Effects of chemical aging on carbonaceous materials: Stability of water-dispersible colloids and their influence on the aggregation of natural-soil colloid.

Although hydrochar and biochar have been used as soil conditioners, there is not a clear understanding of how their properties changes due to aging impacts their colloidal particles behavior on the soil system. From this premise, we produced hydrochar and biochar from the same feedstock (cashew bagasse) and aged with different chemical methods: (i) using hydrogen peroxide, (ii) a mixture of nitric and sulfuric acids, and (iii) hot water. It was analyzed the effects of aging on the stability of the carbonaceous materials (CMs) colloids in aqueous medium with different ionic strength (single systems), as well as the stability of the natural-soil colloid when interacting with biochar and hydrochar colloids (binary systems). A chemical composition (C, H, N, and O content) change in CMs due to the chemically induced aging was observed along with minor structural modifications. Chemical aging could increase the amount of oxygen functional groups for both biochar and hydrochar, though in a different level depending on the methodology applied. In this sense, hydrochar was more susceptive to chemical oxidation than biochar. The effectiveness of chemical aging treatments for biochar increased in the order of water < acid < hydrogen peroxide, whereas for hydrochar the order was water < hydrogen peroxide < acid. While the increase in surface oxidation improved the biochar colloidal stability in water medium at different ionic strengths (single systems), the stability and critical coagulation concentration (CCC) slightly changed for hydrochar. Natural-soil clay (NSC) interactions with oxidized carbonaceous material colloids (binary systems) enhanced NSC stability, which is less likely to aggregate. Therefore, the aging of carbonaceous materials modifies the interaction and dynamics of soil small particles, requiring far more attention to the environmental risks due to their application over time.

Oxidation of hydrochar produced from byproducts of the sugarcane industry for the production of humic-like substances: Characterization and interaction study with Cu(II).

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.

Study of Structural and Optical Properties of Titanate Nanotubes with Erbium under Heat Treatment in Different Atmospheres.

Titanate nanotubes were synthesized and subjected to an ion exchange reaction with erbium salt aqueous solution to obtain titanate nanotubes exchanged with erbium (3+) ions. In order to evaluate the effects of the thermal treatment atmosphere on the structural and optical properties of erbium titanate nanotubes, we subjected them to heat treatment in air and argon atmospheres. For comparison, titanate nanotubes were also treated in the same conditions. A complete structural and optical characterizations of the samples was performed. The characterizations evidenced the preservation of the morphology with the presence of phases of erbium oxides decorating the surface of the nanotubes. Variations in the dimensions of the samples (diameter and interlamellar space) were promoted by the replacement of Na+ by Er3+ and the thermal treatment in different atmospheres. In addition, the optical properties were investigated by UV-Vis absorption spectroscopy and photoluminescence spectroscopy. The results revealed that the band gap of the samples depends on the variation of diameter and sodium content caused by ion exchange and thermal treatment. Furthermore, the luminescence strongly depended on vacancies, evidenced mainly by the calcined erbium titanate nanotubes in argon atmosphere. The presence of these vacancies was confirmed by the determination of Urbach energy. The results suggest the use of thermal treated erbium titanate nanotubes in argon atmosphere in optoelectronics and photonics applications, such as photoluminescent devices, displays, and lasers.

Use of Calotropis procera cysteine peptidases (CpCPs) immobilized on glyoxyl-agarose for cheesemaking.

Calotropis procera cysteine peptidases (CpCPs) have presented several potential biotechnological applications. Here, these enzymes were immobilized on glyoxyl-agarose (glyoxyl-CpCPs) with yields of 90-95 % and the recovered activities ranged from 10 % to 15 %, according to enzyme loadings (5, 10, 20, 40, and 50 mgBSAeq/g). Spectrophotometric assays and SDS-PAGE showed that the casein hydrolysis by glyoxyl-CpCPs was similar to soluble CpCPs. In addition, glyoxyl-CpCPs exhibited similar ratio of milk-clotting activity to proteolytic activity in comparison with soluble CpCPs and chymosin. Even after being stored for six months at 8 °C, the residual proteolytic activity of glyoxyl-CpCPs remained close to 100 %. Atomic force microscopy and dynamic light scattering techniques showed that the process of casein micelle aggregation after treatment with glyoxyl-CpCPs was very similar to its soluble form and chymosin. Glyoxyl-CpCPs performed well after five reaction cycles, producing cheeses with yield, moisture, protein, and fat similar to those produced with chymosin.

