Sodium removal and catalytic properties of HNaZSM-20 zeolite. Comparison with Y zeolite

A series of HNaZSM-20 catalysts with a varying amount of sodium cations were studied. The samples were prepared by ion exchange starting with a NaZSM-20 sample. The observedammonium-sodium exchange efficiency was slightly higher for ZSM-20 than for Y zeolite. The HNaZSM-20 series presentedhigher cracking activities in then-heptane transformation than the corresponding HNaY series. A decrease in theselectivity for coke deposition with sodium removal was also observed.     

Study of the thermal behavior of Al(III) and In(III)-diclofenac complexes in solid state

The Al and In-diclofenac compounds were prepared. Thermogravimetry (TG) and X-ray diffraction powder patterns were used to characterize these compounds. Details concerning the dehydration and thermal decomposition as well as data of kinetic parameters have been described here. The kinetic studies of these stages were evaluated from several heating rates with mass sample of 2 and 5 mg in open crucibles under nitrogen atmosphere. The results of the present study improve the knowledge on these compounds including their dehydration and thermal stability. The obtained data leads to a dependence on the sample mass, which results in two kinetic behavior patterns.     

Selective Sulfenylative Desulfonylation or Decarbalkoxylation of α-Sulfonyl Malonates with DABCO or Bu3N: Reactivity and Conformational Analysis

The study on reactivity of several α-substituted α-sulfonyl malonates toward 1,4-diazabicyclo[2.2.2]octane (DABCO) and Bu₃N is described. The reactivity with DABCO revealed the possible competition between decarbalkoxylation and unexpected desulfonylation, depending on the α-substituent, because of sterical hindrance around the electrophilic centers (SO₂ and CO₂R). The derivatives with crowded α-substituents suffer selective desulfonylation, and a novel and efficient desulfonylation method can be proposed. The dependence of the reactivity of α-sulfonyl malonates on the sterical hindrance around the electrophilic centers is confirmed by conformational analysis (Macromodel/MM2? and Mopac/MP3). The carbanionic mechanism is proved because the corresponding protonated, deuterated, and sulfenylated products were obtained by addition of the corresponding electrophilic agents. Bu₃N showed itself to be a novel selective decarbalkoxylation agent for any α-substituted α-sulfonyl malonate.     

Anaerobic reduction of a sulfonated azo dye, Congo Red, by sulfate-reducing bacteria

The capacity for anaerobic decolorization of a sulfonated azo dye, Congo Red, by a strain of a sulfate-reducing bacterium was evaluated. After optimizing the growth rate of the bacteria on a simple carbon source and terminal electron acceptor pair, lactate and sulfate, respectively, the effect of the dye concentration on their growth rate was analyzed. The decolorization rate was affected by the dye concentration in the growth medium. The azo-bond cleavage mechanism of reductive decolorization with the formation of benzidine was consistent with the results, as this metabolite was identified by high-performance liquid chromatography. Several fractions of the culture medium, including lysed cell extracts, were examined for the capacity to reduce the azo dye. This reduction capacity was found in the culture medium in which the cells had previously grown. The results showed that the mechanism of reductive decolorization of this sulfonated azo dye was extracellular and nonenzymatic, consistent with the production of sulfide anion by the microorganisms while growing on lactate and sulfate. The sulfide anions were the cause of the reduction leading to the disappearance of color in the medium. To increase the rate of decolorization, the presence of ferrous ion was also necessary together with the lactate and sulfate substrates.     

NO Release from trans-[Ru(NH3)4L(NO)]3+ Complexes Upon Reduction (L = 1-Methylimidazole or Benzoimidazole)

The synthesis, characterization and reactivity of trans-[Ru(NH₃)₄(L)NO](PF₆)₃(L = benzoimidazole or 1-methylimidazole in trans position to NO) are presented. ¹H-n.m.r. spectroscopy data indicate that the benzoimidazole and 1-methylimidazole ligands are coordinated to Ru^II through carbon and nitrogen, respectively. The nitrosyl stretching frequencies [(NO) > 1900 cm^–1] suggest that the coordinated nitrosyl has substantial NO⁺ character. The complexes undergo a single-electron reduction (E ⁰–0.245 versus NHE), which involves the coordinated nitrosyl. Dissociation of NO in the reduced species is facilitated by the 1-methylimidazole ligand, which is not observed for the benzoimidazole species. The complex with 1-methylimidazole does not suffer hydroxide attack on the NO⁺, at least at pH values lower than 11.     

Formic and acetic acids in a nitrogen matrix: Enhanced stability of the higher-energy conformer

Formic acid (HCOOH, FA) and acetic acid (CH(3)COOH, AA) are studied in a nitrogen matrix. The infrared (IR) spectra of cis and trans conformers of these carboxylic acids (and also of the HCOOD isotopologue of FA) are reported and analyzed. The higher-energy cis conformer of these molecules is produced by narrowband near-IR excitation of the more stable trans conformer, and the cis-to-trans tunneling decay is evaluated spectroscopically. The tunneling process in both molecules is found to be substantially slower in a nitrogen matrix than in rare-gas matrices, the cis-form decay constants being approximately 55 and 600 times smaller in a nitrogen matrix than in an argon matrix, for FA and AA respectively. The stabilization of the higher-energy cis conformer is discussed in terms of specific interactions with nitrogen molecule binding with the OH group of the carboxylic acid. This model is in agreement with the observed differences in the IR spectra in nitrogen and argon matrices, in particular, the relative frequencies of the νOH and τCOH modes and the relative intensities of the νOH and νC=O bands.     

