An opportunity for acerola pulp (Malpighia emarginata DC) valorization evaluating its performance during the block cryoconcentration by physicochemical, bioactive compounds, HPLC-ESI-MS/MS, and multi-elemental profile analysis.

The present study evaluated the effect of cryoconcentration of pulp blocks of acerola (Malpighia emarginata DC). The study evaluated cryoconcentration in three stages. The cryoconcentrated samples, the ice fractions, and the initial pulp were evaluated for physicochemical composition, bioactive composition, and multielement profile. The cryoconcentrated sample obtained in the third stage of cryoconcentration showed the best results for the concentration factor, process efficiency, total soluble solids content, red color intensity, and increasing of the macro and micronutrients: Cu, Ca, S, Sr, K, Mn, Na, P, Mg, Fe. All stages presented good performance in the total soluble solids content, increase in the titratable acidity of the concentrates, and progressive increase in the intensity of the red color. Generally, higher levels of total phenolic and antioxidant activity were found for the 2nd and 3rd concentrates. The phenolic activity showed an increase of 166.90% in the 3rd stage concentrate compared to fresh pulp, and the antioxidant activity was 112.10% by the ABTS method and 131.60% by the DPPH method, both in the 3rd stage concentrate. The major individual polyphenols were Ferulic acid, Protocatechuic acid, and Taxifolin, with significant increases in the concentration of the compounds in the 2nd and 3rd stage concentrates. In addition, the contents of potentially toxic metals were below detection limits. During the cryoconcentration process, there was a decrease in the values ​​of vitamin C content, moisture content, density, and elements Cu, Sr, and Zn.

Determination of the Concentration of Heavy Metals in Artisanal Cheeses Produced in the Mexican States of Tabasco and Chiapas.

Cheese consumption provides humans with minerals, proteins, carbohydrates, and vitamins. In Mexico, several cheese varieties are produced, each with its texture, scent, and flavor. The artisanal cheeses made in the states of Tabasco and Chiapas-including, among others, the varieties named crema (cream), doble crema (double cream), oaxaca, panela, fresco, bola, poro, cotija, and asadero-have a high demand in the domestic and foreign markets. The intensification of anthropic activity in these states causes an increased emission to the environment of contaminants like heavy metals, which could reach human foodstuffs through the food chains. In particular, heavy metal contents in cheeses consumed daily by these states' local populations might represent a public health risk. Because of that, our objectives in this work were to determine the concentrations of lead, cadmium, nickel, copper, zinc, and iron in artisanal cheeses produced in the states of Tabasco and Chiapas and to determine the values of the hazard quotient (HQ), total hazard quotient (THQ), and cancer risk total (CRT) for adult and young men and women. The results of our analyses of cheese samples from the states of Tabasco and Chiapas showed that the average concentrations (mg kg-1) of cadmium (0.0023 ± 0.002, 0.0023 ± 0.002 mg kg-1, respectively, for each state), lead (0.0047 ± 0.00, 0.0051 ± 0.002), nickel (0.0039 ± 0.0046, 0.0031 ± 0.0039), copper (0.0199 ± 0.021, 0.0202 ± 0.022), zinc (0.1611 ± 0.18, 0.194 ± 0.21), and iron (61.84 ± 4.23, 65.76 ± 6.61 mg kg-1), the first three values lower than the limits established by the FAO/WHO and Codex Alimentarius. The value of THQ that we obtained was less than one, and that of CRT was within the limits established by the US-EPA, which means that the consumption of artisanal cheeses from Tabasco and Chiapas by humans does not imply a risk of disease or cancer.

Comparison of powdered and fresh jambu (Acmella oleracea).

