The effects of lignin removal and drying on the porosity and enzymatic hydrolysis of sugarcane bagasse

The porosity of lignocellulosic materials is a key feature for the enzymatic hydrolysis of the constituent polysaccharides, being affected by its drying and lignin content. Here we evaluated the influence of both parameters in the porosity of sugarcane bagasse, using raw and chlorite-delignified samples. A fraction of these samples was air dried at room temperature and the remainder one was kept wet. All the samples were subjected to porometry (solute exclusion technique), determination of water retention value and assessment of enzymatic saccharification of polysaccharides. Samples with higher lignin contents had lower porosities and exhibited worse enzymatic conversions of polysaccharides. Mild drying collapsed only the smaller pores, which already were inaccessible to enzymes, and therefore did not affect the efficiencies of saccharification. Our results show that the lignin content plays an important role in the porosity of the material and that its removal improves the enzymatic saccharification of the constituent polysaccharides.     

Antitrypanasomal activity of novel benzaldehyde-thiosemicarbazone derivatives from kaurenoic acid

A series of new thiosemicarbazones derived from natural diterpene kaurenoic acid were synthesized and tested against the epimastigote forms of Trypanosoma cruzi to evaluate their antitrypanosomal potential. Seven of the synthesized thiosemicarbazones were more active than kaurenoic acid with IC?? values between 2-24.0 mM. The o-nitro-benzaldehyde-thiosemicarbazone derivative was the most active compound with IC?? of 2.0 mM. The results show that the structural modifications accomplished enhanced the antitrypanosomal activity of these compounds. Besides, the thiocyanate, thiosemicarbazide and the p- methyl, p-methoxy, p-dimethylamine, m-nitro and o-chlorobenzaldehyde-thiosemicarbazone derivatives displayed lower toxicity for LLMCK? cells than kaurenoic acid, exhibing an IC?? of 59.5 mM.     

Sol-Gel Synthesis of Transparent Alumina Gel and Pure Gamma Alumina by Urea Hydrolysis of Aluminum Nitrate

-Alumina was synthesized by a sol-gel method with the aluminum ion hydrolysis control performed by urea. The initial saturated Al³⁺/urea solution presented urea coordinated with the aluminum ion, as shown in the ¹³C NMR and ²⁷Al NMR spectra and longitudinal relaxation times, T ₁, from the latter. The substitution of water molecules in the Al³⁺ coordination shell by urea controlled the hydrolysis process and provided an extensive nucleation during the initial steps of the aluminum hydroxide formation due to urea thermolysis at 90°C. The resulting sol, composed of Al(OH)₃ nanoparticles, coalesced and became a transparent gel permeated by a solution of urea and the polycation ion [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺. The freshly prepared gel was transformed, under heating at 300°C, directly to -alumina, characterized by FTIR, ²⁷Al-MAS-NMR and S_BET techniques, without - or -phases, as a consequence of the high degree of homogeneity of the -alumina precursor.     

Highly luminescent CdTe/CdSe colloidal heteronanocrystals with temperature-dependent emission color

In this work we present the preparation of highly luminescent anisotropic CdTe/CdSe colloidal heteronanocrystals. The reaction conditions used (low temperature, slow precursor addition, and surfactant composition) resulted in a tunable shape from prolate to branched CdTe/CdSe nanocrystals. Upon CdSe shell growth the heteronanocrystals show a gradual evolution from type-I to type-II optical behavior. These heteronanocrystals show a remarkably high photoluminescence quantum yield (up to 82%) and negligible thermally induced quenching up to temperatures as high as 373 K.     

Antioxidant capacity and in vitro prevention of dental plaque formation by extracts and condensed tannins of Paullinia cupana

Chemical evaluation of the semi-purified fraction from the seeds of guaraná, Paullinia cupana H.B.K. var. sorbilis (Mart.) Ducke, yielded the following compounds: caffeine, catechin, epicatechin, ent-epicatechin, and procyanidins B1, B2, B3, B4, A2, and C1. Measurement of the antioxidant activity by reduction of the DPPH radical confirmed the anti-radical properties of the aqueous (AqE) and crude (EBPC) extracts and semi-purified (EPA and EPB) fractions. The EPA fraction showed radical-scavenging activity (RSA) and protected DPPH from discoloration at 5.23 +/- 0.08 (RSD% = 1.49) microg/mL, and for the phosphomolybdenum complex showed a higher Relative Antioxidant Capacity (RAC) at 0.75 +/- 0.01 (1.75). The EPA fraction had a total polyphenolics content of 65.80% +/- 0.62 (RSD% = 0.93). The plant drug showed 5.47% +/- 0.19 (RSD% = 3.51) and 6.19% +/- 0.08 (RSD% = 1.29) for total polyphenolics and methylxanthines, respectively. In vitro assessment of the antibacterial potential of the Paullinia cupana extracts against Streptococcus mutans showed that these could be used in the prevention of bacterial dental plaque.     

