RESUMO

Jatobá-do-cerrado fruit shells, archetypical of lignocellulosic-based biomass, were used as an adsorbent to remove crystal violet (CV) and methylene blue (MB) from water. The adsorbent was characterized using various techniques, and kinetic studies showed dye adsorption followed second-order kinetics. An experimental design investigated the effects of pH and temperature on removal efficiency, with a quadratic model fitting the data best. The results suggest pH influences MB's adsorption capacity more than temperature and at 25 °C and pH 8, MB had a desirability value of 0.89, with 95 % removal efficiency. For CV, temperature had a greater influence, with a desirability value of 0.874 at 25 °C and pH 10, and 95 % removal efficiency. Adsorption isotherm studies revealed maximum adsorption capacities of 123.0 mg·g-1 and 113.0 mg·g-1 for CV and MB, respectively. Experimental thermodynamic parameters indicated an endothermic and spontaneous process which it was supported by quantum chemistry calculations. The protocols developed confirmed the potential for adsorbing CV and MB dyes in water, achieving over 73.1 and 74.4 mg g-1 dyes removal.

Assuntos

RESUMO

Aquatic humic substances (AHS) are defined as an important components of organic matter, being composed as small molecules in a supramolecular structure and can interact with metallic ions, thereby altering the bioavailability of these species. To better understand this behavior, AHS were extracted and characterized from Negro River, located near Manaus city and Carú River, that is situated in Itacoatiara city, an area experiencing increasing anthropogenic actions; both were characterized as blackwater rivers. The AHS were characterized by 13C nuclear magnetic ressonance and thermochemolysis GC-MS to obtain structural characteristics. Interaction studies with Cu (II), Al (III), and Fe (III) were investigated using fluorescence spectroscopy applied to parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy with Fourier transform infrared spectroscopy (2D-COS FTIR). The AHS from dry season had more aromatic fractions not derived from lignin and had higher content of alkyls moities from microbial sources and vegetal tissues of autochthonous origin, while AHS isolated in the rainy season showed more metals in its molecular architecture, lignin units, and polysacharide structures. The study showed that AHS composition from rainy season were able to interact with Al (III), Fe (III), and Cu (II). Two fluorescent components were identified as responsible for interaction: C1 (blue-shifted) and C2 (red-shifted). C1 showed higher complexation capacities but with lower complexation stability constants (KML ranged from 0.3 to 7.9 × 105) than C2 (KML ranged from 3.1 to 10.0 × 105). 2D-COS FTIR showed that the COO- and C-O in phenolic were the most important functional groups for interaction with studied metallic ions.

Assuntos

RESUMO

Cellulose cryogels are promising eco-friendly materials that exhibit low density, high porosity, and renewability. However, the applications of these materials are limited by their lower mechanical and water resistance compared to petrochemical-based lightweight materials. In this work, nanocelluloses were functionalized with cationic and anionic groups, and these nanomaterials were combined to obtain strong and water-resilient cryogels. To prepare the cryogels, anionic and cationic micro- and nanofibrils (CNFs) were produced at three different sizes and combined in various weight ratios, forming electrostatic complexes. The complex phase was concentrated by centrifugation and freeze-dried. Porous and open cellular structures were assembled in all compositions tested (porosity >90 %). Compressive testing revealed that the most resistant cryogels (1.7 MPa) were obtained with equivalent amounts of negatively and positively charged CNFs with lengths between 100 and 1200 nm. The strength at this condition was achieved as CNF electrostatic complexes assembled in thick cells, as observed by synchrotron X-ray tomography. In addition to mechanical strength, electrostatic complexation provided remarkable structural stability in water for the CNF cryogels, without compromising their biodegradability. This route by electrostatic complexation is a practical strategy to combine and concentrate nanocelluloses to tailor biodegradable lightweight materials with high strength and wet stability.

RESUMO

Steroids that take part in the pathways of human steroidogenesis are involved in many biological mechanisms where they interact with calcium. In the present work, the binding selectivities and affinities for calcium of progestagens, mineralocorticoids, androstagens, and estrogens were studied by Electrospray Ionization-Mass Spectrometry (ESI-MS). The adduct profile of each steroid was characterized by high resolution and tandem mass spectrometry. The relative stability of the most important adducts was studied by threshold collision induced dissociation, E1/2. Doubly-charged steroid-calcium complexes [nM + Ca]2+ with n = 1-6 were predominant in the mass spectra. The adduct [5M + Ca]2+ was the base peak for most 3-keto-steroids, while ligands bearing hindered ketones or α-hydroxy-ketones also yielded [nM + Ca + mH2O]2+ with n = 3-4 and m = 0-1. Principal component analysis allowed us to spot the main differences and similarities in the binding behavior of these steroids. The isomers testosterone and dehydroepiandrosterone, androstanolone and epiandrosterone, and 17-α-hydroxyprogesterone and 11-deoxycorticosterone showed remarkable differences in their adduct profiles. Computational modeling of representative adducts was performed by density functional theory methods. The possible binding modes at low and high numbers of steroid ligands were determined by calcium Gas Phase Affinity, and through modeling of the complexes and comparison of their relative stabilities, in agreement with the experimental results.

