FT-Raman, FTIR and density functional theory studies of a hydrogen-bonded formamide: pyridine complex

Raman and IR experiments have been carried out on formamide (FA) and pyridine (Py) mixtures at different compositions. The appearance of a new Raman band at 996 cm(-1) (nu(1) region of Py), whose intensity depends on the FA concentration, is assigned to an FA: Py adduct and this result is in excellent agreement with those of other authors who employed noisy light-based coherent Raman scattering spectroscopy (I((2)) CARS). Another band at 1587 cm(-1) (nu(8) region of Py) has been observed for the first time by using Raman and IR spectroscopies. Its intensity shows the same dependence on the FA concentration and this fact allows us to also attribute it to an FA: Py adduct. The good relationship between the Raman and IR data demonstrates the potential of the vibrational spectroscopy for this kind of study. Owing to higher absolute Raman scattering cross section, the nu(1) region of Py has been chosen for the quantitative analysis and a stoichiometry of 1 : 1 FA: Py is reported. The experimental data are very well supported by the density functional theory (OFT) calculation, which was employed for the first time to the present system. Furthermore, the actual investigation shows an excellent agreement with those reported from computational calculations for similar systems. A comparison with our previous studies confirms that: the solvent dielectric constant determines the stoichiometry of a given Lewis acid-base adduct in the infinite dilution limit. Copyright (C) 2009 John Wiley & Sons, Ltd.

A Graphite-Polyurethane Composite Electrode for the Analysis of Furosemide

A graphite-polyurethane composite electrode has been used for the determination of furosemide, a antihypertensive drug, in pharmaceutical samples by anodic oxidation. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the electrooxidation process at +1.0 V vs. SCE over a wide pH range, with the result that no adsorption of analyte or products occurs, unlike at other carbon-based electrode materials. Quantification was carried out using cyclic voltammetry, differential pulse voltammetry, and square-wave voltammetry. Linear ranges were determined (up to 21 mu mol L-1 with cyclic voltammetry) as well as limits of detection (0.15 mu mol L-1 by differential pulse voltammetry). Four different types of commercial samples were successfully analyzed. Recovery tests were performed which agreed with those obtained by spectrophotometric evaluation. The advantages of this electrode material for repetitive analyzes, due to the fact that no electrode surface renewal is needed owing to the lack of adsorption, are highlighted.

Towards to the trans-bromination of 2-styrylpyridine with a palladacycle intermediary and structure analysis for trans-1,2-dibromo-2-styrylpyridine

The simple halogenation of alkynes in conventional organic reactions gives a blend of cis and trans isomers. It is proposed then, a synthesis of stereospecific halogenation of alkynes in trans position, using palladacycle as intermediaries. The recrystallization of the compound obtained by bromination of 2-Styrylpyridine, with cyclepalladium intermediary results in a single crystal, which is subjected to X-ray diffraction. The crystal packing is established through weak interactions of three types. The first one is of the type pi x pi interactions, from symmetry operation, between the centroids. The second one is of the type C-X center dot center dot center dot pi interactions. And the last type is an anomalous intermolecular interaction between halogens, C-X center dot center dot center dot X-C, with bond distances smaller than the sum of the van der Waals radii. The conformation on the C=C bond is trans and the dihedral angle between the aromatic rings is (with esd approximate) 18.1(3)degrees. (C) 2010 Elsevier B.V. All rights reserved.

Improved Road Design for Future Maintenance - Analysis of Road Barrier Repair Costs

