TG and DSC as tools for confirming hybrid vermiculites derived from intercalation

Vermiculite was prepared to react with aliphatic diamines (ethylene-, trimethylene-, tetramethylene- and hexamethylene-) diamine. The products were characterized by elemental analysis, infrared spectroscopy and X-ray diffraction. The amounts of diamines adsorbed were 0.89, 0.86, 0.79 and 0.68 mmol g^–1, respectively for NH₂(CH₂)⋅nNH₂ where n=2, 3, 4, 6. The basal spacings of the intercalated vermiculites varied between 1300 and 1470 pm. Thermogravimetry and DSC data confirmed intercalation of diamines in gallery space of vermiculite.     

Natural vermiculite as an exchanger support for heavy cations in aqueous solution

The natural highly charged lamellar silicate vermiculite was investigated as an exchanger matrix in doubly distilled water solution to exchange magnesium inside the lamella with the heavy cations copper, nickel, cobalt, and lead at the solid/liquid interface. The extension of each exchange reaction was dependent on time of reaction, pH, and cation concentration. The maximum time presented the following order Pb2+ < Ni2+ < Cu2+ < Co2+, which corresponds to 12, 24, 48, and 72 h, respectively. The best performance was observed for nickel, as represented by the exchange capacity Nf, which gave values 0.59, 0.76, 0.84, and 0.93 mmol g(-1) for Pb2+ < Co2+ < Cu2+ < Ni2+, respectively. This capacity is dependent on pH interval variation from 1 to 9, being significantly increased in alkaline condition. The isotherm data were adjusted to a modified Langmuir equation and from the data the spontaneous Gibbs free energy was calculated. Linear correlations were obtained through Gibbs free energy or the maximum capacity against the cationic radius plot, with the lowest values for the largest cation lead. An exponential correlation was also observed for the maximum capacity versus enthalpy of hydration plot, indicating a difficulty of the less hydrated cation, lead, in exchanging with magnesium inside the lamellar space, as suggested by the proposed mechanism. The saturated matrices with cations presented a decrease in interlayer distance in comparison with the original vermiculite, which can be related to the hydrated phases, characteristic for each cation, with a lowest value for lead.     

Synthesis and characterization of hybrids derived from vermiculite chloropropyl and aliphatic diamines

Silylation of vermiculite surface with organosilane (H₃CO)₃SiR, being R is the corresponding organic moieties –CH₂CH₂CH₂Cl, were carried out to yield organofunctionalized nanomaterial, named as VCl. The product reacted subsequently with three aliphatic diamines H₂N (CH₂)_nNH₂ (n=2, 4 and 6). The new hybrids were characterized by elemental analysis, infrared spectroscopy, X-ray diffraction and thermogravimetry. The grafting chloro derivates onto surface amounted to 2.1 mmol g^–1. The incorporation of alkyl amines was more effective for butyl>ethylene>hexyldiamines. The sequence is in agreement with thermogravimetry and elemental analysis data.     

Methodology to Quantify and Screen the Demineralization of Teeth by Immersing Them in Acidic Drinks (Orange Juice,Coca-Cola™, and Grape Juice): Evaluation by ICP OES

Oral health problems may occur as a result of the ingestion of acid drinks. The objective of this in vitro study was to quantify and screen the concentration of potassium (K), phosphorus (P), calcium (Ca), magnesium (Mg), manganese (Mn), zinc (Zn), iron (Fe), copper (Cu), barium (Ba), lead (Pb), arsenic (As), cadmium (Cd), aluminum (Al), cobalt (Co), chromium (Cr), molybdenum (Mo), sodium (Na), nickel (Ni), selenium (Se), and vanadium (V) released from bovine incisors during an erosive challenge at different times of exposure when immersed in Coca-Cola™, orange juice, and grape juice. A total of 240 samples of bovine incisor teeth were used for the erosive challenge and allocated in groups. Digestion of drinks was performed using microwave-assisted digestion. The content in acidic drinks was monitored before and after the erosive challenge at exposure times of 1, 5, and 60 min using inductively coupled plasma optical emission spectrometry (ICP OES). The drinks’ pH varied slightly during the erosive challenge but remained below the critical value of pH 5 to cause tooth demineralization. The concentrations of elements released from the bovine incisors during the in vitro erosive challenge depend on exposure times when immersed in acidic beverages. For some elements such as Ca, Mn, Zn, Fe, Cu, Ba, Pb, As, and Cd, quantified in acidic drinks, grape juice had greater erosive potential than Coca-Cola™ and orange juice. Quantification and monitoring of chemical elements in bovine teeth can be performed considering a longer erosive time and other types of acidic drinks. Further analysis using human teeth is still not available and must be conducted. The demineralization of teeth not only occurs in acidic beverages; physical and chemical factors play other roles and should be investigated.     

