HPLC-ESI-MS/MS analysis of oxidized di-caffeoylquinic acids generated by metalloporphyrin-catalyzed reactions

This paper reports an HPLC-ESI-MS/MS investigation on the oxidation of 3,5- and 4,5- dicaffeoylquinic acid using iron(III) tetraphenylporphyrin chloride as catalyst. Two major mono-oxidised products of the quinic acid moiety have been identified for both compounds. However, only the 4,5-derivative afforded two different tri-oxo products. Thus, it seems that the oxidation pattern depends on the number and positions of the caffeic acid moieties present in caffeoylquinic acid molecules.

Determinação da matéria-prima utilizada na produção do biodiesel adicionado ao diesel mineral através de monitoramento seletivo de íons

The selective ion monitoring acquisition mode in mass spectrometry was applied to identify, in the diesel complex matrix, the raw materials (vegetable oil and alcohol) that originate biodiesel. Biodiesel samples obtained from babassu, castor, palm and soybean vegetable oils and pure fatty acid methyl and ethyl esters were used to develop this method, using specific fragments in mass spectrometry and the "window system" in gas chromatography. The commercial Brazilian B2 samples were found to be produced with soybean oil, transesterified with methanol.

Amostragem do material particulado e fração orgânica volátil das emissões em motor ciclo diesel sem a utilização de túnel de diluição

Using a sampling method of particulate matter (PM) without the use of a dilution tunnel allows for evaluations of the volatile hydrocarbons (HC) in the emissions of diesel cycle engines. The procedure in this work applied a heated filter with temperature controlled. The volatile compounds are condensed at low temperature, allowing for evaluation of the HC by thermal desorption of the PM and for analysis of the condensed compounds of the exhaust gases.

Estudo de adsorção de compostos sulfurados utilizando um diesel comercial dopado com benzotiofeno e dibenzotiofeno

Desulphurization process by adsorption was studied employing a commercial diesel dooped with 1000 mg/L of benzothiophene and dibenzothiophene. The adsorbents materials employed were three types of activated alumina (acid, basic and neutral). For comparison, adsorption process was made also using oxidized diesel sample. The results showed that the adsorbents were selective for sulphur compounds removal from fuels. The contact time have influence in adsorption process achieving 80% of removal for not oxidized dibenzothiophene. The three studied alumina types showed similar behavior and a greater selective in dibenzothiophene adsorption than benzothiophene. Dibenzothiophene removal is more effective in samples not oxidized, whereas the benzothiophene was almost totally removed in oxidized sample.

Polarizabilidades e primeira hiperpolarizabilidades elétricas dipolares de ésteres E-4-amino-trans-1,3-butadienil-(1',2'-di-hidroxibenzeno) de boro, alumínio e gálio

Static electric dipole polarizabilities and first hyperpolarizabilites have been calculated for the title molecules and their 3' and 4'-nitro derivatives at ab-initio Hartree- Fock/6-31G(d, p) level. The influence of the pivotal p vacant 3A elements (B, Al or Ga) substitution on the electrical properties of these molecules is detailed. The axial vector components of the first hyperpolarizabilities β(0) of the push-pull 4'-nitro derivatives, -18.2×10-32 esu (B), -21.1×10-32 esu (Al) and -20.8×10-32 esu (Ga) are calculated to be as much as fourfold larger then that calculated for the p-nitroaniline, a reference organic molecule for comparison for this type of molecular property.

Caracterização da fusão peritética do cloreto de sódio di-hidratado por curvas de aquecimento

Binary mixture phase diagrams are normally obtained from thermal analysis involving freezing point curves. However, that approach is not always reliable and easy to follow to all kinds of mixtures in any proportion. In fact, even for a simple system, such as NaCl-H2O, this freezing methodology gives mixed results when one starts from a solid-solution system, due mostly to the formation of the NaCl.2H2O, which has an incongruent melting point, and the dependence of its solubility with the temperature. In this work we report a trustworthy, simple and cheap method involving heating curves to drawn the NaCl-H2O phase diagram.

Avaliação da potencialidade de processos pseudo-fenton para remediação de solos contaminados por diesel

The use of the Fenton's reagent process has been investigated for the remediation of a Brazilian soil contaminated by diesel. Laboratory experiments were conducted in batch experiments. Slurries, consisting of 10 g of diesel-contaminated soil and 30 mL of Fenton's Reagent (0.41 mol L-1 H(2)0(2) and 0.18 mol L-1 FeSO4). The experiments were monitored during 24, 48 and 72 h. The efficiency of the Fenton treatment was dependent on the time of contact between soil and Fenton's reagents and matrix characteristics, probably iron content. Data suggested that no iron addition is needed for the application of Fenton-like treatment for the remediation of diesel-contaminated iron rich soils after 72 h reaction.

A topologia molecular QTAIM e a descrição mecânico-quântica de ligações de hidrogênio e ligações de di-hidrogênio

Hydrogen bonds formed through the interaction between a high electronic density center (lone electron pairs, π or pseudo-π bonds) and proton donors cause important electronic and vibrational phenomena in many systems. However, it was demonstrated that proton donors interact with hydrides, such as alkali and alkaline earth metals (BeH2, MgH2, LiH and NaH), what yields a new type of interaction so-called dihydrogen bonds. The characterization of these interactions has been performed at light of the Quantum Theory of Atoms in Molecules (QTAIM), by which the electronic densities ρ are quantified and the intermolecular regions are characterized as closed-shell interactions through the analysis of the Laplacian field ∇2ρ.

