Relação entre transferência de carga e as interações intermoleculares em complexos de hidrogênio heterocíclicos

Hydrogen-bonded complexes formed by the interaction of the heterocyclic molecules C2H4O and C2H5N with HF, HCN, HNC and C2H2 have been studied using density functional theory. The hydrogen bond strength has been analyzed through electron density charge transfer from the proton acceptor to the proton donor. The density charge transfer has been estimated using different methods such as Mulliken population analysis, CHELPG, GAPT and AIM. It has been shown that AIM-estimated charge transfer correlates very well with the hydrogen bond energy and the infrared bathochromic effect of the proton donor stretching frequencies.

Um estudo teórico relativo à não-linearidade da ligação de hidrogênio em sistemas heterocíclicos C2H4O-C2H2 e C2H4S-C2H2

B3LYP/6-31G(d,p) calculations were used to determine the optimized geometries of the C2H4O-C2H2 and C2H4S-C2H2 heterocyclic hydrogen-bonded complexes. Results of structural, rotational, electronic and vibrational parameters indicate that the hydrogen bonding is non-linear due to the pi bond of the acetylene interacting with the hydrogen atoms of the methyl groups of the three-membered rings. Moreover, the theoretical investigation showed that the non-linearity is much more intriguing, since there is a structural disjunction on the acetylene within the heterocyclic system.

Um estudo teórico de propriedades moleculares em complexos de hidrogênio trimoleculares C2H4···2HF, C2H2···2HF e C3h6···2HF

We present a theoretical study of molecular properties in C2H4···2HF, C2H2···2HF and C3H6···2HF trimolecular hydrogen-bonded complexes. From B3LYP/6-311++G(d,p) calculations, the most important structural deformations are related to the C=C (C2H4), C≡C (C2H2), C-C (C3H6) and HF bond lengths. According to the Bader's atoms in molecules and CHELPG calculations, it was identified a tertiary interaction between the fluorine atom of the second hydrofluoric acid molecule and hydrogen atoms of the ethylene and acetylene within the C2H4···2HF and C2H2···2HF complexes, respectively. Additionally, the evaluation of the infrared spectrum characterized the new vibrational modes and bathochromic effect of the HF molecules.

Metodologia AGOA: a modelagem de clusters de hidratação no complexo aziridina···ácido fluorídrico

We present a theoretical study of solvent effect on C2H5N···HF hydrogen-bonded complex through the application of the AGOA methodology. By using the TIP4P model to orientate the configuration of water molecules, the hydration clusters generated by AGOA were obtained through the analysis of the molecular electrostatic potential (MEP) of solute (C2H5N···HF). Thereby, it was calculated the hydration energies on positive and negative MEP fields, which are maxima (PEMmax) and minima (PEMmin) when represent the -CH2- methylene groups and hydrofluoric acid, respectively. By taking into account the higher and lower hydration energy values of -370.6 kJ mol-1 and -74.3 kJ mol-1 for PEMmax and PEMmin of the C2H5N···HF, our analysis shows that these results corroborate the open ring reaction of aziridine, in which the preferential attack of water molecules occurs at the methylene groups of this heterocyclic.

Solvation simplified

The effects of solvents on chemical phenomena is complex because there are various solute-solvent interaction mechanisms. Solvatochromism refers to the effects of solvents on the spectra of probes. The study of this phenomenon sheds light on the relative importance of the solvation mechanisms. Solvation in pure solvents is quantitatively analyzed in terms of a multi-parameter equation. In binary solvent mixtures, solvation is analyzed by considering the organic solvent, S, water, W, and a 1:1 hydrogen bonded species (S-W). The applications of solvatochromism to understand distinct chemical phenomena, reactivity and swelling of cellulose, is briefly discussed.

Using passive techniques for vibration damping in mechanical systems

This paper examines two passive techniques for vibration reduction in mechanical systems: the first one is based on dynamic vibration absorbers (DVAs) and the second uses resonant circuit shunted (RCS) piezoceramics. Genetic algorithms are used to determine the optimal design parameters with respect to performance indexes, which are associated with the dynamical behavior of the system over selected frequency bands. The calculation of the frequency response functions (FRFs) of the composite structure (primary system + DVAs) is performed through a substructure coupling technique. A modal technique is used to determine the frequency response function of the structure containing shunted piezoceramics which are bonded to the primary structure. The use of both techniques simultaneously on the same structure is investigated. The methodology developed is illustrated by numerical applications in which the primary structure is represented by simple Euler-Bernoulli beams. However, the design aspects of vibration control devices presented in this paper can be extended to more complex structures.

Maize nitrogen fertilization in two crop rotation systems under no-till

The objective of this study was to evaluate split nitrogen (N) fertilization of maize applied in band at sowing and top dressing with and without crop rotation, under no-till. The experiment was conducted with six N rates at sowing (0, 20, 30, 40, 50 and 60 kg ha-1) combined with three rates in top dressing (40, 70, 100 kg ha-1) and two management systems: after five cropping sequences of maize and crop rotation (maize + soybean + oat + soybean + corn) in a randomized block design with four replications. The crop rotation system increased yield in approximately 7% in relation to the area without rotation. The split of nitrogen fertilization, in rates above 39 and 54 kg ha-1 at sowing and 70 and 40 kg ha-1 in top dressing, resulted in yield higher than that obtained with the application of 100 kg ha-1 in top dressing. Grain yield was higher with the rates 50 and 70 kg ha-1 of N compared with that obtained with 20 and 100 kg ha-1 at sowing and top dressing, respectively. The rate 70 kg ha-1 of N resulted in the highest yield at the lowest cost compared with the revenues and costs incurred with the rates 40 and 100 kg ha-1.

