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.

Avaliação do efeito radioprotetor do selenito de sódio no processo de reparação tecidual em ratos

OBJETIVO: Avaliar a ação radioprotetora do selenito de sódio no processo de reparação tecidual. MATERIAIS E MÉTODOS: Ratos Wistar foram submetidos a procedimento cirúrgico para a realização de ferida na região dorsal. Os animais foram divididos em quatro grupos experimentais: controle, selênio, irradiado e selênio-irradiado. Os grupos selênio e selênio-irradiado receberam 2,0 mg/kg de selenito de sódio, 48 horas após a cirurgia. Os grupos irradiado e selênio-irradiado foram submetidos à irradiação em dose única de 6 Gy, administrada somente nas bordas das feridas. Após 4, 7, 13 e 21 dias do procedimento cirúrgico, os animais foram sacrificados e avaliados por meio de análise morfológica, histoquímica e birrefringência do tecido. RESULTADOS: O aspecto estrutural e morfológico, assim como a qualidade do tecido e sua maturação através da quantidade e disposição dos feixes de fibras colágenas, juntamente com o seu grau de orientação macromolecular, permitiu observar a presença de intenso retardo provocado pela irradiação, bem como o efeito radioprotetor do selenito de sódio no processo de reparação. CONCLUSÃO: Dentro das condições experimentais utilizadas, o selenito de sódio apresentou-se como radioprotetor eficaz, visto que o processo de reparação no grupo selênio-irradiado comportou-se, histologicamente, semelhante ao grupo controle.

A técnica de dispersão de taylor para estudos de difusão em líquidos e suas aplicações

This paper describes the theoretical basis and the experimental requirements for the application of the Taylor dispersion technique for measurements of diffusion coefficients in liquids, emphasizing its simplicity and accuracy in comparison to other usual techniques. Some examples are discussed describing the use of this methodology on studies of solute-solvent interactions, solute aggregation, solute partitioning into macromolecular systems and on the assessment of nanoparticles sizes.

Hidrólise seletiva de carboxiamidas de resíduos de asparagina e glutamina em colágeno: preparação e caracterização de matrizes aniônicas para uso como biomateriais

This work describes the selective hydrolysis of carboxyamide groups of asparagine and glutamine of collagen matrices for the preparation of negatively charged collagen biomaterials. The reaction was performed in the presence of chloride and sulfate salts of alkaline and alkaline earth metals in aqueous dimethylsulfoxide solution and, selectively hydrolysis of carboxyamide groups of collagen matrices was promoted without cleavage of the peptide bond. The result is a new collagen material with controlled increase in negative charge content. Although triple helix secondary structure of tropocollagen was preserved, significative changes in thermal stabilities were observed in association with a new pattern of tropocollagen macromolecular association, particularly in respect microfibril assembly, thus providing at physiological pH a new type of collagen structure for biomaterial preparation, characterized by different charge and structural contents .

Sistemas transportadores de drogas

Drug delivery system controls the distribution of drugs for optimal therapeutic efficacy. The complex of higly active drugs with macromolecular carriers seems to offer a promising way to optimize their delivery. Dendrimers can be used as drug delivery system and this paper addresses the effectivenes of the approach. The host-guest system improves the solubility of hydrazides and mesoionic 1,3,4-thiadiazolium-2-aminide compounds.

Aplicação da espectroscopia de ressonância magnética nuclear para estudos de difusão molecular em líquidos: a técnica DOSY

Diffusion coefficients provide uniquely detailed and easily interpreted information on molecular organization and phase structure. They are quite sensitive to structural changes, and to binding and association phenomena, in particular for liquid colloidal or macromolecular systems. This paper describes the principles of diffusion measurements in liquids by pulsed magnetic field gradient spin-echo (PFG-SE) NMR spectroscopy. The important PFG-SE technique known as DOSY is presented and discussed. This is a noninvasive technique that can provide individual multicomponent translational diffusion coefficients with good precision in a few minutes, without the need for radioactive isotopic labelling.

