Synthesis, characterization and chemical sensor application of conducting polymers

Polymeric materials that conduct electricity are highly interesting for fundamental studies and beneficial for modern applications in e.g. solar cells, organic field effect transistors (OFETs) as well as in chemical and bio‐sensing. Therefore, it is important to characterize this class of materials with a wide variety of methods. This work summarizes the use of electrochemistry also in combination with spectroscopic methods in synthesis and characterization of electrically conducting polymers and other π‐conjugated systems. The materials studied in this work are intended for organic electronic devices and chemical sensors. Additionally, an important part of the presented work, concerns rational approaches to the development of water‐based inks containing conducting particles. Electrochemical synthesis and electroactivity of conducting polymers can be greatly enhanced in room temperature ionic liquids (RTILs) in comparison to conventional electrolytes. Therefore, poly(para‐phyenylene) (PPP) was electrochemically synthesized in the two representative RTILs: bmimPF6 and bmiTf2N (imidazolium and pyrrolidinium‐based salts, respectively). It was found that the electrochemical synthesis of PPP was significantly enhanced in bmimPF6. Additionally, the results from doping studies of PPP films indicate improved electroactivity in bmimPF6 during oxidation (p‐doping) and in bmiTf2N in the case of reduction (n‐doping). These findings were supported by in situ infrared spectroscopy studies. Conducting poly(benzimidazobenzophenanthroline) (BBL) is a material which can provide relatively high field‐effect mobility of charge carriers in OFET devices. The main disadvantage of this n‐type semiconductor is its limited processability. Therefore in this work BBL was functionalized with poly(ethylene oxide) PEO, varying the length of side chains enabling water dispersions of the studied polymer. It was found that functionalization did not distract the electrochemical activity of the BBL backbone while the processability was improved significantly in comparison to conventional BBL. Another objective was to study highly processable poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) water‐based inks for controlled patterning scaled‐down to nearly a nanodomain with the intention to fabricate various chemical sensors. Developed PEDOT:PSS inks greatly improved printing of nanoarrays and with further modification with quaternary ammonium cations enabled fabrication of PEDOT:PSS‐based chemical sensors for lead (II) ions with enhanced adhesion and stability in aqueous environments. This opens new possibilities for development of PEDOT:PSS films that can be used in bio‐related applications. Polycyclic aromatic hydrocarbons (PAHs) are a broad group of π‐conjugated materials consisting of aromatic rings in the range from naphthalene to even hundred rings in one molecule. The research on this type of materials is intriguing, due to their interesting optical properties and resemblance of graphene. The objective was to use electrochemical synthesis to yield relatively large PAHs and fabricate electroactive films that could be used as template material in chemical sensors. Spectroscopic, electrochemical and electrical investigations evidence formation of highly stable films with fast redox response, consisting of molecules with 40 to 60 carbon atoms. Additionally, this approach in synthesis, starting from relatively small PAH molecules was successfully used in chemical sensor for lead (II).