Jambu, Acmella oleracea (L.), is a low-growing herb plant, with cylindrical, fleshy, decumbent and branched stem varying from 20 to 30 cm in height. It is an abundantly cultivated and consumed vegetable in the northern region of Brazil and usually consumed in preparations of typical foods of the Amazon region. So, this work aimed to compare the chemical composition and physical chemistry of powdered and jambu leaf mass. Acmella oleracea plants were selected, sanitized and their leaves were crushed (without adding water). The mass was dried in an oven with forced air circulation under different conditions of temperature (60, 70 and 80 °C) and relative humidity (13.09, 8.14 and 5.45%, respectively), in two layer thicknesses (0.5 and 1.0 cm). The physical, chemical, physicochemical parameters moisture content, water activity, ash, protein, lipids, pH, total titratable acidity and color were analyzed in powdered and fresh leaves. Contrast test was used to evaluate the interaction between the layer thicknesses at 5% level of significance. Considering the contrasts, the parameters total soluble solids, ash, protein and lipids do not differ from those in the fresh sample, demonstrating that these parameters are not modified or degraded with the drying conditions. The pH and color parameters differed from those of the fresh material, due to degradation, which can be linked to the rise in temperature sensitivity. The moisture content and water activity also differed and were reduced, contributing to conservation of the material. Contrast analysis made it possible to conclude that the physicochemical composition did not undergo modifications through the use of drying. In addition, a powdered material with reduced water activity was obtained.

Optimization of the photocatalytic degradation process of aromatic organic compounds applied to mangrove sediment.

Polycyclic aromatic hydrocarbons (PAHs) are part of a class of organic compounds resistant to natural degradation. In this way, heterogeneous photocatalysis becomes useful to degrade persistent organic pollutants, however it can be influenced by environmental variables (i.e.: organic matter) and experimental factors such as: mass of the photocatalyst and irradiation time. The objective of this research was to use a factorial design 2k as a function of the multiple response (MR) to evaluate simultaneously experimental conditions for the photodegradation of polycyclic aromatic hydrocarbons in contaminated mangrove sediment and its application in oil from Potiguar Basin in Brazil. The sediment samples collected in Belmonte city (Southern Bahia state) were contaminated with 0.25 mg kg-1 of Acenaphthene, Anthracene, Benzo[a]Anthracene, Indene[1,2,3cd]pyrene, Dibenzo[ah]anthracene, Benzo[ghi]pyrene. Factors such as mass of the photocatalyst and irradiation time were evaluated in factorial design 22, with triplicate from the central point, to 1g of the PAH contaminated sediment. After performing the experiments, it was found that the best experimental condition for the degradation of all PAHs indicated by MR was the central point (0.5 g of photocatalyst and 12h of irradiation). For such conditions, the half-life of PAHs varied from 3.51 to 9.37 h and the degradation speed constant between 0.0740 to 0.1973 h-1. The comparison of the optimized methodology between photolysis tests and heterogeneous photocatalysis was performed using the Kruskal-Wallis test, which indicated a difference for the reference solution, where heterogeneous photocatalysis was more efficient in the degradation of PAHs. The optimized methodology was apply in samples contaminated with crude oil from Potiguar Basin, no significant difference was observed in the aromatic fraction, using for the Kruskal-Wallis test. Heterogeneous photocatalysis has shown to be a promising remediation technique to remedy aromatic organic compounds in mangrove sediments.

Exploring the nature of the interactions between the molecules of the sodium dodecyl sulfate and water in crystal phases and in the water/vacuum interface.

The nature of the interaction between the molecules of the sodium dodecyl sulfate surfactant forming two crystal phases, one anhydrous, NaC12H25O4S and the other, NaC12H25O4S.H2O, hydrated with one water molecule for unit cell, has been studied in detail using the quantum theory of atoms in molecules and a localized electron detector function. It was found that for the anhydrous crystal, the head groups of the surfactant molecules are linked into a head-to-head pattern, by a bond path network of Na-O ionic bonds, where each Na+ atom is attached to four S O 4 - groups. For the hydrated crystal, in addition to these four bonds for Na+, two additional ones appear with the oxygen atoms of the water molecules, forming a bond paths network of ionic Na-O bonds, that link the Na+ atoms with the S O 4 - groups and the H2O molecules. Each H2O molecule is bonded to two S O 4 - groups via hydrogen bonds, while the S O 4 - groups are linked to a maximum of four Na+ atoms. The phenomenon of aggregation of the sodium dodecyl sulfate molecules at the liquid water/vacuum interface was studied using NVT molecular dynamics simulations. We have found that for surfactant aggregates, the Na+ ions are linked to a maximum of three SO4 - groups and three water molecules that form Na-O bonds. Unlike hydrated crystal, each of the O atoms that make these Na-O bonds is linked to only one Na+ ion. Despite these differences, like the crystal phases, the surfactant molecules tend to form a head-to-head network pattern of ionic Na-O bonds that link their heads. The present results indicate that the clustering of anionic surfactant at the water/vacuum interface is a consequence of the electrostatic alignment of the cationic and anionic groups as occurs in the crystalline phases of sodium dodecyl sulfate.

