Determination of trace elements in tree rings ofPinus by neutron activation analysis

The elemental composition of pine trees as a function of age was achieved by the tree-ring method. By using instrumental neutron activation analysis, trace elements were determined in individual rings ofPinus elliottii var.elliottii of 32, 14 and 9 years, from an implanted forest ofPinus sp., Buri, São Paulo, far away from industrial pollution. Different components of the system such as needles, pith, bark, soil and litter were also analyzed for 18 elements (As, Br, Ce, Co, Cs, Eu, Fe, Hf, K, La, Mn, Na, Rb, Sc, Sm, Yb, Zn, and Zr). Al, B, Ba, Ca, Fe, K, Mg, and P concentrations were determined by atomic absorption and/or emission spectrometry (AAS; ICP-AES). Some elements have showed similar radial distribution of the concentration for the three ages. Abrupt concentration changes in the pith and ring-bark boundary corresponding to the first and last growth rings were observed.     

Morphological and structural characteristics of diazo dyes at the air-water interface: in situ Brewster angle microscopy and polarized UV/vis analysis

A morphological analysis is presented for Langmuir films of the diazo dyes Sudan 4 (S4), Sudan 3 (S3), and Sudan red (SR), using Brewster angle microscopy. Stable nonmonomolecular structures are formed at the air-water interface denoted as a plateau in the pressure-area isotherms. Monolayer domains are evident by the contrastless image even before the pressure onset, which grow in size until it reached a condensed monolayer. This behavior resembles that of Langmuir films from simple aromatic fatty acids. Films from all the azo dyes display similar features, according to the surface potential isotherms and in situ polarized UV/vis spectroscopy except for the larger area per molecule occupied by S4 and SR. This is attributed to the presence of CH(3) groups that cause steric hindrance modifying the organization of diazo dye molecules at the air-water interface. UV/vis polarized absorption spectroscopy showed preferential orientation of S4 and S3 on the water surface, while SR molecules lie isotropically. For these three diazo dyes, film absorption was negligible at very large areas per molecule, becoming nonzero only at a critical area coinciding with the onset of surface potential. The critical area is ascribed to the formation of a H-bonded network between water molecules and diazo dye headgroups.     

Synthesis of pyrrolidine-substituted benzamides via iodocyclization of β-enaminoesters

Novel 2-, and N-substituted 5-methylene-pyrrolidine benzamides and 2-, 3-, and N-substituted 5-methylene-2-pyrroline benzamides were synthesized for the first time in a straightforward manner and in good yields via iodocyclization of γ- and α-alkenyl-β-enaminoesters, respectively. The key step in the process is the synthesis of the methylene-pyrrolidine iodide and methylene-2-pyrroline iodide intermediates. Functional group inter-conversion of these iodides to their amino analogs, and their subsequent coupling to benzoic acids via EDC, afforded the above pyrrolidine/2-pyrroline-substituted benzamides in yields of around 75%.     

Optimization of acid hydrolysis of sugarcane bagasse and investigations on its fermentability for the production of xylitol by Candida guilliermondii

The dilute-acid hydrolysis of sugarcane bagasse was optimized using a statistical experimental design resulting in hydrolysates containing 57.25 g/L of xylose, which were fermented with a high inoculum concentration (10 g/L of the yeast Candida guilliermondii IM/UFRJ 50088). The addition of urea reduced the time of conversion (t _C) to 75 h (without nitrogen source addition t _C>127 h), and, consequently, improving the rates of xylitol bioproduction. Fermentator experiments, using the optimized conditions, resulted in enhanced conversion rates, reducing t _C to 30 h. The stability of the yeast in the hydrolysate was also verified in a 480-h cultivation.     

Complex Tellurium Salts with Supramolecular Bidimensional Lattices: Synthesis and X‐ray Characterization of (2‐Br‐C5NH5)2[TeX6] (X = Cl,Br)

The reaction of tellurium(IV) tetrahalides with hydrochloric and hydrobromic acid leads to the formation of (H₃O)₂[TeX₆], which reacts subsequently with (2‐Br‐C₅NH₅)⁺X^‐ to afford (2‐Br‐C₅NH₅)₂[TeCl₆] ( 1 ) and (2‐Br‐C₅NH₅)₂[TeBr₆] ( 2 ). The structure of the complex salts were analysed by X‐ray diffractometry affording the centrosymmetric space groups P2₁/n (monoclinic, 1 ) and P1¯ (triclinic, 2 ). Interionic hydrogen bondings hold their lattices in bidimensional supramolecular arrays not yet described in the literature. The lone electron pair of the AX₆E‐system of the hexahalotellurates [TeX₆]^2‐ (X = Cl, Br) seems to be fully delocalized since only small octahedral deviations were observed for the anionic species. The structures of the title compounds were refined with the Te atoms occupying sites with full point symmetry, approximately m3¯m. In both cases the Te atoms enclose centers of inversion and the octahedrally dynamic structures are enforced and stabilized along the supramolecular lattices by the crystal field of the 2‐Br‐pyridinium cations.     