Anti-predator adaptations in aquatic environments

Predation is an important selective force that has led to the evolution of a variety of fascinating anti-predator adaptations, such as many types of protective coloration and prey behaviours. Because the evolution of life has begun in the aquatic environment and many anti-predator adaptations are found already in relative primitive taxa, it is likely that many of these adaptations evolved initially in the aquatic environment. Yet, there has been surprisingly little research on the mechanisms and function of antipredator adaptations in aquatic systems. To understand the function of anti-predator adaptations and natural selection imposed on prey appearance and behaviour, I have investigated how protective coloration can be used, either as such or together with behavioural adaptations, to manipulate predator behaviour and decrease predation risk. To this end I conducted a series of behaviour ecological laboratory experiments in which I manipulated the visual appearance of artificial backgrounds and prey items. In paper I of this thesis, I investigated background choice as an anti-predator strategy, by observing the habitat choice of the least killifish (Heterandria formosa) between pairs of artificial backgrounds, both in the presence and absence of predation threat. It has been suggested that prey could decrease their risk of being detected by predators either by preferring backgrounds into which they blend or by preferring visually complex backgrounds. The least killifish preferred a background that matched their patterning to a background that mismatched it, showing that they are able to respond to cues of visual similarity between their colour pattern and the surrounding environment. Interestingly however, in female least killifish visual complexity of the background was a more important cue for habitat safety and may override or act together with background matching when searching for a safe habitat. It is possible that in females, preference for visually complex backgrounds is associated with lower opportunity costs than preference for matching backgrounds would be. Generally, the least killifish showed stronger preference while under predation threat, indicating that their background choice behaviour is an antipredator adaptation. Many aquatic prey species have eyespots, which are colour patterns that consist of roughly concentric rings and have received their name because they for humans often resemble the vertebrate eye. I investigated the anti-predator function of eyespots against predation by fish in papers II, III and IV. Some eyespots have been suggested to benefit prey by diverting the strikes of predators away from vital parts of the prey body or towards a direction that facilitates prey escape. Although proposed over a century ago, the divertive effect of eyespots has proven to be difficult to show experimentally. In papers II and III, I tested for divertive effect of eyespots towards attacking fish by presenting artificial prey with eyespots to laboratory reared three-spined sticklebacks (Gasterosteus aculeatus). I found that eyespots strongly influenced the behaviour of attacking sticklebacks and effectively drew their strikes towards the eyespots. To further investigate this divertive effect and whether the specific shape of eyespots is important for it, I tested in paper III the response of fish also to other markings than eyespots. I found that eyespots were generally more effective in diverting the first strikes of attacking fish compared to other prey markings. My findings suggest that the common occurrence of eyespots in aquatic prey species can at least partly be explained by the divertive effect of the eyespot shape, possibly together with the relative simple developmental mechanisms underlying circular colour patterns. An eyebar is a stripe that runs through the eye, and this pattern has been suggested to obscure the real eyes of the prey by visually blending parts of the eyes and head of the prey and by creating false edges. In paper III, I show that an eyebar effectively disrupts an eyelike shape. This suggests that eyebars provide an effective way to conceal the eyes and consequently obstruct detection and recognition of prey. This experiment also demonstrates that through concealment of the eyes, eyebars could be used to enhance the divertive effect of eyespots, which can explain the common occurrence of eyebars in many species of fish that have eyespots. Larger eyespots have been shown to intimidate some terrestrial predators, such as passerine birds, either because they resemble the eyes of the predator’s own enemy or because highly salient features may have an intimidating effect. In papers II and IV, I investigated whether the occurrence of eyespots in some aquatic prey could be explained by their intimidating effect predatory fish. In paper IV, I also investigated the reason for the intimidating effect of eyelike prey marks. In paper II, I found no clear intimidating effect of eyespots, whereas in paper IV, using a different approach, I found that sticklebacks hesitated to attack towards eyelike but not towards non-eyelike marks. Importantly, paper IV therefore presents the first rigorous evidence for the idea that eye mimicry, and not merely conspicuousness, underlies the intimidating effect. It also showed that the hesitation shown by fish towards eyelike marks is partly an innate response that is reinforced by encounters with predators. Collectively, this thesis shows that prey colour pattern and the visual appearance of the habitat influence the behaviour of fish. The results demonstrate that protective coloration provides numerous distinctive ways for aquatic prey to escape predation. Thus, visual perception and behaviour of fish are important factors shaping the appearance and behaviours of aquatic prey.