The cost of a road construction over its service life is a function of the design, quality of construction, maintenance strategies and maintenance operations. Unfortunately, designers often neglect a very important aspect which is the possibility to perform future maintenance activities. The focus is mainly on other aspects such as investment costs, traffic safety, aesthetic appearance, regional development and environmental effects. This licentiate thesis is a part of a Ph.D. project entitled “Road Design for lower maintenance costs” that aims to examine how the life-cycle costs can be optimized by selection of appropriate geometrical designs for the roads and their components. The result is expected to give a basis for a new method used in the road planning and design process using life-cycle cost analysis with particular emphasis on road maintenance. The project started with a review of literature with the intention to study conditions causing increased needs for road maintenance, the efforts made by the road authorities to satisfy those needs and the improvement potential by consideration of maintenance aspects during planning and design. An investigation was carried out to identify the problems which obstruct due consideration of maintenance aspects during the road planning and design process. This investigation focused mainly on the road planning and design process at the Swedish Road Administration. However, the road planning and design process in Denmark, Finland and Norway were also roughly evaluated to gain a broader knowledge about the research subject. The investigation was carried out in two phases: data collection and data analysis. Data was collected by semi-structured interviews with expert actors involved in planning, design and maintenance and by a review of design-related documents. Data analyses were carried out using a method called “Change Analysis”. This investigation revealed a complex combination of problems which result in inadequate consideration of maintenance aspects. Several urgent needs for changes to eliminate these problems were identified. Another study was carried out to develop a model for calculation of the repair costs for damages of different road barrier types and to analyse how factors such as road type, speed limits, barrier types, barrier placement, type of road section, alignment and seasonal effects affect the barrier damages and the associated repair costs. This study was carried out using a method called the “Case Study Research Method”. Data was collected from 1087 barrier repairs in two regional offices of the Swedish Road Administration, the Central Region and the Western Region. A table was established for both regions containing the repair cost per vehicle kilometre for different combinations of barrier types, road types and speed limits. This table can be used by the designers in the calculation of the life-cycle costs for different road barrier types.

RWater – A Cyber Enabled Tool For Hydrologic Modeling And Analysis

Existing distributed hydrologic models are complex and computationally demanding for using as a rapid-forecasting policy-decision tool, or even as a class-room educational tool. In addition, platform dependence, specific input/output data structures and non-dynamic data-interaction with pluggable software components inside the existing proprietary frameworks make these models restrictive only to the specialized user groups. RWater is a web-based hydrologic analysis and modeling framework that utilizes the commonly used R software within the HUBzero cyber infrastructure of Purdue University. RWater is designed as an integrated framework for distributed hydrologic simulation, along with subsequent parameter optimization and visualization schemes. RWater provides platform independent web-based interface, flexible data integration capacity, grid-based simulations, and user-extensibility. RWater uses RStudio to simulate hydrologic processes on raster based data obtained through conventional GIS pre-processing. The program integrates Shuffled Complex Evolution (SCE) algorithm for parameter optimization. Moreover, RWater enables users to produce different descriptive statistics and visualization of the outputs at different temporal resolutions. The applicability of RWater will be demonstrated by application on two watersheds in Indiana for multiple rainfall events.

Economic landscapes, what are they? an application to the Brazilian economy and to the sugar cane complex

In assessing the economic impact of a sector or group of sectors on a single or multiregional economy, input-output analysis has proven to be a popular method. . However, there has a problem in displaying all the information that can be obtained from this analytical approach. In this paper, we have tried to set new directions in the use of input-output analysis by presenting an improved way of looking at the economic landscapes. While this is not a new concept, a new meaning is explored in this paper; essentially, it will now be possible to visualize, in a simple picture, all the relations in the economy as well as being able to view how one sector is related to the other sectors/regions in the economy. These relations can be measured in terms of structural changes, production, value added, employment, imports, etc. While all the possibilities cannot be explored in this paper, the basic idea is given here and the smart reader can uncover all the various possibilities. To illustrate the power of analysis provided by the economic landscapes, an application is made to the sugar cane complex using an interregional inputoutput system for the Brazilian economy, constructed for 2 regions (Northeast and Rest of Brazil), for the years of 1985, 1992, and 1995.

Corporate governance development in privately held family businesses: a multiple case analysis

The objective of this study is to better understand and illustrate the process and the motivations for corporate governance implementation in Brazilian privately held family businesses. Three case companies were analyzed through an adapted developmental framework to illustrate the progression in corporate governance in response to changes in the ownership, investment and management dimensions over time. In this development, causal relationships between corporate governance and the three other framework dimensions were identified. It was found that the analyzed companies´ corporate governance implementation was motivated by the need to curb agency costs, whereas a cornerstone in this development was the first generational change. Only after the family businesses have reached the necessary maturity on all three dimensions, corporate governance practices were implemented. Put simply, the analyzed case companies developed formal systems as they grew more complex. This study complements the academic discussions on corporate governance in family businesses by offering Brazilian evidence on its underlying motivations and sequential implementation over time.

