Cytotoxic iron chelators: Characterization of the structure, solution chemistry and redox activity of ligands and iron complexes of the di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) analogues

Di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) and a range of its analogues comprise a series of monobasic acids that are capable of binding iron (Fe) as tridentate (N,N,O) ligands. Recently, we have shown that these chelators are highly cytotoxic, but show selective activity against cancer cells. Particularly interesting was the fact that cytotoxicity of the HPKIH analogues is maintained even after complexation with Fe. To understand the potent anti-tumor activity of these compounds, we have fully characterized their chemical properties. This included examination of the solution chemistry and X-ray crystal structures of both the ligands and Fe complexes from this class and the ability of these complexes to mediate redox reactions. Potentiometric titrations demonstrated that all chelators are present predominantly in their charge-neutral form at physiological pH (7.4), allowing access across biological membranes. Keto-enol tautomerism of the ligands was identified, with the tautomers exhibiting distinctly different protonation constants. Interestingly, the chelators form low-spin (diamagnetic) divalent Fe complexes in solution. The chelators form distorted octahedral complexes with Fe-II, with two tridentate ligands arranged in a meridional fashion. Electrochemistry of the Fe complexes in both aqueous and non-aqueous solutions revealed that the complexes are oxidized to their ferric form at relatively high potentials, but this oxidation is coupled to a rapid reaction with water to form a hydrated (carbinolamine) derivative, leading to irreversible electrochemistry. The Fe complexes of the HPKIH analogues caused marked DNA degradation in the presence of hydrogen peroxide. This observation confirms that Fe complexes from the HPKIH series mediate Fenton chemistry and do not repel DNA. Collectively, studies on the solution chemistry and structure of these HPKIH analogues indicate that they can bind cellular Fe and enhance its redox activity, resulting in oxidative damage to vital biomolecules.

Initial performance of pineapple and utilization of rock phosphate applied in combination with organic compounds to leaf axils

Rock phosphates have low solubility in water, but good solubility in acid. The use of organic compounds together with these phosphorus sources applied to the basal leaf axils of pineapple can increase the solubility of this phosfate source and increase the P availability to the crop. A greenhouse experiment was conducted using Araxá rock phosphate (10 g) in combination or not with solutions containing increasing concentrations of humic acids (0 to 40 mmol L-1 of carbon), with or without citric acid (0.005 mmol L-1), applied to basal leaf axils of pineapple cv. Pérola. Growth and nutritional characteristics of aerial plant parts were assessed. Growth rates of aerial parts and N, P, K, Ca and Mg contents increased curvilinearly with increasing concentration of carbon in the form of humic acids. Maximum values were found for the concentration of 9.3 mmol L-1 of carbon combined with 0.005 mmol L-1 of citric acid and natural phosphate.

A creative solution for rapid and inexpensive model-making in product design processes

Innovative Developments in Virtual and Physical Prototyping

Initial growth of maize in response to application of rock phosphate, vermicompost and endophytic bacteria

Due to the high energy requirement and demand for non-renewable resources for the production of chemical fertilizers, added also to the environmental impact caused by the use of such products, it is important to intensify research on bio-based agricultural inputs. The use of nitrogen-fixing endophytic and phosphate solubilizing bacteria can provide these nutrients to the plants from the air and poorly soluble phosphorus sources, such as phosphate rock. The objective of this study was to evaluate the nutrition and initial growth of maize (Zea mays L.) in response to the inoculation of nitrogen-fixing and rock phosphate solubilizing endophytic bacteria, in single or mixed formulation, applied with vermicompost. The treatments containing bacteria, both diazotrophic and phosphate solubilizing, when compared to controls, showed higher levels of leaf nitrogen and phosphorus in maize, as well as higher growth characteristics. The application of vermicompost showed synergistic effect when combined with endophytic bacteria. Thus, the innovation of the combination of the studied factors may contribute to the early development of maize.