Época de aplicación y toxicidad varietal del herbicida amicarbazone en la caña de azúcar, en Veracruz, México

Durante el ciclo primavera-verano 2005, se establecieron tres experimentos en Úrsulo Galván, Ver., México, con el objetivo de determinar la mejor época de aplicación del herbicida amicarbazone en la caña de azúcar en condiciones de riego e identificar la susceptibilidad de las tres principales variedades cultivadas en el estado a este herbicida. En un experimento, se evaluó el control de malezas con amicarbazone a 0,7, 1,05 y 1,4 kg ha‑1 aplicado en cuatro épocas: preemergencia antes del riego de germinación, preemergencia después del riego de germinación, postemergencia temprana y postemergencia tardía. En los otros experimentos, se evaluó la toxicidad de amicarbazone a 0, 0,7, 1,4 y 2,1 kg ha-1, aplicado en preemergencia y postemergencia en las variedades de caña de azúcar Mex 69-290, CP 72‑2086 y Mex 79-431. El quelite rastrero (Amaranthus lividus) fue mejor controlado con aplicaciones postemergentes de amicarbazone, a partir de 0,7 kg ha-1. Por su parte, el control del zacate Guinea (Megathyrsus maximus) fue bajo en todas las épocas de aplicación. En aplicaciones preemergentes, el amicarbazone hasta 2,1 kg ha-1 fue altamente selectivo a todas las variedades evaluadas, mientras que, cuando fue aplicado en postemergencia, ocasionó ligera toxicidad a las tres variedades de caña de azúcar, la cual fue mayor conforme se incrementó la dosis. Sin embargo, los daños desaparecieron entre los 30 y 45 días después de la aplicación y no ocasionaron reducción permanente en la altura de las plantas.

EFFECTS OF PLANTING DATE AND SPATIAL ARRANGEMENT ON COMMON BEAN (Phaseolus vulgaris) YIELD UNDER WEED-FREE AND WEEDY CONDITIONS

ABSTRACTTo evaluate the effect of planting date and spatial pattern on common bean yield under weed-free and weed-infested conditions, an experiment was conducted in Kelachay, Northern Iran, in 2013. The experimental design was a randomized complete block in a factorial arrangement with three replicates. Factors were planting date (10 August and 20 August), spatial pattern (square and rectangular planting pattern, with a planting distance of 30 x 30 cm and 45 x 20 cm, respectively), and weed management regime (weed-free and weedy conditions, weeded and not weeded throughout the growing season, respectively). Results showed that the main effect of planting date was significant only for pod number per plant and seed number per pod. At the same time, pod number per plant, seed number per pod, pod length, and grain yield were influenced significantly by spatial pattern. Results of ANOVA have also indicated that all traits, except pod length, were influenced significantly by weed-management regimes. Moreover, effect of planting date and spatial pattern were nonsignificant for weed dry weight. Mean comparison has expressed a significant increment in seed yield for square planting arrangement (1,055 kg ha-1) over rectangular (971 kg ha-1). Weeding has also presented an overall 12% and 8% improvement in grain and pod yield over control (weedy check), respectively. Based on the results of this study, weed control, as well as square planting pattern, are recommended for obtaining the highest seed yield in common bean.

GLYPHOSATE DRIFT IN EUCALYPTUS PLANTS

ABSTRACTWith the present study we aim to assess the damage caused to Eucalyptus plants exposed to glyphosate drift in different canopy portions. The drift simulation was carried out through application of 1,080 g ha-1 of glyphosate in five canopy portions (0, 25, 50, 75 and 100% of the low branches), in four areas of cultivation. Areas I and II, plants with 0.91 and 2.98 m, and height of canopy drift exposition of 0.30 and 1.0 m, respectively. In areas III and IV both cultivations were 8.15 m high, varying the height of drift exposition between 2.0 and 2.5 m, respectively. At 30 and 480 days after application (DAA), the survival rate was assessed, and at 300 and 480 DAA diameter at breast height (DBH), height, volume and their respective increment were determined. The medium annual increment (MAI) was determined at 480 DAA. Area I, in which the plants were 0.91 m high, we observed that treatment with 100% of the low branches exposed to drift led to stand reduction of the plants around 18.75 and 38.19% at 30 and 480 DAA, respectively. Areas I and II showed reduction in plant growth in height and DBH, wood volume and MAI, to the extent that there was an increase in the portion of canopy exposed to glyphosate drift. However, in areas III and IV, in which 8.15 m height plants were found, no changes were verified for the evaluated characteristics, regardless of the portion of canopy exposed to glyphosate drift.