Determination of copper in medicinal plants used as dietary supplements by atomic absorption spectrometry with direct flame solid analysis

An alternative device for the direct solid analysis (DSA) for copper determination by flame atomic absorption spectrometry (FAAS) is proposed. Copper was directly determined in commercial medicinal plants used as dietary supplements. The determination of copper in solid samples by DSA–FAAS was made by using a conventional air–acetylene flame. Between 0.05 and 1.5 mg of each test, sample was weighed directly into a small polyethylene vial connected to the device used for solid introduction into the flame. Test samples were introduced into the flame as a dry aerosol using a T-quartz cell set between the burner and the optical path. The T-quartz cell has a slit in the superior part by which the solid aerosol passes to the flame. A transient signal, evaluated as integrated absorbance, is produced and it is totally integrated in 2 s. Background signals always presented absorbance values less than 0.1. It was found a characteristic mass of 0.8 ng Cu and absolute limit of detection of 1.2 ng (3 s), or 1.2 μg g⁻¹ if a sample mass of 1 mg was used. Optimized conditions for air flow rate, flame stoichiometry, and so on were established as well. No excessive grinding of the samples was needed and samples with particle of size less than 80 μm were used throughout. No statistical difference between the results from the proposed system and those obtained by sample digestion and determination by conventional FAAS was observed. With the proposed procedure, more than 50 test samples can be analyzed in 1 h and it can be easily adapted to conventional spectrometers for FAAS.     

Probing the wave function of shallow Li and Na donors in ZnO nanoparticles

Electron paramagnetic resonance and electron nuclear double resonance (ENDOR) experiments on ZnO nanoparticles reveal the presence of shallow donors related to interstitial Li and Na atoms. The shallow character of the wave function is evidenced by the multitude of 67Zn ENDOR lines and further by the hyperfine interactions with the 7Li and 23Na nuclei that are much smaller than for atomic lithium and sodium. In the case of the Li-doped nanoparticles, an increase of the hyperfine interaction with the 7Li nucleus and with the 1H nuclei in the Zn(OH)(2) capping layer is observed when reducing the size of the nanoparticles. This effect is caused by the confinement of the shallow-donor 1s-type wave function that has a Bohr radius of about 1.5 nm, i.e., comparable to the dimension of the nanoparticles.     

Highly corrosion resistant siloxane-polymethyl methacrylate hybrid coatings

Siloxane-polymethyl methacrylate hybrid films were deposited on carbon steel substrates by dip-coating from a sol prepared by acid-catalyzed hydrolytic co-polycondensation of tetraethoxysilane (TEOS) and 3-methacryloxy propyl-trimethoxysilane (MPTS), followed by radical polymerization of methyl methacrylate (MMA). Structural properties of the hybrids were studied using ²⁹Si and ¹³C nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA), as a function of the MMA/MPTS ratio, which ranged between 2 and 10. The efficiency of corrosion protection of hybrid-coated carbon steel was investigated by XPS, potentiodynamic polarization curves and electrochemical impedance spectroscopy after immersion of the material in acidic and neutral saline aqueous solution. The NMR and TGA results indicate a high degree of polycondensation (84%) and elevated thermal stability of 410?°C for the hybrid film with a MMA/MPTS ratio of 8, exhibiting also and excellent adhesion to the substrate. The XPS analysis confirmed the variation of the MMA phase in the hybrid, and showed that no corrosion-induced changes had occurred after 18?days immersion of the coated steel in 3.5% NaCl solution. Potentiodynamic polarization curves have shown that the hybrid coating prepared using a TEOS/MPTS ratio of 8 yielded the best anti-corrosion performance. It acts as a very efficient corrosion barrier, increasing the total impedance by almost 6 orders of magnitude and reducing the current densities by 4 orders of magnitude, compared to the bare electrode. The obtained results are discussed based on the correlation of structural information with impedance data presented for both electrolytes in the form of electrical equivalent circuits.