Exploring different social media users from the millennials’ generation: a cross-cultural behavioral analysis of brazilian users of Facebook and chinese users of RenRen

With the increasing importance of digital communication and its distinct characteristics, marketing tools and strategies adopted by companies have changed dramatically. Among the many digital marketing tools and new media channels available for marketers, the phenomenon known as social media is one of the most complex and enigmatic. It has a range that still is quite unexplored and deeply transforms the present view on the promotion mix (Mangold & Faulds, 2009). Conversations among users on social media directly affect their perceptions on products, services and brands. But more than that, a wide range of other subjects can also become topics of conversations on social media. Hit songs, sporting events, celebrity news and even natural disasters and politics are topics that often become viral on the web. Thus, companies must grasp that, and in order to become more interesting and relevant, they must take part in these conversations inserting their brands in these online dynamic dialogues. This paper focuses on how these social interactions are manifested in the web in to two distinct cultures, Brazil and China. By understanding the similarities and differences of these cultures, this study helps firms to better adjust its marketing efforts across regions, targeting and positioning themselves, not only geographically and culturally, but also across different web platforms (Facebook and RenRen). By examining how companies should focus their efforts according to each segment in social media, firms can also maximize its results in communication and mitigate risks. The findings suggest that differences in cultural dimensions in these two countries directly affect their virtual social networking behavior in many dimensions (Identity, Presence, Relationships, Reputation, Groups, Conversations and Sharing). Accordingly, marketing efforts must be tailored to each comportment and expectations.

Strategic options development and analysis: the case of the brazilian railways

Judging by their success in Europe, Asia and North America, passenger and cargo railways are appreciated as the key to infrastructural development in Brazil. The issues are complex and steeped in uncertainty, as well as political and economic agendas, and a wide array of intersecting issues such as business and unionized interests, agricultural and industrial geographical spreads, as well as the emergence of alternative power sources. Not only are the issues systemic, but railway development itself always comes as a physical network structure. The situation under consideration, in other words, is systemic from both the soft and hard systems point of view, thus promising a rich context for systems studies. As an initial attempt in understanding the situation at hand, the research reported here applied the problem structuring approach known as Strategic Options Development and Analysis (SODA) in order to map and analyze issues facing the Brazilian railways. Strategic options for the future development of the railways were identified and analyzed, and ways forward for future research are proposed. In addition, the report serves as an initial knowledge base that can guide future systemic planning studies in the industry.

Why banks want to be complex

We investigate whether and how bank complexity affects performance and systemic risk. We base the analysis on a complexity measure that captures diversification and diversity, controlling for size and other bank characteristics. We find that more complex banks exhibit a higher profitability, lower risk, and higher market share. Moreover, we show an inversely U-shaped relation between bank complexity and banks’ sensitivity to systemic shocks. The evidence challenges the view that higher bank complexity is per se bad and is consistent with theoretical models that show that diversity in the banking system is critical for financial stability.

Applying supply chain management models in the banking industry: a brazilian case analysis

The study presents the results and recommendations deriving from the application of two supply chain management analysis models as proposed by the Supply Chain Council (SCOR, version 10.0) and by Lambert (1997, Framework for Supply Chain Management) on the logistics of cash transfers in Brazil. Cash transfers consist of the transportation of notes to and from each node of the complex network formed by the bank branches, ATMs, armored transportation providers, the government custodian, Brazilian Central Bank and financial institutions. Although the logistic to sustain these operations is so wide-ranged (country-size), complex and subject to a lot of financial regulations and security procedures, it has been detected that it was probably not fully integrated. Through the use of a primary and a secondary data research and analysis, using the above mentioned models, the study ends up with propositions to strongly improve the operations efficiency