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.

Effect of light and temperature on germination and early growth of Vochysia tucanorum Mart., Vochysiaceae, in cerrado and forest soil under different radiation levels

Vochysia tucanorum Mart. (Vochysiaceae) is a very widely distributed species in the cerrado and forests in Brazil, from the State of Bahia to Paraná. Its seed germination was analysed under eight treatments using different conditions of light and temperature. Up to 73 days, at least ca. 93% of the seeds germinated in all treatments, except under alternating temperatures of 35°/10°C (62%). Light enhanced germination, except under constant temperature of 25°C when seeds are not photoblastic. At this temperature, the highest percentage of germination was found. Initial vegetative growth was analysed by comparing the effects of shading, by means of different percentages of full daylight (100%, 45%, 10.6%, 4.8%), and soils from cerrado and forest. During 123 days, no mortality was recorded and cotyledons persisted on the seedlings of all treatments. In general, the seedlings of V. tucanorum were found to be more or less indifferent to the soil from cerrado or forest and shading seems to promote height increment. However, total dry mass was larger under a radiation of 45% full daylight and smaller under extreme conditions (100% or 4.8% full daylight).

Temporal dynamics of two species of Chaetophoraceae (Chlorophyta) in tropical streams of São Paulo State, Southeastern Brazil

Temporal dynamics of the chaetophoracean green algae Chaetophora elegans (Roth) C.A. Agardh and Stigeoclonium amoenum Kützing populations was investigated biweekly during late autumn trhough early spring (April to October) in two tropical streams from northwestern São Paulo State, southeastern Brazil. Abundances of one population of each species was evaluated by the quadrat technique in terms of percent cover and frequency. The fluctuations were related to the following stream variables: temperature, turbidity, specific conductance, pH, oxygen saturation, depth, substratum type, current velocity, irradiance and nutrients. Percent cover and frequency of C. elegans had lower values throughout the study period and was positively correlated to rainfall. Other correlations (i.e. positive of percent cover with depth and current velocity and negative with irradiance) were consistently found, reinforcing the strong influence of rainfall. On the other hand, percent cover and frequency of S. amoenum had higher values, with maximum growth from June to September. Percent cover was negatively correlated to rainfall. Results suggest the precipitation regime as the most important driving force to temporal changes in both populations, but playing different roles in each one. The gelatinous thallus of C. elegans seem to be favored by the increment of current velocity, since higher flows can improve the nutrient uptake by means of reduction in diffusion shell without promoting excessive drag force. In contrast, tufts of S. amoenum are, presumably, more exposed to drag force, and, consequently, more susceptible to mechanical damage effects due to higher current velocities.

Phenology, litterfall, growth, and root biomass in a tidal floodplain forest in the Amazon estuary

The dynamics of forests subject to inundation appears to be strongly influenced by the frequency and intensity of natural disturbances such as flooding. In a late successional tidal floodplain forest near the Amazon port of Belém, Brazil, we tested this prediction by measuring seasonal patterns of phenology and litterfall in relation to two key variables: rainfall and tide levels. In addition, we estimated the root biomass and the annual growth of the forest community by measuring stem increments over time. Our results showed high correlations between phenological events (flowering and fruiting) and rainfall and tide levels, while correlations between litterfall and these variations were generally weaker. Contrary to our prediction, root biomass to 1 m depth showed no significant differences along the topographic gradient, and the root biomass at all topographic levels was low to intermediate compared with other neotropical forests. Both litterfall and total stem increment were high compared to other tropical forest, indicating the high productivity of this ecosystem.

