Thermodynamic Characterization of Humic Acid-surfactant Interaction: New Insights into the Characteristics and Structure of Humic Acids

ABSTRACT Humic acids (HA) are a component of humic substances (HS), which are found in nearly all soils, sediments, and waters. They play a key role in many, if not most, chemical and physical properties in their environment. Despite the importance of HA, their high complexity makes them a poorly understood system. Therefore, understanding the physicochemical properties and interactions of HA is crucial for determining their fundamental role and obtaining structural details. Cationic surfactants are known to interact electrostatically and hydrophobically with HA. Because they are a very well-known and characterized system, they offer a good choice as molecular probes for studying HA. The objective of this study was to evaluate the interaction between cationic surfactants and HA through isothermal titration calorimetry in a thermodynamic manner, aiming to obtain information about the basic structure of HA, the nature of this interaction, and if HA from different origins show different basic structures. Contrary to what the supramolecular model asserts, HA structure is not loosely held, though it may separate depending on the conditions the HA are subjected to in their milieu. It did not show any division or conformational change when interacting with surfactants. The basic structure of the HA remains virtually the same regardless of the different sources and compositions of these HA.

Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

Modeling of the Fluid-Structure Interaction in Inelastic Piping Systems

In many engineering applications, compliant piping systems conveying liquids are subjected to inelastic deformations due to severe pressure surges such as plastic tubes in modern water supply transmission lines and metallic pipings in nuclear power plants. In these cases the design of such systems may require an adequate modeling of the interactions between the fluid dynamics and the inelastic structural pipe motions. The reliability of the prediction of fluid-pipe behavior depends mainly on the adequacy of the constitutive equations employed in the analysis. In this paper it is proposed a systematic and general approach to consistently incorporate different kinds of inelastic behaviors of the pipe material in a fluid-structure interaction analysis. The main feature of the constitutive equations considered in this work is that a very simple numerical technique can be used for solving the coupled equations describing the dynamics of the fluid and pipe wall. Numerical examples concerning the analysis of polyethylene and stainless steel pipe networks are presented to illustrate the versatility of the proposed approach.

Interaction between information systems and work in the Brazilian banking sector

This article presents the results of a research to understand the conditions of interaction between work and three specific information systems (ISs) used in the Brazilian banking sector. We sought to understand how systems are redesigned in work practices, and how work is modified by the insertion of new systems. Data gathering included 46 semi-structured interviews, together with an analysis of system-related documents. We tried to identify what is behind the practices that modify the ISs and work. The data analysis revealed an operating structure: a combination of different practices ensuring that the interaction between agents and systems will take place. We discovered a structure of reciprocal conversion caused by the increased technical skills of the agent and the humanization of the systems. It is through ongoing adjustment between work and ISs that technology is tailored to the context and people become more prepared to handle with technology.

Composition and structure of the fig wasp community in Amazonia

An understanding of the complex ecological interaction between fig wasps and their host plants in Amazonia requires previous knowledge of their distribution and diversity. The objective of this study was to describe the composition and structure of the wasp community associated with four species of Ficus in the municipal area of Manaus, Amazonas, Brazil. A total of 600 syconia from four species were collected. The study species were: Ficus obtusifolia Kunth; Ficus citrifolia Mill; F. americana subspecies guianensis Desv. form mathewsii; and F. americana subspecies guianensis Desv. form parkeriana. Statistical analyses were used to examine the relationship between fig wasp diversity and syconium diameter, and the effect of non-pollinating wasps on numbers of pollinators and seeds. Forty three species of fig wasp were identified, distributed across seven genera (Pegoscapus, Idarnes, Aepocerus, Physothorax, Anidarnes, Heterandrium , Eurytoma). Idarnes (carme group) was the wasps genus non-pollinator with greatest number of individuals with the greatest number of infested syconia (7409 wasps in 376 syconia). Analysing non-pollinating wasp diversity in relation to fig diameter, a significant difference was observed between the four fig species. Ficus citrifolia and F. americana subspecies guianensis form mathewsii had the smallest diameter but the greatest diversity of fig wasp. Ficus obtusifolia was the only species in which the non-pollinating wasps had a significant negative effect on the number of Pegoscapus sp. and on seed production.

Interaction of Diocleinae Lectins with Glycoproteins Based in Surface Plasmon Resonance

Interaction of glucose/mannose-binding lectins in solution with immobilized glycoproteins was followed in real time using surface plasmon resonance technology. The lectins which share many biochemical and structural features could be clearly differentiated in terms of their specificity for complex glycoconjugates. The most prominent interaction of the lectins with PHA-E comparing with soybean agglutinin, both glycoproteins exhibiting high mannose oligosaccharides, suggests that the whole structure of the glycoproteins themselves, may interfere in affinity. These findings also support the hypothesis that minor amino acid replacements in the primary sequence of the lectins might be responsible for their divergence in fine specificity and biological activities. This is the first report using surface plasmon resonance technology that evidences differences of Diocleinae lectins in respect their fine glycan-specificity.