Analysis an development of a prototype based on media wiki and semantic media wiki integrated with a design modeling that allows modeling of organizations based on demo

In a world where organizations are ever more complex the need for the knowledge of the organizational self is a growing necessity. The DEMO methodology sets a goal in achieving the specification of the organizational self capturing the essence of the organization in way independent of its implementation and also coherent, consistent, complete, modular and objective. But having such organization self notion is of little meaning if this notion is not shared by the organization actors. To achieve this goal in a society that has grown attached to technology and where time is of utmost importance, using a tool such as a semantic Wikipedia may be the perfect way of making the information accessible. However, to establish DEMO methodology in such platform there is a need to create bridges between its modeling components and semantic Wikipedia. It’s in that aspect that our thesis focuses, trying to establish and implement, using a study case, the principles of a way of transforming the DEMO methodology diagrams in comprehensive pages on semantic Wikipedia but keeping them as abstract as possible to allow expansibility and generalization to all diagrams without losing any valuable information so that, if that is the wish, those diagrams may be recreated from the semantic pages and make this process a full cycle.

Reduction capability of soil humic substances from the Rio Negro basin, Brazil, towards Hg(II) studied by a multimethod approach and principal component analysis (PCA)

This paper characterizes humic substances (HS) extracted from soil samples collected in the Rio Negro basin in the state of Amazonas, Brazil, particularly investigating their reduction capabilities towards Hg(II) in order to elucidate potential mercury cycling/volatilization in this environment. For this reason, a multimethod approach was used, consisting of both instrumental methods (elemental analysis, EPR, solid-state NMR, FIA combined with cold-vapor AAS of Hg(0)) and statistical methods such as principal component analysis (PCA) and a central composite factorial planning method. The HS under study were divided into groups, complexing and reducing ones, owing to different distribution of their functionalities. The main functionalities (cor)related with reduction of Hg(II) were phenolic, carboxylic and amide groups, while the groups related with complexation of Hg(II) were ethers, hydroxyls, aldehydes and ketones. The HS extracted from floodable regions of the Rio Negro basin presented a greater capacity to retain (to complex, to adsorb physically and/or chemically) Hg(II), while nonfloodable regions showed a greater capacity to reduce Hg(II), indicating that HS extracted from different types of regions contribute in different ways to the biogeochemical mercury cycle in the basin of the mid-Rio Negro, AM, Brazil. (c) 2007 Published by Elsevier B.V.

Development and pharmacological evaluation of ropivacaine-2-hydroxypropyl-beta-cyclodextrin inclusion complex

Ropivacaine (RVC) is an enantiomerically pure local anesthetic (LA) largely used in surgical procedures, which presents physico-chemical and therapeutic properties similar to those of bupivacaine (BPV), but associated to less systemic toxicity This study focuses on the development and pharmacological evaluation of a RVC in 2-hydroxypropyl-beta-cyclodextrin (HP-P-CD) inclusion complex. Phase-solubility diagrams allowed the determination of the association constant between RVC and HP-beta-CD (9.46 M-1) and showed an increase on RVC solubility upon complexation. Release kinetics revealed a decrease on RVC release rate and reduced hemolytic effects after complexation. (onset at 3.7 mM and 11.2 mM for RVC and RVCHP-beta-CD, respectively) were observed. Differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and X-ray analysis (X-ray) showed the formation and the morphology of the complex. Nuclear magnetic resonance (NMR) and job-plot experiments afforded data regarding inclusion complex stoichiometry (1:1) and topology. Sciatic nerve blockade studies showed that RVCHP-beta-CD was able to reduce the latency without increasing the duration of motor blockade, but prolonging the duration and intensity of the sensory blockade (p < 0.001) induced by the LA in mice. These results identify the RVCHP-beta-CD complex as an effective novel approach to enhance the pharmacological effects of RVC, presenting it as a promising new anesthetic formulation. (c) 2007 Elsevier B.V All rights reserved.

Crystal structure of Bn IV in complex with myristic acid: A Lys49 myotoxic phospholipase A(2) from Bothrops neuwiedi venom

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)