Woody community dynamics in two fragments of "cerrado" stricto sensu over a seven-year period (1995-2002), MA, Brazil

This study was conducted in two fragments of "cerrado" stricto sensu in the Gerais de Balsas Colonization Project, located in southern Maranhão, Brazil. The objective was to evaluate the dynamics of the woody plant community, over seven years (1995-2002). Four transects of 160 × 20 m were monitored. All woody plants with a stem diameter > 3 cm, at 0.30 m above ground level, were recorded. In 1995, 983 and 1,177 stems were sampled in fragments 1 and 2, respectively; in 2002, 1057 and 1406 stems were sampled in the same fragments. In 1995, the Shannon diversity indices (H') were 3.07 and 3.33, in fragments 1 and 2, respectively, reaching their maximum value in 2002 of 3.11 and 3.35. The community of fragment 1 showed an increase of 7.5% in density and 4.4% in basal area between 1995 and 2002, while in fragment 2 there was an increment of 19.4% in density and 23.5% in basal area, over the same period. The annual increment in diameter was 0.13 cm year-1 and 0.17 cm year-1 in fragments 1 and 2, respectively. The mortality rate was 2.73% per year in fragment 1 and 4.88% per year in fragment 2, while the recruitment rate was 3.25% per year and 5.86% per year, respectively. The community presented high recruitment and mortality rates compared to the studies conducted in other sites, indicating a community that was highly dynamic in the period studied.

Role of endothelium in angiotensin II formation by the rat aorta and mesenteric arterial bed

We investigated the angiotensin II (Ang II)-generating system by analyzing the vasoconstrictor effect of Ang II, angiotensin I (Ang I), and tetradecapeptide (TDP) renin substrate in the absence and presence of inhibitors of the renin-angiotensin system in isolated rat aortic rings and mesenteric arterial beds with and without functional endothelium. Ang II, Ang I, and TDP elicited a dose-dependent vasoconstrictor effect in both vascular preparations that was completely blocked by the Ang II receptor antagonist saralasin (50 nM). The angiotensin converting enzyme (ACE) inhibitor captopril (36 µM) completely inhibited the vasoconstrictor effect elicited by Ang I and TDP in aortic rings without affecting that of Ang II. In contrast, captopril (36 µM) significantly reduced (80-90%) the response to bolus injection of Ang I, without affecting those to Ang II and TDP in mesenteric arteries. Mechanical removal of the endothelium greatly potentiated (70-95%) the vasoconstrictor response to Ang II, Ang I, and TDP in aortic rings while these responses were unaffected by the removal of the endothelium of mesenteric arteries with sodium deoxycholate infusion. In addition, endothelium disruption did not change the pattern of response elicited by these peptides in the presence of captopril. These findings indicate that the endothelium may not be essential for Ang II formation in rat mesenteric arteries and aorta, but it may modulate the response to Ang II. Although Ang II formation from Ang I is essentially dependent on ACE in both vessels, our results suggest the existence of an alternative pathway in the mesenteric arterial bed that may play an important role in Ang II generation from TDP in resistance but not in large vessels during ACE inhibition

Effects of estradiol benzoate on 5'-iodothyronine deiodinase activities in female rat anterior pituitary gland, liver and thyroid gland

There is little information on the possible effects of estrogen on the activity of 5'-deiodinase (5'-ID), an enzyme responsible for the generation of T3, the biologically active thyroid hormone. In the present study, anterior pituitary sonicates or hepatic and thyroid microsomes from ovariectomized (OVX) rats treated or not with estradiol benzoate (EB, 0.7 or 14 µg/100 g body weight, sc, for 10 days) were assayed for type I 5'-ID (5'-ID-I) and type II 5'-ID (5'-ID-II, only in pituitary) activities. The 5'-ID activity was evaluated by the release of 125I from deiodinated 125I rT3, using specific assay conditions for type I or type II. Serum TSH and free T3 and free T4 were measured by radioimmunoassay. OVX alone induced a reduction in pituitary 5'-ID-I (control = 723.7 ± 67.9 vs OVX = 413.9 ± 26.9; P<0.05), while the EB-treated OVX group showed activity similar to that of the normal group. Thyroid 5'-ID-I showed the same pattern of changes, but these changes were not statistically significant. Pituitary and hepatic 5'-ID-II did not show major alterations. The treatment with the higher EB dose (14 µg), contrary to the results obtained with the lower dose, had no effect on the reduced pituitary 5'-ID-I of OVX rats. However, it induced an important increment of 5'-ID-I in the thyroid gland (0.8 times higher than that of the normal group: control = 131.9 ± 23.7 vs ovx + EB 14 µg = 248.0 ± 31.2; P<0.05), which is associated with increased serum TSH (0.6-fold vs OVX, P<0.05) but normal serum free T3 and free T4. The data suggest that estrogen is a physiological stimulator of anterior pituitary 5'-ID-I and a potent stimulator of the thyroid enzyme when employed at high doses