Amino-Functionalized Titanate Nanotubes: pH and Kinetic Study of a Promising Adsorbent for Acid Dye in Aqueous Solution.

This work reports the functionalization of sodium titanate nanotubes with amine groups obtained from the reaction of titanate nanotubes with [3-(2-Aminoethylamino)propyl]trimethoxysilane, NaTiNT-2NH, and 3-[2-(2-Aminoethylamino)ethylamino]propyltrimethoxysilane, NaTiNT-3NH. It was verified that the crystalline and morphological structures of NaTiNT were preserved after the functionalization, spectroscopies showed that aminosilane interacted covalently with the surface of NaTiNT, and the incorporation of the aminosilane groups on the surface of NaTiNT can be confirmed. The adsorbent matrices NaTiNT-2NH and NaTiNT-3NH were used to remove the anionic dye from remazol blue R (RB) in aqueous medium, and the highest adsorption capacity was around 365.84 mg g-1 (NaTiNT-2NH) and 440.70 mg g-1 (NaTiNT-3NH) in the range of pH 5.0 to 10.0 and the equilibrium time was reached in 210 min (NaTiNT-2NH) and 270 min (NaTiNT-3NH). Furthermore, the Elovich model, which reports the adsorption in heterogeneous sites and with different activation energies in the chemisorption process, was the most appropriate to describe the adsorption kinetics. Thus, these adsorbent matrices can be used as an alternative potential for dye removal RB in aqueous solution.

Increase of Fluorescence of Humic-Like Substances in Interaction with Cd(II): a Photoinduced Charge Transfer Approach.

Described is the enhancement of fluorescence intensity due to the interaction of a humic-like substance (HLS 1%) extracted from process water (PW) and Cd(II) ions in aqueous solution. Using Canonical Polyadic/Parallel Factor Analysis (CP/PARAFAC), two main components were seen that contributed to fluorescence, the first one increased it and the second one kept it constant in both static and dynamic fluorescence studies. Two-dimensional FTIR analysis indicated that the interaction of HLS 1% and Cd(II) ions occurred in the following order of affinity with the groups: C-O bonds in polysaccharides > C-O bonds in carboxylic acid. The results obtained suggest that the increase in fluorescence intensity and lifetime suggest a photoinduced charge transfer (PCT) between Cd(II) ions and carboxylic acid groups present in HLS 1%.

Insights on Molecular Characteristics of Hydrochars by 13C-NMR and Off-Line TMAH-GC/MS and Assessment of Their Potential Use as Plant Growth Promoters.

Hydrochar is a carbon-based material that can be used as soil amendment. Since the physical-chemical properties of hydrochar are mainly assigned to process parameters, we aimed at evaluating the organic fraction of different hydrochars through 13C-NMR and off-line TMAH-GC/MS. Four hydrochars produced with sugarcane bagasse, vinasse and sulfuric or phosphoric acids were analyzed to elucidate the main molecular features. Germination and initial growth of maize seedlings were assessed using hydrochar water-soluble fraction to evaluate their potential use as growth promoters. The hydrochars prepared with phosphoric acid showed larger amounts of bioavailable lignin-derived structures. Although no differences were shown about the percentage of maize seeds germination, the hydrochar produced with phosphoric acid promoted a better seedling growth. For this sample, the greatest relative percentage of benzene derivatives and phenolic compounds were associated to hormone-like effects, responsible for stimulating shoot and root elongation. The reactions parameters proved to be determinant for the organic composition of hydrochar, exerting a strict influence on molecular features and plant growth response.

Synthesis of silver-cerium titanate nanotubes and their surface properties and antibacterial applications.

Nano-heterostructures of titanate nanotubes were synthesized and they revealed a complex structure with the formation of TiO2 (anatase), CeO2, Ag2O and metallic silver nanoparticles on the outer walls and intercalation of Ce4+ and Ag+ into the interlayer spaces of the nanotubes by microwave-assisted hydrothermal process and subjected to ion exchange reactions. To the best of our knowledge, this is the first reported silver and cerium co-exchanged titanate nanotubes for bio-applications. The co-ion exchange processes preserved the original tubular structure of titanate nanotubes with significant changes of the superficial as well as interlamellar environment. This study opens up possibility of synthesizing complex, functional nano-heterostructure with the scope of modification of the final structure, especially the amount and oxidation state of the intercalated cation (Ce4+, Ce3+ and Ag+) as well as the quantity and variety of the decorating nanoparticles (CeO2, Ag2O or metallic Ag). The interplay of which, in turn, can lead to important biological properties and applications, owing to their ion-liberation capacity. The samples were tested in antibacterial activity with two different kind of bacteria (gram positive and negative), cell cytotoxicity and adhesion, and it was found that the nano-heterostructure formed shows high antibacterial activity with low cytotoxicity and high cell adhesion, which makes it a promising material for further health applications.