Photolysis, tautomerism and conformational analysis of dehydroacetic acid and a comparison with 2-hydroxyacetophenone and 2-acetyl-1,3-cyclohexanodione.

The purpose of this work was to determine the tautomerism, the conformational analysis and photoreactivity of dehydroacetic acid (DHAA, 1). For that reason, the photolysis of DHAA (1) was performed at 254 nm and compared with two structurally similar compounds: 2-hydroxyacetophenone (HAP, 2) and 2-acetyl-1,3-cyclohexanodione (ACH, 3). We confirmed the degradation of 1 to acetic acid and we propose a mechanism on the assumption that a [2+2] cyclodimerization occurs (after UV light absorption) followed by some consecutive Norrish Type I cleavages, affording ketenes that end-up in acetic acid. The UV absorption study was conducted for all three compounds to gain insight about their electronic transitions, both experimentally and with computational simulations using TDDFT (B3LYP/6-31+G(d,p)) methods. A detailed analysis of the different tautomers and isomers that can be present in solution and the MOs involved in the electronic transitions was also achieved. The HOMO→LUMO transition was the least energetic optically active transition for 1 and 2, whereas 3 was recognized to have a HOMO-1→LUMO transition. These transitions were all of n→π∗ character.

Interaction between glyphosate and montmorillonite in the presence of artificial seawater.

Glyphosate (N- (phosphonomethyl) glycine) is one of the most widely used herbicides in the world. In the literature, there are several studies describing the interaction between glyphosate and clay minerals. However, there is a lack of data of this interaction in marine environments. In this research, we examined the adsorption of glyphosate onto montmorillonite in the presence of artificial seawater. Mössbauer data showed that the interaction of the phosphonate group of glyphosate with Fe2+ of montmorillonite prevents its oxidation to Fe3+. X-ray diffractograms showed that glyphosate adsorption takes place only onto the montmorillonite surface and not in its interlayers. Infrared spectroscopy data demonstrate that the interaction between glyphosate and montmorillonite could be through the amino group. FT-IR spectra of aqueous solutions of salts of seawater showed that Ca2+ interacts with glyphosate of the phosphonate group, thus causing an increase in its adsorption onto montmorillonite. However, glyphosate dissolved in 0.50 mol L-1 NaCl and 0.034 mol L-1MgCl2 solutions showed the lowest adsorption onto montmorillonite. In addition, the adsorption of glyphosate onto montmorillonite decreased when the NaCl concentration increased. The results fitted the Sips isotherm model, probably because the Ca2+ interacts with glyphosate, making the adsorption process more homogeneous. Thus, n values for Freundlich and Sips isotherm models decreased with an increase in ionic strength. Glyphosate and ions of artificial seawater increased the pHpzc of montmorillonite.

Do-it-yourself methodology for calorimeter construction based in Arduino data acquisition device for introductory chemical laboratories.

Many experimental thermochemical laboratories require monitoring temperatures during a reaction or physical procedure. Nowadays, there are many alternatives to fulfill this requirement; however, they are expensive for basic scholars and first-year undergraduates. In this paper, we describe an inexpensive and useful data acquisition device developed with the open-source Arduino software. In this work, we presented a methodology for easy calorimeter construction based in Arduino data acquisition device for introductory chemical laboratories, we used an LM35 transistor as a temperature sensor connected to an Arduino UNO microcontroller for temperature sensing and an aquarium air pump for agitation of reaction system. Besides, the hardware required for implementation is explained in detail. The device was built using the (DIY) do-it -yourself method, and the complete system had a total cost under $40. We showed details of all components for data acquisition construction. Finally, we tested the device in order to determine the exothermic dissolution heat (ΔH) for NaOH in water.

