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.     

Multistep adsorption of anionic dyes on silica/chitosan hybrid. 1. Comparative kinetic data from liquid- and solid-phase models

In this work, a hybrid silica/chitosan was synthesized and characterized by nitrogen elemental analysis and thermal analysis (TG, DTG, DTA, and DSC) and BET surface area. The hybrid was used in adsorption studies of two anionic dyes from aqueous solutions. A rise of temperature accelerates mass transfer of dyes into the hybrid. However, the maximum adsorption capacities reach similar values from 25 to 55 degrees C. The kinetic data were first evaluated in relation to the decrease of the time-related residual concentration of the dyes in solution, where the second-order model has presented the best fitting. The solid-phase interaction of dye data presents a rough fitting to the traditional first-order Lagergren kinetic model. However, a modified Avrami kinetic equation was successfully fitted to the kinetic quantities, where from five to seven kinetic regions were found. A pore-diffusion model has also demonstrated that the diffusion is the rate-controlling interaction mechanism. However, the experimental-calculated comparative values are the best way to evaluate a specific aqueous- or solid-phase kinetic model.     

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.     

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.     

Preparation of the Ca–diclofenac complex in solid state

Two ONNO type naphtaldehyde derivative Schiff base compounds were reduced and two symmetric phenol-amine ligands containing naphthalene groups were obtained; bis-N,N′[(2-hydroxy-1-naphtyl) methyl]-1,3-propanediamine (NAFL^H) and bis-N,N′[(2-hydroxy-1-naphtyl) methyl]-2,2′-dimetyhyl-1,3-propanediamine (NAFLDM^H). Homotrinuclear Ni(II) complexes of these ligands were prepared. The solid-state molecular structures of representative nickel complex of NAFLDM^H were determined using single crystal X-ray diffraction analysis. The terminal Ni(II) ions were found to be situated in between the donor atoms of the organic ligand. The central Ni(II) ion was observed to be bonded via two different μ-bridges. The phenolic oxygens and carboxylate ion were seen to form two different μ-bridges. TG analysis proved that the compounds have different thermal characteristics than those cited in literature. The complexes showed extreme exothermic degradation reactions in inert atmosphere. The complexes are ruptured with a two stepped exothermic reaction which appears huge heat over 300 °C. The heat appeared in O₂ atmosphere is observed to be higher than the heat appeared in inert atmosphere. Revealed heat is observed to be higher than the conventional explosive materials.     

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.     

Assessment of pharmacokinetic interaction between piracetam and l‐carnitine in healthy subjects

A rapid, sensitive and specific method for quantifying piracetam in human plasma using Piracetam d‐8 as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by one‐step precipitation of protein using an acetonitrile (100%). The extracts were analyzed by high‐performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC‐MS/MS). The method had a chromatographic run time of 3.8 min and a linear calibration curve over the range 0.5–50 µg/mL (r > 0.99). This LC‐MS‐MS procedure was used to assess the bioavailability of two piracetam formulations: piracetam + l‐carnitine (Piracar®; 270/330 mg tablet) and piracetam (Nootropil®; 800 mg tablet) in healthy volunteers of both sexes. The geometric means with corresponding 90% confidence interval (CI) for test/reference percentage ratios were 88.49% (90% CI = 81.19 – 96.46) for peak concentration/dose and 102.55% (90% CI = 100.62 – 104.51) for AUC_inf/dose. The limit of quantitation of 0.5 µg/mL is well suited for pharmacokinetic studies in healthy volunteers. It was concluded that piracetam (Piracar®; 270/330 mg tablet) has a bioavailability equivalent to the piracetam (Nootropil®; 800 mg tablet) formulation with regard to both the rate and the extent of absorption. Copyright © 2015 John Wiley & Sons, Ltd.     

A multi-commuted flow injection system with a multi-channel propulsion unit placed before detection: Spectrophotometric determination of ammonium

A flow system with a multi-channel peristaltic pump placed before the solenoid valves is proposed to overcome some limitations attributed to multi-commuted flow injection systems: the negative pressure can lead to the formation of unwanted air bubbles and limits the use of devices for separation processes (gas diffusion, dialysis or ion-exchange). The proposed approach was applied to the colorimetric determination of ammonium nitrogen. In alkaline medium, ammonium is converted into ammonia, which diffuses over the membrane, causing a pH change and subsequently a colour change in the acceptor stream (bromothymol blue solution). The system allowed the re-circulation of the acceptor solution and was applied to ammonium determination in surface and tap water, providing relative standard deviations lower than 1.5%. A stopped flow approach in the acceptor stream was adopted to attain a low quantification limit (42 μg L⁻¹) and a linear dynamic range of 50–1000 μg L⁻¹ with a determination rate of 20 h⁻¹.     

Influence of inhibitory compounds and minor sugars on xylitol production by <Emphasis Type="Italic">Debaryomyces hansenii</Emphasis>

To obtain in-depth information on the overall metabolic behavior of the new good xylitol producer Debaryomyces hansenii UFV-170, batch bioconversions were carried out using semisynthetic media with compositions simulating those of typical acidic hemicellulose hydrolysates of sugarcane bagasse. For this purpose, we used media containing glucose (4.3–6.5 g/L), xylose (60.1–92.1 g/L), or arabinose (5.9–9.2 g/L), or binary or ternary mixtures of them in either the presence or absence of typical inhibitors of acidic hydrolysates, such as furfural (1.0–5.0 g/L), hydroxymethylfurfural (0.01–0.30 g/L), acetic acid (0.5–3.0 g/L), and vanillin (0.5–3.0 g/L). D. hansenii exhibited a good tolerance to high sugar concentrations as well as to the presence of inhibiting compounds in the fermentation media. It was able to produce xylitol only from xylose, arabitol from arabinose, and no glucitol from glucose. Arabinose metabolization was incomplete, while ethanol was mainly produced from glucose and, to a lesser less extent, from xylose and arabinose. The results suggest potential application of this strain in xyloseto-xylitol bioconversion from complex xylose media from lignocellulosic materials.     

A New ent‐Kaurane Diterpene from Stems of Alibertia macrophylla K. Schum. (Rubiaceae)

Phytochemical investigations of the stems of a specimen of Alibertia macrophylla led to the isolation and characterization of the new diterpene ent‐kaurane‐2β,3α,16α‐triol ( 1 ), along with triterpenes 2 – 8 , iridoids 9 – 12 , and phenolic acids 13 – 15 . The structure of 1 was established based on spectroscopic studies (¹H‐ and ¹³C‐NMR, IR, and HR‐ESI‐MS). This is the first report of the isolation of a diterpene from the Alibertia genus in Rubiaceae.