Growth and nutrient uptake of coffee seedlings cultivated in nutrient solution with and without silicon addition

In recent years, the application of silicon (Si) in crops, including coffee, has become a common practice. The objective of this study was to assess the silicon uptake by coffee seedlings and its effects on plant growth, water and macro and micronutrient uptake. The research was conducted using nutrient solution in a greenhouse at the Departamento de Fitotecnia da Universidade Federal de Viçosa, in a completely randomized design with two treatments (with and without silicon) and three replications. Each plot consisted of three plants grown in a 800 mL vessel containing the treatment solutions. At every three days, water consumption, the concentration of OH - and the depletion of Si and K were assessed in the nutrient solutions. After 33 days, the plants were assessed with regard to their fresh and dry weight of leaves, roots and stem, shoot height and total length of the plant (shoot and root). Number of leaves and internodes, and the content and accumulation of silicon, macro, and micronutrients were also determined. The consumption of water, the amount of potassium uptake and, biomass accumulation were greater in plants grown in solution without silicon addition. However, the concentration of OH- in the solution and the amount of silicon uptake were greater in plants grown in solution with added silicon. Silicon accumulation was greater in leaves than in stem and roots. Silicon decreased coffee plant accumulation of phosphorus, potassium, calcium, zinc, copper and iron.

Initial performance of maize in response to NPK fertilization combined with Herbaspirillum seropedicae

The inoculation with plant growth-promoting bacteria can be a technological approach useful for increasing the production of maize. The objective of this study was to evaluate the initial performance of maize in response to application of doses of NPK combined with the inoculation of the diazotrophic bacteria Herbaspirillum seropedicae in an greenhouse experiment. The experiment consisted of six fertilizer levels: 0, 25, 50, 75, 100 and 200% of the recommended dose of NPK applied to maize inoculated and non-inoculated with H. seropedicae. At 30 days after the treatment application, the growth characteristics and nutritional status of the plants were evaluated. Plant development was influenced by fertilization, but it was enhanced by combination with the bacteria, which resulted in significant increases in the dry mass of shoots (7%) and leaf area (9%) when compared with non-inoculated plants. The results showed increases in the concentration of N (11%), P (30%) and K (17%) of maize plants in response to bacterial inoculation together with NPK compared with plants that were applied fertilize only. The greater consistency and stability response of the host plant to bacterization in the presence of chemical fertilizer indicate a promissory biotechnological approach for improving the initial growth and adaptation of maize to the cultivation environment.

Effect of N and K doses in nutritive solution on growth, production and coffee bean size

An adequate supply of nutrients is essential for obtaining high yields of coffee. The objective of this study was to evaluate the effect of N, K and the N:K ratio on vegetative and reproductive growth of coffee. For this purpose, coffee plants were grown in nutrient solution containing K in the concentrations of 1.08; 2.15; 3.23 and 5.38 mmol L-1 combined with a dose of 6 mmol L-1 N, resulting in the N:K ratios (w/w): 1:0.5; 1:1; 1:1.5 and 1:2.5. The control treatment consisted of the doses 3 and 1.61 mmol L-1 of N and K respectively, resulting in the N:K ratio (w/w) 1.0:1.5. The following variables were evaluated: height, stem diameter, number of nodes of the eighth plagiotrofic branch (index branch), pairs of plagiotrofic branches and number of nodes in the orthotropic branch every three weeks from the beginning of the experiment. Additionally, it was evaluated the chemical composition of processed beans and leaves between the flowering and the rapid expansion stage of the cherry beans, production of cherry beans per plant and classification of beans according to the size. N influenced mainly the characteristics of vegetative growth and K influenced mainly the reproductive growth evaluated by the production. The lowest production resulted in the highest percentages of beans retained on sieves with holes larger than 16/64", while the highest production promoted an increase in the percentage of beans retained on sieves with holes smaller than 16/64".

