on both the shoot sizes evaluated. However, the application of S-metolachlor on 33 cm shoots gave higher selectivity to 'Baianinha' cassava plants.

Effect of selectivity of herbicides and plant growth regulators used in sugarcane crops on immature stages of Trichogramma galloi (Hymenoptera: Trichogrammatidae)

Herbicides and plant growth regulators are often used in sugarcane management. However, the use of non-selective pesticides can cause adverse effects on the efficiency of beneficial insects in integrated pest management. Within this context, this study aimed to evaluate the effect of such products on the immature stages of the parasitoid Trichogramma galloi. Eggs of Diatraea saccharalis containing the parasitoid at the egg-larva stage and at the prepupal and pupal stages were immersed in test solutions of the following pesticides (maximum recommended doses for sugarcane): herbicides clomazone and diuron + hexazinone, and plant growth regulators trinexapac-ethyl and sulfometuron-methyl. The biological properties evaluated were emergence (F1 and F2) and number of eggs parasitized by T. galloi (F1). The products were classified according to percentage of reduction in emergence and parasitism: harmless (<30%), slightly harmful (30-79%), moderately harmful (80-99%) and harmful (>99%). The pesticides evaluated were considered to be harmless or slightly harmful to immature T. galloi and, thus, their use should be preferred for preserving this parasitoid species in sugarcane management programs.

Selectivity of chemical weed control systems in conventional cotton

Cotton is highly susceptible to the interference imposed by weed community, being therefore essential to adopt control measures ensuring the crop yield. Herbicides are the primary method of weed control in large-scale areas of production, and usually more than one herbicide application is necessary due to the extensive crop cycle. This study aimed to evaluate the selectivity of different chemical weed control systems for conventional cotton. The experiment took place in the field in a randomized block design, with twenty nine treatments and four replications in a split plot layout (adjacent double check). Results showed that triple mixtures in pre-emergence increased the chance of observing reductions in the cotton yield. To avoid reductions in crop yield, users should proceed to a maximum mixture of two herbicides in pre-emergence, followed by S-metolachlor over the top, followed by one post-emergence mixture application of pyrithiobac-sodium + trifloxysulfuron-sodium.

Trinexapac-Ethyl and Sulfometuron-Methyl Selectivity to Young Eucalyptus Plants

Trinexapac-ethyl and sulfometuron-methyl are the most widely used ripeners in sugarcane. The application is performed by airborne spraying. Thus, if weather conditions are unfavorable, spray drift to neighboring areas may occur. The objective of this study was to assess the selectivity of the plant growth regulators trinexapac-ethyl and sulfometuron-methyl, used as sugarcane ripeners, to eucalyptus (Eucalyptus urograndis) young plants. The experiment was installed in an eucalyptus commercial yield area, in the municipality of Tambaú, state of São Paulo, Brazil, and arranged in a 2 x 8 factorial design in randomized blocks with four replications. The treatments studied were trinexapac-ethyl and sulfometuron-methyl, sprayed in eight doses, 0; 1.0; 2.5; 5.0; 10; 25; 50 and 100% of the dose used in sugarcane as ripeners (200 g ha-1 of trinexapac-ethyl and 15 g ha-1 of sulfometuron-methyl). Chemical ripeners were applied on eucalyptus plants with 48 cm in height on average; 10.1 branches; 4.5 mm of stem diameter and 44.3 cm of crown diameter, at 46 days after seeding. Trinexapac-ethyl was selective to eucalyptus and stimulated crown diameter growth. At higher doses, sulfometuron-methyl promoted severe noticeable injuries in eucalyptus plants, such as apical bud death. However, during the assessment period the plants recovered and the visual symptoms of phytotoxicity and growth alterations were not observed at 60 days after application. The plant growth regulators trinexapac-ethyl and sulfometuron-methyl were selective to eucalyptus young plants.