The glucocorticoid derivative with the phthalimide group cationic nanocrystal for ophthalmic application: a design space development approach

The glucocorticoid derivative of budesonide with a phthalimide group is a drug candidate to treat inflammatory eye diseases; nevertheless, it presents low water solubility. Drug nanocrystals have been proposed to overcome this hurdle. The development of an innovative ophthalmic anti-inflammatory nanosuspension was performed using a design space approach. We obtained the particle size reduction of this glucocorticoid derivative on a nanometer scale (approximately 165.0 nm), applying wet bead milling on a super reduced scale. The design of experiment supported the optimization of the formula evaluating the parameters that influence reducing the particle size and also allowed determining the design space. Considering the two statistical models developed and the size range obtained, we proposed that the optimized formulation for the glucocorticoid derivative nanosuspension may be 1.0 wt% glucocorticoid derivative and 0.092 wt% cetylpyridinium chloride. This formulation was characterized by the morphological, physical–chemical, and mucoadhesive in vitro test and showed potential for ophthalmic use with reduced frequency of product application, improved efficiency, and safety, which may promote better patient compliance.     

Biotransformation of (−)β-pinene by Aspergillus niger ATCC 9642

The main objective of this work was to investigate the biotransformations of (−)α-pinene, (−)β-pinene, and (+) limonene by Aspergillus niger ATCC 9642. The culture conditions involved—concentration of cosolvent (EtOH), substrate applied, and sequential addition of substrates—were investigated. Adaptation of the precultures with small amounts of substrate was also studied. The experiments were performed in conical flasks with liquid cultures. This strain of A. niger was able to convert only (−)β-pinene into α-terpineol. An optimum conversion of (−)β-pinene into α-terpineol of about 4% was obtained when the substrate was applied as a diluted solution in EtOH and sequential addition of substrate was used.     

Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface

The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.     

Molecular-level control of the photoluminescence from PPV nanostructured films

The fabrication of varied molecular architectures in layer-by-layer (LbL) films is exploited to control the photoluminescence (PL) of poly(p-phenylene vinylene) (PPV) in an unprecedented way. This was achieved by controlling the F?rster energy transfer between PPV layers (donors) and layers of a commercial azodye, Brilliant Yellow (BY) (acceptors). Energy transfer was controlled by inserting spacer layers of inert polymers between PPV and BY layers and by photoaligning the BY molecules via trans-cis-trans isomerization. The PPV/BY LbL films displayed polarized PL whose intensity could be varied almost continuously by changing the time of photoalignment, which was carried out by impinging a linearly polarized laser light simultaneously to the PL experiments. For PPV/BY films with no spacer layers, PL was completely quenched, but its intensity increased with the number of spacing layers. Further increase in PL was obtained by photoaligning the BY molecules perpendicularly to the PPV molecules. This minimizes energy transfer, since F?rster processes are directional, dipole-dependent resonant transfers. Energy transfer is also controlled by imparting a preferential orientation of the PPV chains on PPV/BY LbL films deposited onto flexible Teflon substrates that may be stretched.     

A new electrolytic dissolution of aluminum alloys and determination of some constituents by inductively coupled plasma optical emission spectrometry

The new electrolytic dissolution in batch of aluminum alloys samples as grains or turns and the determination of Fe, Cu, Mn, Mg, Cr, Ni, Zn, Pb and Ti by ICP OES was investigated. In on-line electrodissolution procedures described in the literature, samples were restricted to be in the form of solid blocks or plates with one polished flat face. Here, the sample was loaded in the barrel of a modified disposable syringe (the anodic semi-cell) and pressed with a modified plunger fitted with a platinum disk to establish electrical contact with the analyte. This arrangement was introduced in a beaker containing the electrolyte (1 mol L⁻¹ HNO₃) and a platinum wire as the cathode. The resulting solution from electrodissolution (0.6 A) was used for the ICP OES determinations. The influence of the aluminum concentration increase on the determination of the elements was evaluated. Electrodissolution of certified reference materials and commercial samples revealed relative errors lower than 10% for the elements Fe, Cu, Mg, Ni, Cr, Zn and Ti (when their content is above 0.1%). Higher inaccuracies (>10%) were observed for Mn and for Fe in B.C.S. 268/1 reference material certified. The proposed method presented a relative standard deviations (R.S.D.) lower or circa 10% to all of the elements (except Pb). In comparison with traditional acid dissolution, the proposed electrodissolution method is relatively fast (about 30 min), it is clean (there is no projection of solution) and simple (heating and fumes exhaust system were not necessaries).