A creative solution for rapid and inexpensive model-making in product design processes

Rapid prototyping (RP) is an approach for automatically building a physical object through solid freeform fabrication. Nowadays, RP has become a vital aspect of most product development processes, due to the significant competitive advantages it offers compared to traditional manual model making. Even in academic environments, it is important to be able to quickly create accurate physical representations of concept solutions. Some of these can be used for simple visual validation, while others can be employed for ergonomic assessment by potential users or even for physical testing. However, the cost of traditional RP methods prevents their use in most academic environments on a regular basis, and even for very preliminary prototypes in many small companies. That results in delaying the first physical prototypes to later stages, or creating very rough mock-ups which are not as useful as they could be. In this paper we propose an approach for rapid and inexpensive model-making, which was developed in an academic context, and which can be employed for a variety of objects.

Modifying fish gelatin electrospun membranes for biomedical applications: cross- linking and swelling behavior

Development of suitable membranes is a fundamental requisite for tissue and biomedical engineering applications. This work presents fish gelatin random and aligned electrospun membranes cross-linked with glutaraldehyde (GA). It was observed that the fiber average diameter and the morphology is not influenced by the GA exposure time and presents fibers with an average diameter around 250 nm. Moreover, when the gelatin mats are immersed in a phosphate buffered saline solution (PBS), they can retain as much as 12 times its initial weight of solution almost instantaneously, but the material microstructure of the fiber mats changes from the characteristic fibrous to an almost spherical porous structure. Cross-linked gelatin electrospun fiber mats and films showed a water vapor permeability of 1.37 ± 0.02 and 0.13 ± 0.10 (g.mm)/(m2.h.kPa), respectively. Finally, the processing technique and cross-linking process does not inhibit MC-3T3-E1 cell adhesion. Preliminary cell culture results showed good cell adhesion and proliferation in the cross-linked random and aligned gelatin fiber mats.

Kinetics of solute leachate from imbibing Caesalpinia echinata Lam. (Brazilwood) seeds

The electrical conductivity of leachates from imbibing seeds has been used as a vigor test for several species. The adaptation of this methodology to different species requires knowledge on the leaching kinetics of electrolytes. For Brazilwood seeds, the classic method was not satisfactory and rapid tests are essential because they have low storage capacity at room temperature. Leaching kinetics during seed imbibition is a function of physiological quality, presence or absence of seed coat, imbibing temperature and the initial moisture content of seed. In this study, the electrolyte leaching rate of six different categories of seeds, from two regions, was evaluated in seeds with and without seed coat and incubated with different moisture contents and at different temperatures. The results showed that the electrolyte leaching rate in Brazilwood seeds is independent of the physiological quality, the presence or absence of seed coat and imbibition temperature, but these factors changed the total amount of electrolytes leached. The leaching rate increased in the first few minutes of imbibition, suggesting that the adjustment of the methodology must consider the reduction in imbibition time, reduction in temperature, use of a controlled and slower pre-imbibition, and replacement of the imbibition solution after the first few minutes.

Automatic modeling of pectus excavatum corrective prosthesis using artificial neural networks

Pectus excavatum is the most common deformity of the thorax. Pre-operative diagnosis usually includes Computed Tomography (CT) to successfully employ a thoracic prosthesis for anterior chest wall remodeling. Aiming at the elimination of radiation exposure, this paper presents a novel methodology for the replacement of CT by a 3D laser scanner (radiation-free) for prosthesis modeling. The complete elimination of CT is based on an accurate determination of ribs position and prosthesis placement region through skin surface points. The developed solution resorts to a normalized and combined outcome of an artificial neural network (ANN) set. Each ANN model was trained with data vectors from 165 male patients and using soft tissue thicknesses (STT) comprising information from the skin and rib cage (automatically determined by image processing algorithms). Tests revealed that ribs position for prosthesis placement and modeling can be estimated with an average error of 5.0 ± 3.6 mm. One also showed that the ANN performance can be improved by introducing a manually determined initial STT value in the ANN normalization procedure (average error of 2.82 ± 0.76 mm). Such error range is well below current prosthesis manual modeling (approximately 11 mm), which can provide a valuable and radiation-free procedure for prosthesis personalization.