Selectivity of Saflufenacil for Sweet Sorghum and Potential use of Na-Bentazon as a Safener

The objective of this study was to assess the selectivity herbicide saflufenacil for two sweet sorghum hybrids, when sprayed in preemergence and postemergence, besides the use of Na-bentazon as a 'safener' for saflufenacil. Three experiments were conducted, in pots, maintained in an ambient condition (second and third experiments) and in a greenhouse (first experiment). In each experiment a completely randomized distribution was used, with four replicates. In the first (2 x 6 factorial) two hybrids of sweet sorghum (CVSW 80007 and CVSW 80147) and six dosages (0; 35; 52.5; 70; 87.5 and 105 g ha-1) of saflufenacil were studied, applied in preemergence of the plants. In the second (2 x 5 factorial) the same hybrids of sweet sorghum sprayed in postemergence with saflufenacil (0; 35; 52.5; 70 and 87.5 g h-1) were assessed. In the third (4 x 5 factorial) the association of Na-bentazon (0; 240; 480 and 720 g ha-1) to saflufenacil (0.35; 52.5; 70 and 87.5 g ha-1) was studied, when sprayed in postemergence on the sweet sorghum plants (CVSW 80007). Hybrid CVSW 80147 was more tolerant to saflufenacil than hybrid CVSW 800007, in preemergence or postemergence applications. The variables that best assessed the sensibility of the sweet sorghum to saflufenacil were number of emerged plants, for preemergence applications, and dry matter of stem for postemergence. Na-bentazon showed promise for use as 'safener' in postemergence applications of saflufenacil in sweet sorghum for dosages up to 70 g ha-1.

SELECTIVITY OF FOMESAFEN TO COTTON

ABSTRACT The aim of this work was to evaluate the selectivity of fomesafen alone or in a tank mixture with other preemergent herbicides, with or without S-metolachlor application in early postemergence in cotton plant, cultivar DP 555 BG RR(r). The design utilized was a randomized complete block, organized in a split-plot arrangement, with four replications. For that, 24 herbicides were evaluated with fomesafen (0.45 and 0.625 kg ha-1), prometryn (1.25 kg ha-1), diuron (1.25 kg ha-1), trifluralin (1.8 kg ha-1), and S-metolachlor (0.77 kg ha-1), applied as preemergent, with or without S-metolachlor (0.77 kg ha-1) applied in early postemergence. The variables evaluated were: phytotoxicity, insertion height of the first reproductive branch, plant height, stand, number of reproductive branches per plant, number of bolls per plant, bolls weight, and productivity of cotton seed. Fomesafen alone or in a tank mixture with preemergent prometryn, diuron, trifluralin and S-metolachlor was selective to cotton plant. Preemergent fomesafen isolated application followed by the application of S-metolachlor in early postemergence was also selective. However, on average, preemergent tank mixtures applied in association with preemergent S-metolachlor early application was not selective to cotton crop.

SULFENTRAZONE SELECTIVITY AND EFFICIENCY IN CASSAVA CROPS IN SANDY AND CLAYEY SOILS

ABSTRACT Weeds have the potential to dramatically interfere in cassava cultivation, reducing its productive potential; however, there are few studies on the selective herbicides in this crop. Therefore, the objective was to evaluate in this work the selectivity and efficiency of sulfentrazone in cassava crops grown in sandy and clayey soils. Two experiments were carried out: The first one was carried out in sandy soil conditions in the conventional system; and the second one was carried out in clayey soil conditions in the no-tillage system. The experimental design was a randomized block with four replications. The treatments consisted in doses of 250, 500, 750 and 1,000 g ha-1 of sulfentrazone, and weeded and non-weeded controls. Sulfentrazone application in cassava crops has linearly reduced the production of roots in a proportion of 0.0153 and 0.0107 t ha-1 at each increment in grams of the active ingredient, respectively. It was concluded that sulfentrazone was not selective for cassava crops grown both in sandy and in clayey soil; however, it was highly effective in weed control in both soils.