Quantitative evaluation of the surface stability and morphological changes of Cu2O particles.

Cu2O low-index surfaces periodic models have been simulated based on density functional theory. The calculated surfaces energies allowed estimating the morphology by means of the Wulff theorem as well as the investigation of possible paths of morphological changes. Therefore, systematic morphology diagrams and change paths according to the energy modulation in relation to the surfaces stabilizations were elaborated. The applicability of this strategy was exemplified by comparing the obtained results with experimental available data from the literature. The morphology diagrams with the quantitative energetic point of view can be used as a guide to support experimental works in order to understand the relation between surface interactions and crystal growth.

Kinetic triplet of Colombian sawmill wastes using thermogravimetric analysis.

The potential of sawmill wastes as a raw material in pyrolysis process is presented in this study. Non-isothermal thermogravimetric analysis (TGA and DTG) and isoconversional methods were employed to determine triplet kinetic (activation energy, reaction model and pre-exponential factor). Through TGA and DTG, the conversion degree is described as a function of temperature for five heating rates (10, 20, 30, 40 and 50 o C/min) and four model-free methods (Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Friedman, and Vyazovkin) with temperatures ranging from 25 to 1000 ° C were employed. Isoconversional lines were built for every method at different isoconversional degrees α ∈ [ 0,1 ] . The activation energy E was found as a function of α in the interval χ I I = [ 0.2 , 0.7 ] where each isoconversional methods were in agreement and the estimated error was sufficiently small. Findings show the same activation energy profile independently of the isoconversional method. In particular the total variation of E in χ I I was as follows: 209.909-228.238 kJ/mol (FWO); 211.235-229.277 kJ/mol (KAS); 223.050-188.512 kJ/mol (Friedman), and 211.449 kJ/mol-229.512 kJ/mol (Vyazovkin). The reaction model of the process in χ I I matched with a two-dimensional diffusion ( D 2 ) by using a master-plot analysis. The calculated and reported parameters are fundamental information for the pyrolysis reactor design using Sawmill wastes as feedstock.

Polypropylene and tire powder composite for use in automotive industry.

In this work, we study and characterize 20%- and 30%-reinforced rubber tire powder and polypropylene composite to apply it in the engine encapsulation of commercial vehicles. We produce a prototype with 20% of rubber tire powder due to its better processability and carry out external noise analysis and the results show it is similar to the already available material and within the limits established by law, besides presenting a substantial 54-weight% decrease. In addition, the material guarantees a minimization of sound pollution - through the attenuation of noise by the composite - and environmental, by the reduction of inappropriate disposal of waste tires.

Influence of magnetic field on barium sulfate incrustation from aqueous solutions.

The formation of scales in the petroleum industry, such as those composed of calcium and barium sulfates, may reduce productivity since these sediments can partially or totally obstruct the pipes. The mitigation of these inorganic precipitates can be accomplished by using scale inhibitors or by non-intrusive physical technologies. Here, we investigated the influence of magnetic field on the incrustations of barium sulfate by analyzing the concentration of barium and sulfate ions, the solution flow rate, the capillary tube geometry, and the magnetic field intensity in a homemade experimental unit supported on the monitoring of the dynamic differential pressure. The results show that the saline concentration and the flow rate of the solutions and the geometry of the capillary tube have a significant influence on the dynamics of barium sulfate incrustation. The presence of the magnetic field tends to prolong the induction time of the barium sulfate precipitation. A semi-empirical model was used to describe the effect of the studied variables on the barium sulfate incrustation behavior. The X-ray diffraction data of the precipitated particles analyzed using the Rietveld method suggest that the use of the magnetic field favor the formation of more crystalline particles and with smaller crystallite size than those formed in the absence of a magnetic field. Optical and scanning electron microscopy measurements also corroborate with these findings. The results from this study suggest that magnetic fields can be of interest in practical crystallization processes of barium sulfate and successfully applied to decrease the speed of barium sulfate incrustation in pipelines.