Hydraulic conductivity in response to exchangeable sodium percentage and solution salt concentration

Hydraulic conductivity is determined in laboratory assays to estimate the flow of water in saturated soils. However, the results of this analysis, when using distilled or deionized water, may not correspond to field conditions in soils with high concentrations of soluble salts. This study therefore set out to determine the hydraulic conductivity in laboratory conditions using solutions of different electrical conductivities in six soils representative of the State of Pernambuco, with the exchangeable sodium percentage adjusted in the range of 5-30%. The results showed an increase in hydraulic conductivity with both decreasing exchangeable sodium percentage and increasing electrical conductivity in the solution. The response to the treatments was more pronounced in soils with higher proportion of more active clays. Determination of hydraulic conductivity in laboratory is routinely performed with deionized or distilled water. However, in salt affected soils, these determinations should be carried out using solutions of electrical conductivity different from 0 dS m-1, with values close to those determined in the saturation extracts.

Automatic modeling of pectus excavatum corrective prosthesis using artificial neural networks

Pectus excavatum is the most common deformity of the thorax. Pre-operative diagnosis usually includes Computed Tomography (CT) to successfully employ a thoracic prosthesis for anterior chest wall remodeling. Aiming at the elimination of radiation exposure, this paper presents a novel methodology for the replacement of CT by a 3D laser scanner (radiation-free) for prosthesis modeling. The complete elimination of CT is based on an accurate determination of ribs position and prosthesis placement region through skin surface points. The developed solution resorts to a normalized and combined outcome of an artificial neural network (ANN) set. Each ANN model was trained with data vectors from 165 male patients and using soft tissue thicknesses (STT) comprising information from the skin and rib cage (automatically determined by image processing algorithms). Tests revealed that ribs position for prosthesis placement and modeling can be estimated with an average error of 5.0 ± 3.6 mm. One also showed that the ANN performance can be improved by introducing a manually determined initial STT value in the ANN normalization procedure (average error of 2.82 ± 0.76 mm). Such error range is well below current prosthesis manual modeling (approximately 11 mm), which can provide a valuable and radiation-free procedure for prosthesis personalization.

Initial performance of corn in response to treatment of seeds with humic acids isolated from bokashi

ABSTRACT The humified organic matter presents bioactivity similar to the auxinic effect. As bokashi is produced by a special process of humification, information is needed about the bioactive potential of its humic acids. The objective of this work was studying the initial performance of corn-indicator plants in response to the application of different concentrations of humic acids isolated from bokashi. The corn seeds were treated for 16 hours with solutions containing 0, 10, 20, 30, 40 and 80 mmol L-1 of C in the form of humic acids. Then, the seeds were planted in pots of 1 dm3 containing corrected and fertilized soil, in greenhouse. Growth characteristics of shoot and root systems were evaluated. The results showed that the humic acids extracted from bokashi had positive effects on the initial performance of corn.

Effect of plant-biostimulant on cassava initial growth

ABSTRACT Biostimulants are complex substances that promote hormonal balance in plants, favor the genetic potential expression, and enhance growth of shoots and root system. The use of these plant growth promoters in crops can increase quantitatively and qualitatively crop production. Therefore, the aim of this study was to evaluate the effect of a commercial biostimulant on the initial growth of cassava. The experiment was arranged in a 2 x 5 factorial design, corresponding to two cassava cultivars (Cacau-UFV and Coimbra) and five biostimulant concentrations (0, 4, 8, 12 and 16 mL L-1). At 90 days after planting, the characteristics leaf area, plant height, stem diameter, leaf number, total dry matter and dry matter of roots, stems and leaves were evaluated. The biostimulant promoted linear increases in plant height, leaf number, leaf area, total dry matter, dry matter of stems, leaves and roots. The cultivar Cacau-UFV had a higher growth rate than the cultivar Coimbra. The growth promoter stimulated the early growth of the cassava crop.