Aplicação do modelo Tucker-3 para a análise da biodegradação de diesel

Tucker-3 model offers several advantages for analysis of environmental data but its interpretation is still challenging. A Tucker-3 model was applied to a biodegradation experiment involving a large number of overlapped chromatographic peaks and a temporal variation. The Tucker-3 model allowed the data to be decomposed in two processes: evaporation and biodegradation. The results suggest that linear hydrocarbons were those biodegraded first and demonstrate that the data analysis can be simplified by interpreting the elements of the core array. The approach discussed in this work can be applied in similar problems involving multi-way data in other areas of chemistry.

Identificação de adulteração de biocombustível por adição de óleo residual ao diesel por espectrofluorimetria total 3D e análise das componentes principais

Total spectrofluorimetry associated to Principal Components Analysis (PCA) were used to classify into different groups the samples of diesel oil, biodiesel, vegetal oil and residual oil, as well as, to identify addition of non-transesterified residual vegetable oil, instead of biodiesel, to the diesel oil. Using this method, the samples of diesel oil, mixtures of biodiesel in diesel and mixtures of residual oil in diesel were separated into well-defined groups.

Diesel/biodiesel soot oxidation with ceo2 and ceo2-zro2-modified cordierites: a facile way of accounting for their catalytic ability in fuel combustion processes

CeO2 and mixed CeO2-ZrO2 nanopowders were synthesized and efficiently deposited onto cordierite substrates, with the evaluation of their morphologic and structural properties through XRD, SEM, and FTIR. The modified substrates were employed as outer heterogeneous catalysts for reducing the soot originated from the diesel and diesel/biodiesel blends incomplete combustion. Their activity was evaluated in a diesel stationary motor, and a comparative analysis of the soot emission was carried out through diffuse reflectance spectroscopy. The analyses have shown that the catalyst-impregnated cordierite samples are very efficient for soot oxidation, being capable of reducing the soot emission in more than 60%.

Estudos de biodegradação de óleo diesel por consórcio microbiano coletado em Porto Velho - RO, amazônia

The goal of this research was to evaluate the biodegradation of diesel by a microbial consortium collected in a region close to distributors of fuel. The experiments were monitored by SPME-GC-FID and SPME-GC-MS. The consortium showed a high potential for production of biosurfactants, presenting an emulsification index of 53%. The consortium degraded completely n-alkanes, while dimethylnaphtalene, hepthyl-cyclohexane and 2,6,10-trimethyl-undecane were partially degraded and pristane was not degraded. From this consortium five strains were isolated and identified as Acinetobacter baumannii. Based on this initial investigation this consortium appears to be effective for bioremediation in Porto Velho - RO region.

Synthesis of quinoxaline 1,4-di-N-oxide derivatives on solid support using room temperature and microwave-assisted solvent-free procedures

We describe the synthesis of 12 new ethyl and methyl quinoxaline-7-carboxylate 1,4-di-N-oxide derivatives on solid supports with room temperature and microwave-assisted solvent-free procedures. Results show that solid supports have good catalytic activity in the formation of quinoxaline 1,4-di-N-oxide derivatives. We found that florisil and montmorillonite KSF and K10 could be used as new, easily available, inexpensive alternatives of catalysts. Additionally, room temperature and microwave-irradiation solvent-free synthesis was more efficient than a conventional procedure (Beirut reaction), reducing reaction time and increasing yield.

Uso da cromatografia gasosa bidimensional abrangente (GC×GC) na caracterização de misturas biodiesel/diesel: aplicação ao biodiesel de sebo bovino

The growth of biodiesel market and the implementation of regulations related to biodiesel production and biodiesel/diesel blending has encouraged the development of appropriate analytical methods to control the composition of this type of mixture. In this study, an evaluation of the potential of GC×GC for the characterization of samples of beef tallow biodiesel and the composition of blends of biodiesel/diesel is presented. The methodology was applied to beef tallow biodiesel and its mixtures with petrodiesel, ranging from B2 to B50. Results allowed not only the identification and quantification of the biodiesel esters, but also the biodiesel percentage in biodiesel/diesel blends.

Phenolic compounds from Sidastrum micranthum (A. St.-Hil.) fryxell and evaluation of acacetin and 7,4'-Di-O-methylisoscutellarein as motulator of bacterial drug resistence

From the aerial parts of Sidastrum micranthum (A. St.-Hil.) Fryxell (Malvaceae) were isolated m-methoxy-p-hydroxy-benzaldehyde, o-hydroxy-benzoic acid, acacetin, quercetin, 7,4′-Di-O-methylisoscutellarein, genkwanin and tiliroside. These compounds were identified by data analyses of spectroscopic methods. Although acacetin and 7,4′-Di-O-methylisoscutellarein did not display relevant antibacterial activity (MIC = 256 µg/mL), they modulated the activity of antibiotics, i.e. in combination with antibiotics at 64 µg/mL (¼ MIC), a two-fold reduction in the MIC was observed for norfloxacin and ethidium bromide; regarding tetracycline and erythromycin a two-fold reduction in the MIC was observed only with 7,4′-Di-O-methylisoscutellarein.