Ternary surface complex: coadsorption of Cu(II), Zn(II), Cd(II) and nitrilotris(methylenephosphonic) acid onto boehmite

This work studies the effect of NTMP (nitrilotris(methylenephosphonic acid)) on the adsorption of Cu(II), Zn(II), and Cd(II) onto boehmite in the pH range 5-9.5. The data were analyzed using the 2-pK constant capacitance model (CCM) assuming ternary surface complex formation. Under stoichiometric conditions, NTMP is more effective for removing Cu(II) than Zn(II) from solution and the contribution of ternary surface complexes are important to model the adsorption of both metals. Under nonstoichiometric conditions and high surface loading with a Me(II)/NTMP ratio of 1:5, Cu(II) and Zn(II) adsorption is significantly suppressed. In the case of Cd(II) the free metal adsorption is the most dominant species.

Geração de mesoporos em zeólitas ZSM-5 e seus efeitos na conversão do etanol em olefinas

Developing mesoporosity in HZSM-5 zeolites is an alternative for improving their catalytic performance on chemical reactions. In this work, alkaline and thermal treatments were used to produce mesoporosity. These treatments increased mesoporous area and volume. They also influenced the acid properties of the samples. Concerning catalytic performance, treatments modified reaction product distribution. Whereas alkaline treatment favored formation of olefins and increased propene ratio in the beginning of the reaction, thermal treatment resulted in formation of only ethylene due to the low acidity of the sample.

Xylitol from rice husks by acid hydrolysis and Candida yeast fermentation

An investigation was conducted into the production of xylose by acid hydrolysis of rice husks and its subsequent bioconversion to xylitol. The parameters were optimised using the response surface methodology. The fermentation stage took place with the aid of the yeast species Candida guilliermondii and Candida tropicalis. An evaluation of the influence of several biomass pre-treatments was also performed. The effects of the acid concentration and hydrolysate pH on xylitol global yield were also assessed, and the highest yield of xylitol was 64.0% (w/w). The main products, xylose and xylitol, were identified and quantified by means of liquid chromatography.

Improved method to obtain pfaffic acid as a marker for quality control

Pfaffic acid, a marker of Hebanthe eriantha (Brazilian ginseng), was first isolated in 1983 but is not yet commercially available. This lack of availability compromises the quality control of this plant and its derivatives. This paper proposes a process for pfaffic acid isolation from roots of H. eriantha at a purity suitable for analytical purposes. The steps involved in this process included extraction, hydrolysis, fractionation and purification by preparative HPLC. This process led to isolation of pfaffic acid with a chromatographic purity of 98.5% in a 0.25% yield from dried roots of H. eriantha; this yield is more than forty times higher than that of the current method in the literature.

UV determination of epinephrine, uric acid, and acetaminophen in pharmaceutical formulations and some human body fluids using multivariate calibration

In this work, a spectrophotometric methodology was applied in order to determine epinephrine (EP), uric acid (UA), and acetaminophen (AC) in pharmaceutical formulations and spiked human serum, plasma, and urine by using a multivariate approach. Multivariate calibration methods such as partial least squares (PLS) methods and its derivates were used to obtain a model for simultaneous determination of EP, UA and AC with good figures of merit and mixture design was in the range of 1.8 - 35.3, 1.7 - 16.8, and 1.5 - 12.1 µg mL-1. The 2nd derivate PLS showed recoveries of 95.3 - 103.3, 93.3 - 104.0, and 94.0 - 105.5 µg mL-1 for EP, UA, and AC, respectively.

TUNGSTOPHOSPHORIC ACID HETEROGENIZED ONTO NH4ZSM5 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE PHOTOCATALYTIC DEGRADATION OF DYES

Materials based on tungstophosphoric acid (TPA) immobilized on NH4ZSM5 zeolite were prepared by wet impregnation of the zeolite matrix with TPA aqueous solutions. Their concentration was varied in order to obtain TPA contents of 5%, 10%, 20%, and 30% w/w in the solid. The materials were characterized by N2 adsorption-desorption isotherms, XRD, FT-IR, 31P MAS-NMR, TGA-DSC, DRS-UV-Vis, and the acidic behavior was studied by potentiometric titration with n-butylamine. The BET surface area (SBET) decreased when the TPA content was raised as a result of zeolite pore blocking. The X-ray diffraction patterns of the solids modified with TPA only presented the characteristic peaks of NH4ZSM5 zeolites, and an additional set of peaks assigned to the presence of (NH4)3PW12O40. According to the Fourier transform infrared and 31P magic angle spinning-nuclear magnetic resonance spectra, the main species present in the samples was the [PW12O40]3- anion, which was partially transformed into the [P2W21O71]6- anion during the synthesis and drying steps. The thermal stability of the NH4ZSM5TPA materials was similar to that of their parent zeolites. Moreover, the samples with the highest TPA content exhibited band gap energy values similar to those reported for TiO2. The immobilization of TPA on NH4ZSM5 zeolite allowed the obtention of catalysts with high photocatalytic activity in the degradation of methyl orange dye (MO) in water, at 25 ºC. These can be reused at least three times without any significant decrease in degree of degradation.