Changes in the TBARs content and superoxide dismutase, catalase and glutathione peroxidase activities in the lymphoid organs and skeletal muscles of adrenodemedullated rats

Thiobarbituric acid reactant substances (TBARs) content, and the activities of glucose-6-phosphate dehydrogenase (G6PDh), citrate synthase (CS), Cu/Zn- and Mn-superoxide dismutase (SOD), catalase, and glutathione peroxidase (GPX) were measured in the lymphoid organs (thymus, spleen, and mesenteric lymph nodes (MLN)) and skeletal muscles (gastrocnemius and soleus) of adrenodemedullated (ADM) rats. The results were compared with those obtained for sham-operated rats. TBARs content was reduced by adrenodemedullation in the lymphoid organs (MLN (28%), thymus (40%) and spleen (42%)) and gastrocnemius muscle (67%). G6PDh activity was enhanced in the MLN (69%) and reduced in the spleen (28%) and soleus muscle (75%). CS activity was reduced in all tissues (MLN (75%), spleen (71%), gastrocnemius (61%) and soleus (43%)), except in the thymus which displayed an increment of 56%. Cu/Zn-SOD activity was increased in the MLN (126%), thymus (223%), spleen (80%) and gastrocnemius muscle (360%) and was reduced in the soleus muscle (31%). Mn-SOD activity was decreased in the MLN (67%) and spleen (26%) and increased in the thymus (142%), whereas catalase activity was reduced in the MLN (76%), thymus (54%) and soleus muscle (47%). It is particularly noteworthy that in ADM rats the activity of glutathione peroxidase was not detectable by the method used. These data are consistent with the possibility that epinephrine might play a role in the oxidative stress of the lymphoid organs. Whether this fact represents an important mechanism for the establishment of impaired immune function during stress remains to be elucidated.

Immunization by subcutaneous implants of polyester-polyurethane sponges coupled with antigen

A new protocol is described for immunization of outbred Swiss mice. The procedure is based on subcutaneous implantation of antigen-coupled polyester-polyurethane sponges cut into disks of 10 mm in diameter vs 2 mm in thickness. Antigen coupling was performed by overnight incubation of the sponge with a solution of ovalbumin (Ova) (2 mg/ml) diluted in sodium carbonate buffer, pH 9.6. The amount of ovalbumin that was taken up by the sponge was between 71.4 to 82.5 µg. This was estimated by comparing the Ova absorbance at 280 nm in coating buffer solutions before and after incubation. To compare the efficiency of the proposed method, experimental groups immunized with the antigen in the presence of adjuvants (10 µg in Al(OH)3 or 100 µg in complete Freund's adjuvant (CFA)) were run in parallel. The data obtained after the 3rd week of immunization indicate that both cellular and humoral immune responses were achieved. These were assayed by antigen-induced footpad swelling and ELISA (specific antibodies), respectively. The levels of both immune responses elicited were similar to the responses observed in mice immunized with ovalbumin in the presence of Al(OH)3. The method might represent an advantage when immunizing with pathogenic antigens. Preliminary experiments have suggested that the antigen remains immobilized or bound to the sponge for a long period of time, since there is an increment on the cell population inside the sponges after boosting the animals. If so, the undesirable effects of immunization would be reduced.