Hydrophobic nanoprecipitates formed by benzoylphenylureas and ß-cyclodextrin inclusion compounds: synthesis, characterization and toxicity against aedes aegypti larvae.

The aim of this work was to synthesize and characterize the inclusion compounds formed by the complexation of ß-cyclodextrin (ßCD) with insecticides from the class of benzoylphenylureas (BPUs), named novaluron (NOV) and diflubenzuron (DIF), beyond evaluate their larvicidal activity against Aedes aegypti larvae. Solid state characterization by FTIR showed changes in the main peaks of BPUs and ßCD, suggesting the formation of inclusion compounds in solid phase. DTA and TGA thermal analysis showed changes in temperatures of BPUs decomposition as result of molecular interactions. 1H NMR experiments allowed to observe the occurrence of interactions in solution through changes in chemical shifts of BPUs aromatic hydrogens. However, the presence of H-H intermolecular correlations in 2D ROESY was found only for the DIF/ßCD complex, suggesting different topology for each complex. Such hypothesis was corroborated by thermodynamic analysis using ITC, which showed different profile of titration curves, beyond endothermic and exothermic interactions for NOV/ßCD and DIF/ßCD complexes, respectively. DLS titrations of BPUs or BPUs/ßCD DMSO solutions in aqueous solution demonstrated that the spontaneously formed hydrophobic nanoprecipitates (HNPs) have different profile of sizes depending on the BPU/ßCD system, corroborating also with the hypothesis about the existence of different topologies for each complex. Finally, the HNPs of inclusion compounds showed to be more efficient than free BPUs, allowing proposing a new insecticide formulation.

Sulfonated and gamma-irradiated waste expanded polystyrene with iron oxide nanoparticles, for removal of indigo carmine dye in textile wastewater.

In this work, waste expanded polystyrene (WEPS) was irradiated with gamma rays, ranging doses from 100 kGy to 1,000 kGy. After irradiation, the WEPS had decrease on its glass transition temperature (Tg), as consequence of the scissions of its polymer chains. Then, the irradiated WEPS was sulfonated, and its degree of sulfonation (DS) was measured. The highest DS value, 46.6%, was obtained for an irradiation dose of 200 kGy. The sulfonated and irradiated polystyrene (denominated as iS-WEPS), was used as a support of iron oxide nanoparticles. Such composite system was denominated (FeO-NPs + iS-WEPS). The results show nanoparticle sizes of 31.5 nm containing 21.97% iron oxide. The composites followed a pseudo-second order model, with a maximum adsorption capacity of 20 mg/g, and an equilibrium time of 30 min, according to the Langmuir model. Moreover, the optimal conditions followed by the Fenton process were: pH = 3.2, H2O2 concentration = 0.32 mM/L, composite concentration (FeO-NPs + iS-WEPS) = 2 g/L, and a reaction time 20 min. Finally, 99% removal of indigo carmine dye was achieved, and a reduction of 83% of COD in textile wastewater.

Solid adenine and seawater salts exposed to gamma radiation: An FT-IR and EPR spectroscopy analysis for prebiotic chemistry.

Solids of adenine obtained from distilled water and seawater lyophilized solutions were γ irradiated at a 94.52 kGy dose. Results indicate that pure solid adenine had a low degradation rate, likewise the solid containing seawater salts. However, EPR spectroscopy analysis suggests a high interaction of the radiation with seawater salts, by radical formation in sulfate ions. These outcomes are of interest for prebiotic chemistry, since ions could have played important roles in chemical evolution. In addition, Martian soil is rich in sulphate salts, thus these salts could protected organic molecules being degraded by γ-radiation.

Thermodynamic study of adsorption of nickel ions onto carbon aerogels.