Assuntos

RESUMO

Alginate is a biopolymer widely used on delivery systems when bioactive protection at acidic pH is required, while chitosan can enhance mucoadhesion and controlled release at alkaline pHs. In this work, alginate ionotropic gelation and electrostatic complexation to chitosan were evaluated concomitantly or in a two-step approach to improve the delivery properties of systems in different pHs. The effect of pH on alginate gelation and chitosan interactions were also evaluated. Alginate microspheres were prepared by ionotropic gelation in CaCl2 at different pH values (2.5 and 6.0) by extrusion. Complexation with chitosan was carried out during alginate ionotropic gelation (one-step approach) or after alginate gel formation (two-step approach). Alginate microparticles without chitosan showed larger pores and lower mechanical strength. Extruded microspheres at pH 6.0 were more stable to pH and showed smaller pores than the formed at pH 2.5. One-step production retained a large amount of bioactive at pH 7.0 and resulted in lower release at the pH of intestinal digestion. The two-step approach retained less amount of bioactive but confer more protection to the pH of the stomach phase and higher release in pH of the intestinal phase than one-step samples. These results indicate that the formation of alginate gels by ionotropic gelation followed by the complexation with chitosan (in two-step) is promising for the transport and delivery of bioactives into intestinal conditions, whereas the ionotropic gelation concomitantly to electrostatic complexation (one-step approach) is indicated to the delivery of bioactives into lower pH environments.

Assuntos

RESUMO

Anthocyanins are a class of compounds potentially used as food dyes. Thus, this study aimed to obtain and characterize natural extracts from Melinis minutiflora inflorescence (M), Plinia. cauliflora peel (JP) and P. cauliflora peel and seeds (JPS) and apply them as natural food dyes in gelatins. The extracts did not show statistically significant differences in pH values and water activity. The M and JPS extracts showed similar values of anthocyanins and total phenolic compounds and were higher than those from the JP extract. The M and JPS extracts showed a bathochromic effect, which was not observed for the JP extract. The bathochromic effect may indicate a possible complexation of anthocyanins. The color composition analysis revealed that the JP extract has a higher absorbance at a wavelength of 520 nm, indirectly suggesting the presence of more monomeric anthocyanins in its composition. The extract application test in gelatin did not change the texture properties of the gelatins. In addition, our findings revealed that the JPS extract had the best color stability after ten days of analysis, indicating that anthocyanin complexation with the phenolic compounds of P. cauliflora seeds contributed more effectively to anthocyanin stability in the model used.

Assuntos

RESUMO

The comprehension of the factors affecting the adsorption of ethanol over metals and metal alloys is a crucial step for the rational development of new catalysts for hydrogen production through ethanol reforming. In this work, we analyze the effect of combining Pt and Sn on a metal cluster on the complexation energy and reactivity for OH dehydrogenation of ethanol. Metal clusters of Pt10, Sn10 and Pt5Sn5 had their putative minimum located with the help of the artificial bee colony algorithm. Whereas the isolated Pt cluster shows a high degree of polarization (ESP surface), the Sn cluster shows a quite uniform electron density surface. The PtSn cluster is strongly polarized, with Pt atoms withdrawing electron density of Sn atoms. Complexation occurs with the oxygen atom of ethanol directed towards the point of highest electron potential in the ESP surface. Pt presents the highest complexation energy, -20.90 kcal/mol, against only -7.83 kcal/mol (at the B97-3c level). For the PtSn cluster, the value is intermediate, namely -12.39 kcal/mol. The more malleable electron density of Pt and its electron affinity are responsible for its highest complexation energy. These characteristics are partially transferred to the PtSn cluster. QTAIM results show that, for the PtSn cluster, the O-H bond in ethanol is somewhat weaker than for pure Pt and Sn. As a consequence, the energy barrier for the O-H dehydrogenation has its lowest value for the PtSn cluster, which shows that the alloying of two metals can lead to quite quite unexpected results opening the perspective for a more rational fine tuning of catalysts properties.

