Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M(13). First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first- principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M(13) structures. Several new lower energy configurations were identified, e. g., Pd(13), W(13), Pt(13), etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au(13), we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.

Multi-objective analysis of impacts of distributed generation placement on the operational characteristics of networks for distribution system planning

Recent advances in energy technology generation and new directions in electricity regulation have made distributed generation (DG) more widespread, with consequent significant impacts on the operational characteristics of distribution networks. For this reason, new methods for identifying such impacts are needed, together with research and development of new tools and resources to maintain and facilitate continued expansion towards DG. This paper presents a study aimed at determining appropriate DG sites for distribution systems. The main considerations which determine DG sites are also presented, together with an account of the advantages gained from correct DG placement. The paper intends to define some quantitative and qualitative parameters evaluated by Digsilent (R), GARP3 (R) and DSA-GD software. A multi-objective approach based on the Bellman-Zadeh algorithm and fuzzy logic is used to determine appropriate DG sites. The study also aims to find acceptable DG locations both for distribution system feeders, as well as for nodes inside a given feeder. (C) 2010 Elsevier Ltd. All rights reserved.

Friction loss correction in flowing well discharge tests

Artesian confined aquifers do not need pumping energy, and water from the aquifer flows naturally at the wellhead. This study proposes correcting the method for analyzing flowing well tests presented by Jacob and Lohman (1952) by considering the head losses due to friction in the well casing. The application of the proposed correction allowed the determination of a transmissivity (T = 411 m(2)/d) and storage coefficient (S = 3 x 10(-4)) which appear to be representative for the confined Guarani Aquifer in the study area. Ignoring the correction due to head losses in the well casing, the error in transmissivity evaluation is about 18%. For the storage coefficient the error is of 5 orders of magnitude, resulting in physically unacceptable value. The effect of the proposed correction on the calculated radius of the cone of depression and corresponding well interference is also discussed.

Assessment of energy efficiency in electric storage water heaters

Nowadays there are several ways of supplying hot water for showers in residential buildings. One of them is the use of electric storage water heaters (boilers). This equipment raises the water temperature in a reservoir (tank) using the heat generated by an electric resistance. The behavior of this equipment in Brazil is still a research object and there is not a standard in the country to regulate its efficiency. In this context, an experimental program was conducted aiming to collect power consumption data to evaluate its performance. The boilers underwent an operation cycle to simulate a usage condition aiming to collect parameters for calculating the efficiency. This 1-day cycle was composed of the following phases: hot water withdrawal, reheating and standby heat loss. The methods allowed the identification of different parameters concerning the boilers work, such as: standby heat loss in 24 h, hot water withdrawal rate, reheating time and energy efficiency. The average energy efficiency obtained was of 75%. The lowest efficiency was of 62% for boiler 2 and the highest was of 85% for boiler 9. (C) 2008 Elsevier B.V. All rights reserved.

Interface excess and polymorphic stability of nanosized zirconia-magnesia

Controlling the phase stability of ZrO2 nanoparticles is of major importance in the development of new ZrO2-based nanotechnologies. Because of the fact that in nanoparticles the surface accounts for a larger fraction of the total atoms, the relative phase stability can be controlled throughout the surface composition, which can be toned by surface excess of one of the components of the system., The objective of this work is to delineate a relationship between surface excess (or solid solution) of MgO relative to ZrO2 and the polymorphic stability of (ZrO2)(1-x) - (MgO), nanopowders, where 0.0 <= x <= 0.6. The nanopowders were prepared by a liquid precursor method at 500 degrees C and characterized by N-2 adsorption (BET), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), and Raman spectroscopy. For pure ZrO2 samples, both tetragonal and monoclinic polymorphs were detected, as expected considering the literature. For MgO molar fractions varying from 0.05 to 0.10, extensive solid solution could not be detected, and a ZrO2 surface energy reduction, caused by Mg surface excess detected by XPS, promoted tetragonal polymorph thermodynamic stabilization with relation to monoclinic. For MgO molar fractions higher than 0.10 and up to 0.40, Mg solid solution could be detected and induced cubic phase stabilization. MgO periclase was observed only at x = 0.6. A discussion based on the relationship between the surface excess, surface energy, and polymorph stability is presented.