Development of a Validated Stability-Indicating LC Assay and Stress Degradation Studies of Linezolid in Tablets

This paper describes the validation of an isocratic LC method for the assay of linezolid in tablets. Validation parameters such as linearity, precision, accuracy, specificity, limit of detection, limit of quantitation and robustness were determined. LC was carried out by reversed phase technique on an RP-18 column with a mobile phase composed of 1% acetic acid:methanol:acetonitrile (50:25:25, v/v/v). Linezolid and your combination drug product were exposed to acid, base, oxidation, dry heat and photolytic stress conditions. A linear response (r > 0.9999) was observed in the range of 8.0–20.0 μg mL⁻¹. The retention time of linezolid was 4.6 min. The method showed good recoveries and intra- and inter-day relative standard deviations were less than 1.0%. The LOD and LOQ were 0.21 and 0.63 μg mL⁻¹, respectively. The developed LC method for determination of related substances and assay determination of linezolid can be used to evaluate the quality of regular production samples. It can also be used to test the stability samples of linezolid.

     

Use of Fourier transform infrared spectroscopy and chemometrics to discriminate clinical isolates of bacteria of the Burkholderia cepacia complex from different species and ribopatterns

A methodology for the discrimination of Burkholderia cepacia complex (Bcc) clinical isolates at the species level and at the ribopattern level using Fourier transform infrared (FTIR) spectroscopy and chemometrics analysis was assessed in this study. Different Bcc sequential isolates collected at the Santa Maria Hospital (HSM), in Portugal, from clinically infected cystic fibrosis (CF) patients were previously classified by established molecular methods at the species level and differentiated at the strain level, based on their ribopatterns. A set of 185 of these isolates, representing four different Bcc species (Burkholderia cepacia, Burkholderia cenocepacia (recA lineages III-A and III-B), Burkholderia multivorans and Burkholderia stabilis), was analyzed by FTIR and results were processed with chemometric methods. Ten reference strains of these species were used to test the FTIR method. The discrimination at the species level led to misclassification error rates of 10% and 32% for the HSM isolates and reference strains, respectively, clearly indicating that the FTIR classification method was unable to generalize results for the reference strains. Infrared spectra of HSM isolates were further analyzed in terms of the discrimination according to the ribopattern. Results showed misclassification error rates of 4%, 2%, and 8% for B. cepacia, B. cenocepacia III-A, and B. cenocepacia III-B ribopatterns, respectively. These results demonstrated good FTIR spectroscopy discrimination capacity at the ribopattern level, for the HSM isolates but showed difficulty at the species level, especially when the reference strains were included. Remarkably, this methodology was found to discriminate isolates belonging to the same species and ribopattern that were collected from the same patient during prolonged colonization, opening the door to the identification of chemical modifications resulting from adaptation strategies to the CF lung stressing environment, in particular to aggressive and prolonged antibiotic therapy. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Production of Cellulolytic Enzymes by <Emphasis Type="Italic">Aspergillus phoenicis</Emphasis> in Grape Waste using Response Surface Methodology

The production of cellulolytic enzymes by the fungus Aspergillus phoenicis was investigated. Grape waste from the winemaking industry was chosen as the growth substrate among several agro-industrial byproducts. A 2 × 2 central composite design was performed, utilizing the amount of grape waste and peptone as independent variables. The fungus was cultivated in submerged fermentation at 30 °C and 120 rpm for 120 h, and the activities of total cellulases, endoglucanases, and β-glucosidases were measured. Total cellulases were positively influenced by the linear increase of peptone concentration and decrease at axial concentrations of grape waste and peptone. Maximum activity of endoglucanase was observed by a linear increase of both grape waste and peptone concentrations. Concentrations of grape waste between 5 and 15 g/L had a positive effect on the production of β-glucosidase; peptone had no significant effects. The optimum production of the three cellulolytic activities was observed at values near the central point. A. phoenicis has the potential for the production of cellulases utilizing grape waste as the growth substrate.     

Synthesis and Characterization of Polymeric Materials from Vegetable Oils

Although the petrochemical polymers have revolutionized the technological development, the intensive use of these materials have contributed to the global pollution. In this context, researches involving ecofriendliness materials are growing up, as well as, a current interest in developing materials from inexpensive and renewable resources, such as vegetable oils. In this work, is described the synthesis of polymeric materials by thermal polymerization from linseed oil (Linum usitatissimum L.) and passion fruit oil (Passiflora edulis) and their characterization by gas chromatographic (GC), Fourier transform infrared (FTIR) spectroscopy, solubility in organic solvents, thermogravimetry (TG), differential scanning calorimetry (DSC) and Raman spectroscopy. The TG curve shows that those polymeric materials present two stages of decomposition. DSC plots of the vegetable oils showed some endothermic and exothermic transitions which are not present in the DSC curves corresponding to oil-based polymers. The Raman spectra of the polymers indicate declining of absorbance in the region of CC stretching (∼1600 cm⁻¹). This absorption was used to estimate the degree of polymerization (79% and 67.5% for linseed and passion fruit oils, respectively).