Assuntos

RESUMO

The adsorption characteristics of titanium dioxide nanoparticles (nano-TiO2) for the removal of Pb(II) from irrigation water were investigated in this work. To accomplish this, several adsorption factors, such as contact time and pH, were tested to assess adsorption efficiencies and mechanisms. Before and after the adsorption experiments, commercial nano-TiO2 was studied using X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), energy dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). The outcomes showed that anatase nano-TiO2 was remarkably efficient in cleaning Pb(II) from water, with a removal efficiency of more than 99% after only one hour of contact time at a pH of 6.5. Adsorption isotherms and kinetic adsorption data matched the Langmuir and Sips models quite well, showing that the adsorption process occurred at homogenous sites on the surface of nano-TiO2 by forming a Pb(II) adsorbate monolayer. The XRD and TEM analysis of nano-TiO2 following the adsorption procedure revealed a non-affected single phase (anatase) with crystallite sizes of 9.9 nm and particle sizes of 22.46 nm, respectively. According to the XPS data and analyzed adsorption data, Pb ions accumulated on the surface of nano-TiO2 through a three-step mechanism involving ion exchange and hydrogen bonding mechanisms. Overall, the findings indicate that nano-TiO2 has the potential to be used as an effective and long-lasting mesoporous adsorbent in the treatment and cleaning of Pb(II) from water bodies.

RESUMO

Humic-like substances (HLS) are molecules extracted in an alkaline medium from different materials that have not been subjected to the natural process of humification that occurs in the soil. HLS have the potential to be used as organic fertilizers due to their ability to incorporate micronutrients such as Cu(II) and Co(II); in addition, they represent an alternative for the remediation of contaminated areas due to their high affinity for metals. HLS can be extracted from hydrochar (HC) but only with low yields of approximately 5%. Therefore, the present study aimed to increase the amount of HLS extracted from the HC produced from byproducts of the sugarcane industry through the oxidation of HC with HNO3. HLS extracted from oxidized and unoxidized HC were characterized by CHNS analysis and 13C CPMAS NMR. The interaction between HLS and Cu(II) was studied by molecular fluorescence quenching (EEM-PARAFAC) and applying the Ryan and Weber complexation model. The oxidation of HC with HNO3 allowed high yields of extracted HLS of above 80%. The oxidation carried out with 30% HNO3 for 2 h showed the best result, since the HLS30%(2h) were extracted with a very high yield (88.3%) in a short period of time. Oxidation promoted a decrease in HLS aromaticity and an increase in oxygen and nitrogen groups. HLS showed high affinity for Cu(II), as evidenced by the high logK values (between 5.5 and 5.9). HLS extracted from oxidized HCs showed higher complexation capacity due to the greater incorporation of the oxygenated groups promoted by oxidation, which are fundamental during the interaction with metallic cations. Therefore, the oxidation of HC substantially increased the production of HLS, representing a big advance for the production of carbonaceous materials with higher added value from byproducts of the sugarcane industry produced on a large scale in Brazil.

Assuntos

RESUMO

Complexation of dissolved organic matter (DOM) with cations and minerals contributes to the stabilization of carbon in soils, and can enable the transport of metals in the environment. Hence, a proper understanding of mechanisms that control DOM binding properties in the soil is important for major environmental challenges, such as climate change and stream pollution. However, the role of DOM source in those mechanisms remains understudied. Here, we consider poorly drained tropical Podzols as a model environment to isolate effects of aluminium and DOM on sorption and desorption processes in podzolisation. We collected E- and Bh-horizons from a Brazilian coastal Podzol under tropical rainforest to conduct a column experiment, and percolated the columns with DOM collected from a stream (Stream), peat water (Peat), litter (Litter) and charred litter (Char). To quantify sorption and desorption from the columns, leachates were analysed for DOC content, aluminium content, pH, and the amount of fulvic acid relative to humic acid. The results showed large differences in DOC retention between DOM-types, which were consistent over all columns. Retention of DOC in the column varied between 25 % and 92 % for DOM-type Stream, between 33 % and 63 % for DOM-type Peat, between 22 % and 47 % for DOM-type Litter, and between 8 % and 49 % for DOM-type Char. Similarly, desorption from columns with B-horizon material highly differed between DOM-types. Percolation with DOM-types Stream and Peat caused a release of native DOC from B columns that was higher than in those percolated with water only. On the other hand, percolation of B columns with DOM-types Litter and Char caused a net DOC retention. These differences reflect that certain DOM-types hindered desorption, while other DOM-types caused active desorption. The large differences in sorption/desorption between DOM-types implies that changes in environmental conditions may highly influence the fate of soil carbon in Podzols.