SSPBE: um programa para solução numérica da equação de Poisson-Boltzmann em simetria esférica com modelo de adsorção

A Fortran77 program, SSPBE, designed to solve the spherically symmetric Poisson-Boltzmann equation using cell model for ionic macromolecular aggregates or macroions is presented. The program includes an adsorption model for ions at the aggregate surface. The working algorithm solves the Poisson-Boltzmann equation in the integral representation using the Picard iteration method. Input parameters are introduced via an ASCII file, sspbe.txt. Output files yield the radial distances versus mean field potentials and average molar ion concentrations, the molar concentration of ions at the cell boundary, the self-consistent degree of ion adsorption from the surface and other related data. Ion binding to ionic, zwitterionic and reverse micelles are presented as representative examples of the applications of the SSPBE program.

Câncer e agentes antineoplásicos ciclo-celular específicos e ciclo-celular não específicos que interagem com o DNA: uma introdução

The chemotherapy agents against cancer may be classified as "cell cycle-specific" or "cell cycle-nonspecific". Nevertheless, several of them have their biological activity related to any kind of action on DNA such as: antimetabolic agents (DNA synthesis inhibition), inherently reactive agents (DNA alkylating electrophilic traps for macromolecular nucleophiles from DNA through inter-strand cross-linking - ISC - alkylation) and intercalating agents (drug-DNA interactions inherent to the binding made due to the agent penetration in to the minor groove of the double helix). The earliest and perhaps most extensively studied and most heavily employed clinical anticancer agents in use today are the DNA inter-strand cross-linking agents.

Peptídeos cíclicos de biomassa vegetal: características, diversidade, biossíntese e atividades biológicas

Natural peptides are outstanding as the most promising macromolecules in the search for new drugs, especially those of cyclic nature. The higher plants revealed a very peculiar composition of their cyclic peptides, which distinguish themselves by a "head-to-tail" cyclization. It is possible to define two groups of cyclic peptides from plant biomass. Those called in this review as Eucyclopeptides formed by 2-12 amino acid, and Cyclotides considered as circular polypeptides, composed of 29-37 amino acid that retain three disulfides bridges in an arrangement known as cyclic cystine knot. Searching for plant peptides should form into a subject for scientific research in the forefront of great importance for bioprospecting natural products macromolecular.

Relevância de compostos de baixa massa molar produzidos por fungos e envolvidos na biodegradação da madeira

Over the last decade, evidences have been shown that the wood biodegradation by fungi is not only a result of the action of their enzymatic machinery but also of various low molecular weight non-enzymatic compounds, especially in fungi that promote brown and white decay, which in nature are the major wood decaying microorganisms. The present review focuses on the recent theories involving these low molecular weight compounds that act direct or synergistically with lignocellulolytic enzymes to attack the wood main macromolecular constituents, their relevance as potential degradative systems, in the overall wood biodegradation, and also outlines their potential biotechnological applications.

Polímeros com capacidade de reconhecimento molecular no controlo da libertação de fármacos. Parte 1: síntese e caracterização

Molecularly imprinted polymers (MIPs) consist of synthetic macromolecular matrix, obtained through molecular imprinting-based methods that show ability to selectively recognize important biological molecules and its application in the drug delivery field is under development. In the present review the main aspects related to the synthesis and characterization of MIPs are studied. The fundamental variables participating in the synthesis process, such as template molecule, functional monomers, cross-linking agents, solvents and imprinting approaches are discussed. Moreover, the main available methods for MIPs chemical and morphological characterization are presented and the importance of the obtained information is discussed.