Performance, carcass traits and costs of Suffolk lambs finishing systems with early weaning and controlled suckling

The performance, carcass traits and finishing costs of Suffolk lambs were evaluated in three systems: (1) lambs weaned with 22 kg of body weight (BW) and supplemented with concentrate on pasture until slaughter; (2) lambs weaned with 22 kg BW and fed in feedlot until slaughter; (3) lambs maintained in controlled nursing after 22 kg BW and creep fed in feedlot until slaughter. Average daily gain (ADG) was 224 g/d for lambs weaned and supplemented with concentrate on pasture, 386 g/d for lambs weaned in feedlot and 481 g/d for lambs under controlled nursing. Empty body weight and visceral fat deposition were highest in lambs from feedlot systems. Carcass weights and carcass yields were highest for lambs in controlled nursing. Finishing total costs were highest in controlled nursing and lowest in the system with weaning in feedlot. High concentrate diet associated with controlled nursing in feedlot allowed lambs to reach the growth potential and carcasses with higher weights, higher yields and higher fat content. After weaning, lambs in feedlot fed with high concentrate diet had higher weight gain than lambs supplemented with concentrate on pasture. Carcasses produced under these two systems presented the same characteristics. The system with weaning in feedlot showed the lowest cost per kg carcass.

Production and photosynthetic activity of Mimosa Verde and Mimosa Roxa lettuce in two farming systems

Lettuce (Lactuca sativa L.) is the most commonly consumed leaf vegetable in the Brazilian diet, and it is a good source of vitamins and minerals. It is widely grown in the conventional farming system. However, the hydroponic farming system has been gaining importance in the market, wining confidence from consumers, who are becoming increasingly more demanding on food quality. The objective of this study was to evaluate the performance of two lettuce cultivars on hydroponic and conventional farming systems for the production of fresh mass (FM) and dry mass (DM), photosynthesis, contents of chlorophyll and anthocyanin. The following two experiments were carried out: hydroponics farming (HF) and conventional farming (CF), performed in protect and unprotect environments, respectively, in Florianópolis, SC. Mimosa Verde cultivar (MV) showed greater fresh mass than Mimosa Roxa (MR), in both farming systems and the two cultivars presented better performance in the hydroponic system (287.7 g MV and 139.1 g MR) than the conventional system (129.7 g MV and 111.8 g MR). Mimosa Verde cultivar presented lower average contents of total chlorophyll (7.7 mg g-¹ FM) than Mimosa Roxa (11.8 mg g-¹FM), and both cultivars displayed higher means for this variable in the hydroponic farming system. Mimosa Roxa presented higher contents of anthocyanin in the conventional system (88.24 mg g-¹ FM) than the ones in the hydroponic system (36.89 mg g-¹ FM). The best results for CO2 net assimilation rate regarded to photosyntheticaly active photon flux density were found in the hydroponic system, for both lettuce cultivars. Variation in the contents of chlorophyll were also found. Those variations were higher in the protected system than in the hydroponic system and contents of anthocyanin were higher in the conventional system.

Economic viability of the third milking in systems of production using closed-circuit mechanical milking

This study aimed to analyze the economic viability of the third milking in production systems using mechanical milking in a closed circuit, aiming to provide technicians and farmers with information to assist them in decision-making. Specifically, it intended: (a) to estimate the cost of one milking; (b) to estimate the cost of the third milking; (c) to develop a mathematical equation to estimate the minimum amount of milk produced with two milkings, from which it would be economically feasible to do the third milking. Data were collected from three dairy farms, from November 2010 to March 2011, keeping a twice-a-day milking frequency, with three data collections in each farm, totalizing nine collections. Considering the average data, it would be feasible to do the third milking if the average milk yield per day of lactating cows in a twice-a-day milking frequency was greater than or equal to 24.43 kg of milk.

Agronomic performance of common bean in straw mulch systems and topdressing nitrogen rates in no-tillage

ABSTRACTIn no-tillage systems, straw coverage on soil surface is the key to success, and the choice of crops for rotation is crucial to achieve the sustainability and quality that conservation agriculture requires. The objective of this study was to evaluate the agronomic performance of the common bean cultivar IAC Formoso sown in succession to three straw mulch systems (corn alone, corn/Urochloa ruziziensisintercrop and U. ruziziensisalone) and topdress nitrogen rates (0; 40; 80; 120 and 160 kg ha-1N), at the four-leaf stage, three years after the implementation of no-tillage. The experiment was arranged in a randomized block split plot design, with three replications. Common bean highest yields were achieved in succession to U. ruziziensisalone and intercropped with corn. The corn/U. ruziziensisintercrop provided both straw and seed production, allowing for quality no-tillage. Topdressed nitrogen influenced the common bean yield when in succession to corn alone, U. ruziziensisalone and corn/U. ruziziensisintercrop in no-tillage.