Chemical derivatization of galactoglucomannan for functional materials

In the framework of the biorefinery concept researchers aspire to optimize the utilization of plant materials, such as agricultural wastes and wood. For most of the known processes, the first steps in the valorisation of biomass are the extraction and purification of the individual components. The obtained raw products by means of a controlled separation can consecutively be modified to result in biofuels or biogas for energy production, but also in value-added products such as additives and important building blocks for the chemical and material industries. Considerable efforts are undertaken in order to substitute the use of oil-based starting materials or at least minimize their processing for the production of everyday goods. Wood is one of the raw materials, which have gained large attention in the last decades and its composition has been studied in detail. Nowadays, the extraction of water-soluble hemicelluloses from wood is well known and so for example xylan can be obtained from hardwoods and O-acetyl galactoglucomannans (GGMs) from softwoods. The aim of this work was to develop water-soluble amphiphilic materials of GGM and to assess their potential use as additives. Furthermore, GGM was also applied as a crosslinker in the synthesis of functional hydrogels for the removal of toxic metals and metalloid ions from aqueous solutions. The distinguished products were obtained by several chemical approaches and analysed by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), size exclusion chromatography (SEC), thermal gravimetric analysis (TGA), scanning electron microscope SEM, among others. Bio-based surfactants were produced by applying GGM and different fatty acids as starting materials. On one hand, GGM-grafted-fatty acids were prepared by esterification and on the other hand, well-defined GGM-block-fatty acid derivatives were obtained by linking amino-functional fatty acids to the reducing end of GGM. The reaction conditions for the syntheses were optimized and the resultant amphiphilic GGM derivatives were evaluated concerning their ability to reduce the surface tension of water as surfactants. Furthermore, the block-structured derivatives were tested in respect to their applicability as additives for the surface modification of cellulosic materials. Besides the GGM surfactants with a bio-based hydrophilic and a bio-based hydrophobic part, also GGM block-structured derivatives with a synthetic hydrophobic tail, consisting of a polydimethylsiloxane chain, were prepared and assessed for the hydrophobization of surface of nanofibrillated cellulose films. In order to generate GGM block-structured derivatives containing a synthetic tail with distinguished physical and chemical properties, as well as a tailored chain length, a controlled polymerization method was used. Therefore, firstly an initiator group was introduced at the reducing end of the GGM and consecutively single electron transfer-living radical polymerization (SET-LRP) was performed by applying three different monomers in individual reactions. For the accomplishment of the synthesis and the analysis of the products, challenges related to the solubility of the reactants had to be overcome. Overall, a synthesis route for the production of GGM block-copolymers bearing different synthetic polymer chains was developed and several derivatives were obtained. Moreover, GGM with different molar masses were, after modification, used as a crosslinker in the synthesis of functional hydrogels. Hereby, a cationic monomer was used during the free radical polymerization and the resultant hydrogels were successfully tested for the removal of chromium and arsenic ions from aqueous solutions. The hydrogel synthesis was tailored and materials with distinguished physical properties, such as the swelling rate, were obtained after purification. The results generated in this work underline the potential of bio-based products and the urge to continue carrying out research in order to be able to use more green chemicals for the manufacturing of biorenewable and biodegradable daily products.

Studies in selectivity of lipases in preparation of cyanohydrins, sugar conjugates and secondary alcohols

Biocatalysis can be applied in organic synthetic chemistry to counter challenges posed by increased demands towards chemo-, regio- and stereoselectivity, not forgetting the need for greener chemistry. During the last 30 years, biocatalysis with the use of enzymes as chiral catalysts has become more common in chemistry laboratories and industrial processes. In this thesis, the use of lipases as versatile biocatalysts in the acylation of alcohols is examined both in the light of literature examples and four original publications. In the first part of the work presented in this thesis lipases were utilized in two examples concerning secondary alcohols. First, the kinetic resolution of heterocyclic aromatic secondary alcohols through transesterification was thoroughly examined including the studies of competing hydrolysis and esterification reactions. In another example, lipases were utilized in the formation of a dynamic systemic resolution (DSR) process which in turn was used as a developmental tool in the optimization of the dynamic kinetic resolution (DKR) of five heterocyclic aromatic cyanohydrins in one pot for the preparation of cyanohydrin esters as single enantiomers. In the second part of the work, the regio- and stereoselectivity of lipases was used to form sugar conjugates of glyceric and β-amino acids. The primary hydroxyl groups of methyl α-D-galacto-, -gluco- and -mannopyranosides were now acylated trough lipasecatalyzed transesterification and enantioselective lipase-catalyzed ring-opening of β- lactams, respectively.