INTERAÇÕES FÁRMACO-RECEPTOR: APLICAÇÕES DE TÉCNICAS COMPUTACIONAIS EM AULA PRÁTICA SOBRE A EVOLUÇÃO DOS INIBIDORES DA ENZIMA CONVERSORA DE ANGIOTENSINA

Teaching classes and events regarding the molecular aspects of drug-receptor interactions is not an easy task. The ligand stereochemistry and the spatial arrangement of the macromolecular targets highly increase the complexity of the process. In this context, the use of alternative and more playful approaches could allow students to gain a more thorough understanding of this important topic in medicinal chemistry. Herein, we describe a practical teaching approach that uses computational strategies as a tool for drug-receptor interaction studies performed for angiotencsin converting enzyme inhibitors (ACEi). Firstly, the students learn how to find the crystallographic structure (enzyme-ligand complex). Then, they proceed to the treatment of crude crystallographic data. Thereafter, they learn how to analyze the positioning of the drug on the active site of the enzyme, looking for regions related to the molecular recognition. At the end of the study, students can summarize the molecular requirements for the interaction and the structure-activity relationships of the studied drugs.

Is hypoxia a stressor to American bullfrog tadpoles?

The aim of this study was to evaluate alterations to the physiological profile of cortisol in pro-metamorphose phase tadpoles of Lithobates catesbeianus exposed to hypoxia stressor in a capture experiment and in a crowding experiment. The capture study was performed by the treatments: stress due to individual capture with a hand net, stress due to batch capture with a hand net and stress due to capture by emptying. Three simultaneous replicates was done witch 12 animals were sampled (6 normoxia - immediately blood collection) and 6 hypoxia - blood collection after 15 min of air exposition) in two collection times with 5 days by intervals. The crowding study was performed by the treatments 1 tadpole L-1, 5 tadpoles L-1 and 10 tadpoles L-1. Three simultaneous replicates was done witch 8 animals (4 normoxia and 4 hypoxia) were sampled in the zero moment (ZM) - blood collection before the experiment, 6 animals/treatment (3 normoxia and 3 hypoxia) to 4 and 8 days and 18 animals/treatment (9 normoxia and 9 hypoxia) to 12 days. The average values to plasmatic cortisol varying from 1.7 to 5.1ng mL-1 (capture study) and 1.0 to 4.2ng mL-1 (crowding study). It concludes that the biomarker tested (cortisol) showed no alterations front of the stressor used. Alternatively, a larger response pattern to these stimuli may have been expressed in another level of an unmeasured hormone (corticosterone). And the bullfrog has great ability to adapt to different management compared to other aquatic organisms, which demonstrates the plasticity of these animals.

Initialism as a mechanism of weed interference: can a crop plant be blinded?

Initialism is a new word proposed to indicate the "shade-avoidance syndrome". Plants detect the presence of neighbor plants very early in the growing season through changes in light quality. They modify the allocation of photosynthesis products privileging shoot growth over the roots. One of the hypotheses of the authors is that, when weed management is timely scheduled, a "blind" crop could be more productive because it would avoid an imbalance on the shoot:root ratio (S:R). Two strategies were developed to test this hypothesis: a) to use the classical Yoda's Law to screen several crops for insensitivity to S:R imbalance; b) to evaluate several growth regulators to control the plant responses to crowding. Experimental results confirm that both strategies can yield insensitive plants. The possibilities of the use of this knowledge are discussed.

Effect of urea on biomimetic aggregates

The effect of urea on biomimetic aggregates (aqueous and reversed micelles, vesicles and monolayers) was investigated to obtain insights into the effect of the denaturant on structured macromolecules. Direct evidence obtained from light scattering (static and dynamic), monolayer maximum isothermal compression and ionic conductivity measurements, together with indirect evidence from fluorescence photodissociation, fluorescence suppression, and thermal reactions, strongly indicates the direct interaction mechanism of urea with the aggregates. Preferential solvation of the surfactant headgroups by urea results in an increase in the monomer dissociation degree (when applied), which leads to an increase in the area per headgroup and also in the loss of counterion affinities