Improved moisture and hydrocarbons barrier of epoxy resin-based coating

To improve the surface characteristics of epoxy resin coatings, a treatment by fluorine-containing plasma was used to develop a coating with low surface free energy and improved chemical resistance. Through the coating analysis it was possible to verify information about the CF(n) bond formation and the fluorination depth. The best plasma process parameters presented the best fluorination depth, 90 nm, and fluorine concentration was nearly 30%. The improvement in contact angle of water was 50% and of raw petroleum was 130%. Salt spray test proves that the coating fluorination decreases the chance of substrate corrosion.

Synthesis and evaluation of sesquiterpene lactone inhibitors of phospholipase A(2) from Bothrops jararacussu

Several sesquiterpene lactone were synthesized and their inhibitive activities on phospholipase A(2) (PLA(2)) from Bothrops jararacussu venom were evaluated. Compounds Lac01 and Lac02 were efficient against PLA(2) edema-inducing, enzymatic and myotoxic activities and it reduces around 85% of myotoxicity and around 70% of edema-inducing activity. Lac05-Lac08 presented lower efficiency in inhibiting the biological activities studied and reduce the myotoxic and edema-inducing activities around only 15%. The enzymatic activity was significantly reduced. The values of inhibition constants (K(1)) for Lac01 and Lac02 were approximately 740 mu M, and for compounds Lac05-Lac08 the inhibition constants were approximately 7.622-9.240 mu M. The enzymatic kinetic studies show that the sesquiterpene lactones inhibit PLA(2) in a non-competitive manner. Some aspects of the structure-activity relationships (topologic, molecular and electronic parameters) were obtained using ab initio quantum calculations and analyzed by chemometric methods (HCA and PCA). The quantum chemistry calculations show that compounds with a higher capacity of inhibiting PLA(2) (Lac01-Lac04) present lower values of highest occupied molecular orbital (HOMO) energy and molecular volume (VOL) and bigger values of hydrophobicity (LogP). These results indicate some topologic aspects of the binding site of sesquiterpene lactone derivatives and PLA(2). (C) 2010 Elsevier Ltd. All rights reserved.

Long-term nutritional assessment of patients with severe short bowel syndrome managed with home enteral nutrition and oral intake

Background: Parenteral nutrition (PN) is used to control the nutritional state after severe intestinal resections. Whenever possible, enteral nutrition (EN) is used to promote intestinal rehabilitation and reduce PN dependency. Our aim is to verify whether EN + oral intake (01) in severe short bowel syndrome (SBS) surgical adult patients can maintain adequate nutritional status in the long term. Methods: This longitudinal retrospective study included 10 patients followed for 7 post-operative years. Body mass index (BMI), percentage of involuntary loss of usual body weight (UWL), free fat mass (FFM), and fat mass (FM) composition assessed by bioelectric impedance, and laboratory tests were evaluated at 6, 12, 24, 36, 48, 60, 72, and 84 months after surgery. Energy and protein offered in HPN and at long term by HEN+ oral intake (01), was evaluated at the same periods. The statistical model of generalized estimating equations with p <0,05 was used. Results: With long term EN + 01 there was a progressive increase in the UWL, a decrease in BMI, FFM, and FM (p < 0,05). PN weaning was possible in eight patients. Infection due to central venous catheter (CVC) contamination was the most common complication (1.2 episodes CVC/patient/year). There was an increase in energy and protein intake supply provided by HEN+OI (p <0.05). All patients survived for at least 2 years, seven for 5 years and six for 7 years of follow-up. Conclusions: In the long term SBS surgical adult patients fed with HEN+OI couldn`t maintain adequate nutritional status with loss of FM and FFM. (Nutr Hosp. 2011;26:834-842) DOI:10.3305/nh.2011.26.4.5153