Enthalpies of formation of adducts of antimony(III) iodide with pyridine and methyl-pyridines

Solid adducts of formula SbI₃·L (L = pyridine or 2-, 3- or 4-methylpyridine abbreviated as Py, 2MPy, 3MPy or 4MPy) were synthesized and characterized by elemental analysis, IR spectroscopy and thermal analysis. IR data showed that coordination to antimony is through nitrogen. Thermal degradation of adducts starts at 431, 423, 413 and 411 K for Py, 2MPy, 3MPy and 4MPy, respectively. Reaction-solution calorimetry was used to evaluate the enthalpy change of reaction: SbI₃(cr) + L(l) = SbI₃·L(cr), 61.13 ± 1.75, −82.60 ± 1.55, −67.50 ± 0.97 and −74.10 ± 1.19 kJ mol⁻¹, respectively. Enthalpy change values for decomposition of adducts, lattice enthalpies and enthalpies of the Lewis acid-base reaction in the gas phase were calculated through appropriate thermochemical cycles. Mean SbN bond enthalpies were estimated as 134 ± 3, 154 ± 3, 140 ± 3 and 147 ± 4 kJ mol⁻¹, for Py, 2MPy, 3MPy and 4MPy, respectively.     

Correlations between data of <Superscript>29</Superscript>Si NMR and thermogravimetry for silica/monetite nanocomposites

Silica/monetite nanocomposites were synthesized through controlled hydrolysis of tetraethoxysilane at concentrations of 5, 10, 15, and 20% mol/mol of calcium phosphate forming the solids named CaPSil1, CaPSil2, CaPSil3, and CaPSil4, respectively. XRD patterns showed formation of nanocomposites with a decrease in crystallinity. The NMR ²⁹Si spectra suggested an increase in the content of incorporated silica with reduction of Q³ (–SiOH) signal, which contributes for mass loss, in agreement with thermogravimetry. The incorporation of silica increased the chemical stability of the precursor phosphate in an acidic medium.     

Photochemical formation of hydroxyl radicals in tissue extracts of the coral Galaxea fascicularis

Various stresses induce the formation of reactive oxygen species (ROS) in biological cells. In addition to stress-induced ROS, we studied the photochemical formation of hydroxyl radicals (˙OH), the most potent ROS, in coral tissues using phosphate buffer-extracted solutions and a simulated sunlight irradiation system. ˙OH formation was seen in extracts of both coral host and endosymbiont zooxanthellae. This study is the first to report quantitative measurements of ˙OH photoformation in coral tissue extracts. Our results indicated that whether or not coral bleaching occurred, coral tissues and symbiotic zooxanthellae have the potential to photochemically produce ˙OH under sunlight. However, no significant difference was found in the protein content-normalized formation rates of ˙OH between corals incubated under different temperatures and irradiance conditions. ˙OH formation rates were reduced by 40% by reducing the UV radiation in the illumination. It was indicated that UV radiation strongly affected ˙OH formation in coral tissue and zooxanthellae, in addition to its formation through photoinhibition processes.     

Thioglycolic acid grafted onto silica gel and its properties in relation to extracting cations from ethanolic solution determined by calorimetric technique

Thioglycolic acid was immobilized onto silica gel surface using 3-aminopropyltrimethoxysilane as precursor silylating agent to yield silica. The amount of thioglycolic acid immobilized was 1.03 mmol per gram of silica. This new surface displayed a chelating moiety containing nitrogen, sulfur, and oxygen basic centers which are potentially capable of extracting cations from ethanolic solution, such as MCl3 ( M=Fe, Cr, and Mo). This process of extraction was carried out by the batch method when similar chemisorption isotherms were observed for all cations. The data were adjusted to a modified Langmuir equation. The sequence of the maximum retention capacity was Cr(III) > Mo(III) > Fe(III). The same adsorption was determined by calorimetric titration and the enthalpic values of -35.75 +/- 0.02, 32.90 +/- 0.15, and -84.08 +/- 0.12 kJmol(-1) for chromium, molybdenum, and iron, respectively, were obtained. From the calculated Gibbs free energy -23.4 +/- 0.2, -27.2 +/- 0.2, and -32.7 +/- 0.3 kJmol(-1), the variations in entropy obtained were 42 +/- 1, 201 +/- 1, 172 +/- 1 JK(-1)mol(-1) for the same sequence. All thermodynamic values are in agreement with the spontaneity of the proposed cation-basic center interactions for these chelating processes.     

Chemisorption and thermodynamic data of the interaction between a chelate free acidic center with basic groups attached to grafted silicas

The molecule 2-aminoethanethiol was added to the grafted silylant agent [(3-chlorosilylpropyl)trimethoxysilane] (cpts) onto silica gel(triple bond SilCl), obtaining a surface (triple bond SilSNH(2)) and giving 0.70 mmol g(-1) of nitrogen; the surface of silica was modified with [(3-mercaptosilylpropyl)trimethoxysilane] (mpts) with surface (triple bond SilSH), giving 0.78 mmol g(-1) of sulphur. Both matrices, (triple bond SilSNH(2)) and (triple bond SilSH), adsorb copper and cobalt acetylacetonates from ethanolic solution. Adsorption, using a batchwise process, showed that copper chelate was the most adsorbed. The interactions between the basic centers attached to organic chains of these modified silicas with the cations in the chelates Me(acac)(2) [M=Cu and Co] were followed through calorimetric titrations. Exothermic enthalpic results were obtained for the triple bond SilSNH(2) matrix. The spontaneity of these systems was reflected in negative free Gibbs energy and positive from entropic values.