On the formation of protein corona on colloidal nanoparticles stabilized by depletant polymers.

To counter the undesired colloidal destabilization of nanoparticles in biologically-compatible media of high ionic strength (i.e. NaCl, phosphate buffer), polymers can be added to nanoparticle suspensions that will be used in biomedical applications. In these suspensions, polymers can promote high colloidal stability by manifestation of steric and/or depletion forces. However, little is known about the influence of these polymers on the interactions between nanoparticles and the biological components of the organism, such as proteins and cells. In this work, it was shown that the addition of the polymers (i) Pluronic-F127 (PF127), (ii) polyethylene glycol (PEG) of different molecular weights - 1.5, 12 and 35 kDa - and (iii) the protein bovine serum albumin (BSA) on colloidal silica nanoparticles (CSNPs; 135 nm) dispersed in phosphate-buffered saline (PBS) largely alter their colloidal stability through different mechanisms. Although all polymers were adsorbed on the CSNP surface, BSA maintained the CSNP dispersion in the medium by electrosteric stabilization mechanisms, while PEG and PF127 led to the occurrence of depletion forces between the particles. In addition, it was found that the interactions between polymers and CSNPs did not prevent proteins to access the nanoparticles' surface and have minimal effect on the formation of the protein corona when they were incubated in human blood plasma. On the other hand, BSA had a greater effect on the CSNP protein corona profile compared to other polymers (PEG and PF127). Together, these results confirm that biocompatible polymers PEG and PF127 can be used as colloidal stabilizing agents for nanoparticles since they preserve the accessibility of biomolecules to the nanoparticle surface, and they have little effect on the protein corona composition.

In situ growth of manganese oxide nanosheets over titanium dioxide nanofibers and their performance as active material for supercapacitor.

In recent years, electrochemical energy devices, i.e. batteries, fuel cells, solar cells, and supercapacitors, have attracted considerable attention of scientific community. The architecture of active materials plays a crucial role for improving supercapacitors performance. Herein, titanium dioxide (TiO2) nanofibers (1D) have been synthesized by electrospinning process and used as a backbone to manganese dioxide (MnO2) nanosheets (2D) growth through hydrothermal method. This strategy allows the obtaining of 1D/2D heterostructure architecture, which has demonstrated superior electrochemical performance in relation to pristine MnO2. The highest electrochemical performance is due to the synergic effect between the metal oxides, where TiO2 nanofibers provide electrochemical stability for active MnO2 phase. Thus, the designed TiO2@MnO2 structure can reach maximum specific capacitance of 525 F·g-1 at a current density of 0.25 A·g-1, and it demonstrates an excellent stability by retaining 81% of the initial capacitance with coulombic efficiency of 91%. Therefore, the novel architecture of TiO2@MnO2 based on nanofibers and nanosheets exhibits superior electrochemical properties to be used in supercapacitor applications.

Large-field electron imaging and X-ray elemental mapping unveil the morphology, structure, and fractal features of a Cretaceous fossil at the centimeter scale.

We used here a scanning electron microscopy approach that detected backscattered electrons (BSEs) and X-rays (from ionization processes) along a large-field (LF) scan, applied on a Cretaceous fossil of a shrimp (area ∼280 mm(2)) from the Araripe Sedimentary Basin. High-definition LF images from BSEs and X-rays were essentially generated by assembling thousands of magnified images that covered the whole area of the fossil, thus unveiling morphological and compositional aspects at length scales from micrometers to centimeters. Morphological features of the shrimp such as pleopods, pereopods, and antennae located at near-surface layers (undetected by photography techniques) were unveiled in detail by LF BSE images and in calcium and phosphorus elemental maps (mineralized as hydroxyapatite). LF elemental maps for zinc and sulfur indicated a rare fossilization event observed for the first time in fossils from the Araripe Sedimentary Basin: the mineralization of zinc sulfide interfacing to hydroxyapatite in the fossil. Finally, a dimensional analysis of the phosphorus map led to an important finding: the existence of a fractal characteristic (D = 1.63) for the hydroxyapatite-matrix interface, a result of physical-geological events occurring with spatial scale invariance on the specimen, over millions of years.