SYNTHESIS AND BIOLOGICAL EVALUATION OF SPIRO[INDOLINE-3,4’-PYRANO[2,3-C:6,5-C’]DIPYRAZOL]- 2-ONES IN THE PRESENCE OF SBA-Pr-SO3H AS A NANOCATALYST

Sulfonic acid functionalized SBA-15 nanoporous material (SBA-Pr-SO3H) with a large pore size of 6 nm, a high surface area, high selectivity, and excellent chemical and thermal stability was applied as an efficient heterogeneous nanoporous acid catalyst in the reaction of isatin with pyrazolones under mild reaction conditions. A novel class of symmetrical spiro[indoline-3,4'-pyrano[2,3-c:6,5-c']dipyrazol]-2-one derivatives was successfully obtained in high yields. Comparison of these results with those reported in the literature shows that the current method is efficient, and results in better reaction times and yields of the desired products. Other advantages of this new method are its operational simplicity, easy work-up procedure, and the use of SBA-Pr-SO3H as a reusable and environmentally benign nanoreactor, such that the reaction proceeds easily in its nanopores. We also tested the antimicrobial activity of the prepared compounds using the disc diffusion method, and some of the synthesized compounds exhibited the best results against B. subtilis and S. aureus.

2-(4-IODO-2,5-DIMETOXIFENIL)-N-[(2-METOXIFENIL)METIL]ETAMINA OU 25I-NBOME: CARACTERIZAÇÃO QUÍMICA DE UMA DESIGNER DRUG

Drug trafficking and the introduction of new drugs onto the illicit market are one of the main challenges of the forensic community. In this study, the chemical profile of a new designer drug, 2-(4-iodine-2,5-dimethoxyphenyl)-n-[(2-methoxyphenyl)methyl]etamine or 25I-NBOMe was explored using thin layer chromatography (TLC), ultraviolet-visible spectrophotometry (UV-Vis), attenuated total reflection with Fourier transform infrared spectroscopy(ATR-FTIR), gas chromatography mass spectrometry (GC-MS) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). First, the TLC technique was effective for identifying spots related to 25C-, 25B- and 25I-NBOMe compounds, all with the same retention factor, Rf ≈ 0.50. No spot was detected for 2,5-dimethoxy-4-bromoamphetamine, 2,5-Dimethoxy-4-chloroamphetamine or lysergic acid diethylamide compounds. ATR-FTIR preserved the physical-chemical properties of the material, whereas GC-MS and ESI-MS showed better analytical selectivity. ESI(+)FT-ICR MS was used to identify the exact mass (m/z428.1706 for the [M + H]+ ion), molecular formula (M = C18H22INO3), degree of unsaturation (DBE = 8) and the chemical structure (from collision induced dissociation, CID, experiments) of the 25I-NBOMe compound. Furthermore, the ATR-FTIR and CID results suggested the presence of isomers, where a second structure is proposed as an isomer of the 25I-NBOMe molecule.

Amperometric biosensor for ascorbic acid

A L-ascorbic acid biosensor based on ascorbate oxidase has been developed. The enzyme was extracted from the mesocarp of cucumber (Cucumis sativus) by using 0.05 mol L-1 phosphate buffer, pH 5.8 containing 0.5 mol L-1 NaCl. After the dialysis versus phosphate buffer 0.05 mol L-1 pH 5.8, the enzyme was immobilized onto nylon net through glutaraldehyde covalent bond. The membrane was coupled to an O2 electrode and the yielding reaction monitored by oxygen depletion at -600 mV using flow injection analysis optimized to 0.1 mol L-1 phosphate buffer pH 5.8, as the carrier solution and flow-rate of 0.5 mL min-1. The ascorbic acid calibration curve was linear from 1.2x10-4 to 1.0x10-3 mol L-1. The evaluation of biosensor lifetime leads to 500 injections. Commercial pharmaceutical samples were analyzed with the proposed method and the results were compared with those obtained by high-performance liquid chromatography (HPLC).

Comparative analysis of the trypanocidal activity and chemical properties of E-lychnophoric acid and its derivatives using theoretical calculations

E-Lychnophoric acid 1, its derivative ester 2 and alcohol 3 killed 100% of trypomastigote blood forms of Trypanosoma cruzi at the concentrations of 13.86, 5.68, and 6.48 µg/mL, respectively. Conformational distribution calculations (AM1) of 1, 2 and 3 gave minimum energies for the conformers a, b, c, and d, which differ from each other only in the cyclononene ring geometry. Calculations (DFT/BLYP/6-31G*) of geometry optimization and chemical properties were performed for conformers of 1, 2, and 3. The theoretical results were numerically compared to the trypanocidal activity. Calculated values of atomic charge, orbital population, and vibrational frequencies showed that the C-4-C-5 pi-endocyclic bond does not affect the trypanocidal activity of the studied compounds. Nevertheless, the structure of the group at C-4 strongly influences the activity. However, the theoretical results indicated that the intra-ring (C-1 and C-9) and pi-exocycle (C-8 and C-14) carbons of caryophyllene-type structures promote the trypanocidal activity of these compounds.