In this work, 8 samples of carbon aerogels with different ratios of catalyst versus resorcinol (R/C) from 25 to 1500 were used. The textural properties were evaluated from N2 adsorption isotherms in 77 K, as well as the chemical ones, where the surface chemistry was evaluated through the Boehm titrations. The results were analyzed and related to the adsorption of the nickel (II) ion from aqueous solution. The experimental results show that the aerogel samples can be divided into two series with different properties: Series I, mainly microporous (low ratio R/C) and Series II (high ratio R/C) mainly microporous but with a contribution of mesoporosity. The specific surface area varied between 64 and 990 m2 g-1. The experimental results show that prepared aerogels have an adequate adsorption capacity towards nickel (II) ions. The behavior of the kinetics of Ni(II) adsorption on carbon aerogels adjusts in a better way the kinetic model of pseudo-second order since it is the one that presents the value of the highest R2 correlation coefficient. The calorimetric data shows that the greater the area developed in carbons aerogels the enthalpy increases.

Phosphorus as a promoter of a nickel catalyst to obtain 1-phenylethanol from chemoselective hydrogenation of acetophenone.

Two catalysts were prepared using monodisperse pre-synthetized nanoparticles of metallic nickel and nickel phosphides with the same average diameter. Both nanoparticles species were deposited on the same support: mesoporous silica nano-spheres of MCM-41. This support is suitable to inhibit agglomeration and sintering processes during preparation steps. Therefore, two supported and activated catalysts with the same average nanoparticles diameter were obtained. They differ only in the nature of the active species: metallic nickel and nickel phosphides. The effect of the presence of a second element (phosphorus), more electronegative than nickel, on the activity and selectivity in the chemoselective hydrogenation of acetophenone was studied. The reaction conditions were: H2 pressure of 1 MPa, 80 °C using n-heptane as solvent. With the aim to understand the catalytic results, nanoparticles, support and catalysts were carefully characterized by X-ray diffraction, diffuse light scattering, transmission electron microcopy, high resolution transmission electron microcopy, selected area electron diffraction, scanning electron microcopy, Fourier transformer infrared spectroscopy, N2 adsorption at -196 °C, atomic absorption, H2 and CO chemisorption and volumetric oxidation. Considering these results and geometric and electronic characteristics of the surface of both active species, a change in the adsorption intermediate state of acetophenone in presence of phosphorus is proposed to explain the hydrogenation chemoselectivity of nickel phospides.

Formation of dendrimer-guest complexes as a strategy to increase the solubility of a phenazine N, N'-dioxide derivative with antitumor activity.

Poly(amidoamine) and Poly(propylenimine) dendrimers with different generations and peripheral groups were studied as solubility enhancers and nanocarriers for 7-bromo-2-hydroxy-phenazine N 5,N 10-dioxide. This compound possesses potential antitumoral and anti-trypanosomal activity, but its low solubility in physiological media precludes its possible application as therapeutic drug. The amino terminated dendrimers association with the active compounds as observed trough NMR studies showed that electrostatic interactions are essential in the solubilization enhancement process. The obtaining of a stable and no cytotoxic formulation makes the drug-carried association a suitable strategy for the generation of a drug delivery system for phenazine derivatives.

Raman spectroscopy and electronic microscopy structural studies of Caucasian and Afro human hair.

Human hair fibre is subjected to various structural modifications due to the application of chemicals such as dyes, shampoos and bleaches and/or physical procedures such as heating, and often more than one procedure is performed on the same hair. The present work aims to analyze the changes incurred in hair samples of two ethnic groups, namely Caucasian and Afro, before and after different treatments such as thermal, bleaching and straightening. In addition to observing the damage caused by each treatment separately, the study of samples that received all three treatments was carried out. For molecular structural characterization, the Raman vibrational spectroscopic technique was used and scanning electron microscopy (SEM) was used for morphological analysis of the hair fibres. This investigation has shown, through vibrational spectroscopy, that several important bonds have been modified, such as the S-S, C-S, C-C and S-O bonds as well as the secondary structures of proteins that have indergone changes in their conformation as a result of the treatment. Hair from the two ethnic groups showed small differences in relation to each applied treatment. Excessive heat generated a higher rate of Raman spectral band intensity changes when compared to the other treatments and it was observed that the action of several treatments on the same hair fibres resulted in even more pronounced structural changes. Finally, scanning electron microscopy showed that each treatment caused a different morphological deformation pattern on the capillary surface of the human hair.