Structure-based drug design studies of the interactions ofent-kaurane diterpenes derived from Wedelia paludosa with the Plasmodium falciparumsarco/endoplasmic reticulum Ca2+-ATPase PfATP6

Malaria is responsible for more deaths around the world than any other parasitic disease. Due to the emergence of strains that are resistant to the current chemotherapeutic antimalarial arsenal, the search for new antimalarial drugs remains urgent though hampered by a lack of knowledge regarding the molecular mechanisms of artemisinin resistance. Semisynthetic compounds derived from diterpenes from the medicinal plant Wedelia paludosawere tested in silico against the Plasmodium falciparumCa2+-ATPase, PfATP6. This protein was constructed by comparative modelling using the three-dimensional structure of a homologous protein, 1IWO, as a scaffold. Compound 21 showed the best docking scores, indicating a better interaction with PfATP6 than that of thapsigargin, the natural inhibitor. Inhibition of PfATP6 by diterpene compounds could promote a change in calcium homeostasis, leading to parasite death. These data suggest PfATP6 as a potential target for the antimalarial ent-kaurane diterpenes.

Bubble-Bubble Interaction in Horizontal Two-Phase Slug Flow

Modelling of the slug structure requires a new effort on fundamental research. To clarify some aspects of the horizontal slug flow, an experimental study of the behaviour of two isolated bubbles in a single-phase liquid flow was performed. This procedure was adopted to avoid the overlap of different phenomena induced by a train of long bubbles. The experimental facility consists of a 90-m horizontal PVC pipe with internal diameter of 0,053 m. The behaviour of two single air bubbles travelling in a water flow was studied. Focus was given on the influence of the distance between the bubbles on the velocity of the second bubble. This study allows the understanding of the mechanism of overtaking that takes place right after the slug formation and that precedes the coalescence of bubbles in a slug flow. The results show that bubbles placed behind a liquid slug smaller than a critical value move faster than the leading one. Otherwise, they move slower than the leading one.

A study of the interaction between Helicobacter pylori and components of the human fibrinolytic system

The interaction of plasminogen, tissue plasminogen activator (t-PA) and urokinase with a clinical strain of Helicobacter pylori was studied. Plasminogen bound to the surface of H. pylori cells in a concentration-dependent manner and could be activated to the enzymatic form, plasmin, by t-PA. Affinity chromatography assays revealed a plasminogen-binding protein of 58.9 kDa in water extracts of surface proteins. Surface-associated plasmin activity, detected with the chromogenic substrate CBS 00.65, was observed only when plasminogen and an exogenous activator were added to the cell suspension. The two physiologic plasminogen activators, t-PA and urokinase, were also shown to bind to and remain active on the surface of bacterial cells. epsilon-Aminocaproic acid caused partial inhibition of t-PA binding, suggesting that the kringle 2 structure of this activator is involved in the interaction with surface receptors. The activation of plasminogen by t-PA, but not urokinase, strongly depended on the presence of cells and a 25-fold enhancer effect on the initial velocity of activation by t-PA compared to urokinase was established. Furthermore, a relationship between cell concentration and the initial velocity of activation was demonstrated. These findings support the concept that plasminogen activation by t-PA on the bacterial surface is a surface-dependent reaction which offers catalytic advantages.

Effect of race, genetic population structure, and genetic models in two-locus association studies: clustering of functional renin-angiotensin system gene variants in hypertension association studies

Previous genetic association studies have overlooked the potential for biased results when analyzing different population structures in ethnically diverse populations. The purpose of the present study was to quantify this bias in two-locus association studies conducted on an admixtured urban population. We studied the genetic structure distribution of angiotensin-converting enzyme insertion/deletion (ACE I/D) and angiotensinogen methionine/threonine (M/T) polymorphisms in 382 subjects from three subgroups in a highly admixtured urban population. Group I included 150 white subjects; group II, 142 mulatto subjects, and group III, 90 black subjects. We conducted sample size simulation studies using these data in different genetic models of gene action and interaction and used genetic distance calculation algorithms to help determine the population structure for the studied loci. Our results showed a statistically different population structure distribution of both ACE I/D (P = 0.02, OR = 1.56, 95% CI = 1.05-2.33 for the D allele, white versus black subgroup) and angiotensinogen M/T polymorphism (P = 0.007, OR = 1.71, 95% CI = 1.14-2.58 for the T allele, white versus black subgroup). Different sample sizes are predicted to be determinant of the power to detect a given genotypic association with a particular phenotype when conducting two-locus association studies in admixtured populations. In addition, the postulated genetic model is also a major determinant of the power to detect any association in a given sample size. The present simulation study helped to demonstrate the complex interrelation among ethnicity, power of the association, and the postulated genetic model of action of a particular allele in the context of clustering studies. This information is essential for the correct planning and interpretation of future association studies conducted on this population.

Blastocyst-endometrium interaction: intertwining a cytokine network

The successful implantation of the blastocyst depends on adequate interactions between the embryo and the uterus. The development of the embryo begins with the fertilized ovum, a single totipotent cell which undergoes mitosis and gives rise to a multicellular structure named blastocyst. At the same time, increasing concentrations of ovarian steroid hormones initiate a complex signaling cascade that stimulates the differentiation of endometrial stromal cells to decidual cells, preparing the uterus to lodge the embryo. Studies in humans and in other mammals have shown that cytokines and growth factors are produced by the pre-implantation embryo and cells of the reproductive tract; however, the interactions between these factors that converge for successful implantation are not well understood. This review focuses on the actions of interleukin-1, leukemia inhibitory factor, epidermal growth factor, heparin-binding epidermal growth factor, and vascular endothelial growth factor, and on the network of their interactions leading to early embryo development, peri-implantatory endometrial changes, embryo implantation and trophoblast differentiation. We also propose therapeutical approaches based on current knowledge on cytokine interactions.