Ascorbic acid determination using a carbon paste electrode modified with iron(III) ions adsorbed on humic acid

An amperometric sensor was constructed, by using humic acids to immobilize Fe3+ ions on a carbon paste electrode (CPE-HA-Fe), and used for ascorbic acid (H2A) determination. The cyclic voltammogram of the electrode showed electrochemical response due to the Fe3+/Fe2+ couple at E1/2=+0.78 V vs SCE, using 0.5 mol L-1 KCl and 0.2 mol L-1 acetate/0.020 mol L-1 phosphate buffer, at pH = 5.4, as supporting electrolyte. When H2A is added to the electrolyte solution it is observed an oxidation process. The oxidation current, obtained by chronoamperommetry at +0.87 V vs SCE, is proportional to the concentration, represented by the equation I(µA) = 7.6286 [H2A] (mmol L-1) + 1.9583, r = 0.9996, for concentrations between 0.0 and 1.4 mmol L-1. The electrode showed high stability and was used for H2A determination in a natural orange juice.

Potentiometric and conductometric studies on the system acid-isopolytungstate and the formation of lanthanum tungstates

The stoichiometry of the polyanions formed by the action of nitric acid on sodium tungstate (< 0.01M) has been studied by means of electrometric techniques involving pH-potentiometric and conductometric titrations. The well defined inflections and breaks in the titration curves provide evidence for the existence of the polyanions, para-W12O41(10-) and meta-W12O39(6-) corresponding to the ratio of H+:WO4(2-) as 7:6 and 9:6 in the pH ranges 5.7-6.0 and 3.6-4.1, respectively. The interaction of lanthanum nitrate with sodium tungstate solutions, at specific pH levels 8.0, 5.9 and 4.0 was also studied by pH and conductometric titrations, in aqueous and alcoholic media, with each of the reagents alternatively used as titrant. The electrometric experiments provide definite evidence of the formation of normal-La2O3.3WO3, para-5La2O3.36WO3 and meta-La2O3.12WO3 tungstates in the vicinity of pH 6.3, 5.0 and 4.2, respectively. Analytical investigations on the precipitates formed confirm the results of the electrometric study.

Anacardic acid derivatives from Brazilian propolis and their antibacterial activity

Propolis is a sticky, gummy, resinous substance collected by honeybees (Apis mellifera L.) from various plant sources, which has excellent medicinal properties. This paper describes the isolation and identification of triterpenoids and anacardic acid derivatives from Brazilian propolis and their antibacterial activity. Their structures were elucidated by ¹H and 13C NMR, including uni- and bidimensional techniques; in addition, comparisons were made with data from academic literature. These compounds were identified as: cardanols (1a + 1b), cardols (2a + 2b), monoene anacardic acid (3), a-amirine (4), b-amirine (5), cycloartenol (6), 24-methylene-cycloartenol (7) and lupeol (8). The determination of the position of the double bond after a reaction with Dimethyl disulfide (DMDS) is described for the phenol derivatives. The ethanolic extract was tested in vitro for antimicrobial activity by using the disc diffusion method and it showed significant results against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Shigella spp.

Mathematical equation correction to spectral and transport interferences in high-resolution continuum source flame atomic absorption spectrometry: determination of lead in phosphoric acid

In this work, a new mathematical equation correction approach for overcoming spectral and transport interferences was proposed. The proposal was applied to eliminate spectral interference caused by PO molecules at the 217.0005 nm Pb line, and the transport interference caused by variations in phosphoric acid concentrations. Correction may be necessary at 217.0005 nm to account for the contribution of PO, since Atotal217.0005 nm = A Pb217.0005 nm + A PO217.0005 nm. This may be easily done by measuring other PO wavelengths (e.g. 217.0458 nm) and calculating the relative contribution of PO absorbance (A PO) to the total absorbance (Atotal) at 217.0005 nm: A Pb217.0005 nm = Atotal217.0005 nm - A PO217.0005 nm = Atotal217.0005 nm - k (A PO217.0458 nm). The correction factor k is calculated from slopes of calibration curves built up for phosphorous (P) standard solutions measured at 217.0005 and 217.0458 nm, i.e. k = (slope217.0005 nm/slope217.0458 nm). For wavelength integrated absorbance of 3 pixels, sample aspiration rate of 5.0 ml min-1, analytical curves in the 0.1 - 1.0 mg L-1 Pb range with linearity better than 0.9990 were consistently obtained. Calibration curves for P at 217.0005 and 217.0458 nm with linearity better than 0.998 were obtained. Relative standard deviations (RSD) of measurements (n = 12) in the range of 1.4 - 4.3% and 2.0 - 6.0% without and with mathematical equation correction approach were obtained respectively. The limit of detection calculated to analytical line at 217.0005 nm was 10 µg L-1 Pb. Recoveries for Pb spikes were in the 97.5 - 100% and 105 - 230% intervals with and without mathematical equation correction approach, respectively.