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Profiling fatty acids in vegetable oils by reactive pyrolysis-gas chromatography with dimethyl carbonate and titanium silicate.

A novel methodology in on-line pyrolysis-gas chromatography (Py-GC) for the fast analysis of fatty acids in vegetable oils with minimal sample treatment and the use of non-toxic reagents is described. Pyrolysis at 500 degrees C for 10 s of sub-microgram quantity of vegetable oil dissolved in dimethyl carbonate (DMC) and in the presence of nanopowder titanium silicon oxide resulted in the production of fatty acid methyl esters (FAMEs) as unique products. Pyrolysis performed by means of a resistively heated filament pyrolyser interfaced to a GC-MS apparatus enabled the direct analysis of evolved FAMEs. The DMC/Py-GC-MS analysis was tested on soybean, coconut, linseed, walnut and olive oil and the results compared to the classical BF(3)-methanol as reference methodology. The DMC method exhibited a lower precision and was biased towards lower levels of polyunsaturated fatty acids (PUFA) in comparison to the BF(3)-methanol method, but was more advantageous in terms of reduced sample treatment, waste generation and risk factors of employed chemicals.

Fatty Acids↗

Competitive metal binding to a silicate-immobilized humic material.

The investigation of the competitive binding of metal ions to a biogenic material comprised of organic peat immobilized in a polysilicate matrix was undertaken. This material was packed into 5.0mL bed-volume columns using 40-60mesh size particles. Two separate mixtures of metal ions were studied by monitoring the solution pH and the concentration of each metal in the effluent as a function of the volume of influent introduced to the material. These mixtures contained either the metal ions Ca(2+), Mg(2+), and Cu(2+) or the ions Cu(2+), Hg(2+), and Pb(2+). A general order of binding affinities was determined to be Mg(2+)<Ca(2+)<<Cu(2+)<Pb(2+)<Hg(2+). Comparisons of amounts of metal ions bound and protons released indicated the initial release of two protons for each divalent metal ion bound. However, prolonged exposure of the material to the metal solutions yielded a molar ratio of 1:1. This suggests the involvement of ion exchange sites followed by that of sites using an alternate binding mechanism. The presence of binding sites with varied mechanisms and metal ion affinities was further illustrated through the initial binding and subsequent release of lower affinity metal ions (e.g., Mg(2+) and Ca(2+)).

Adsorption↗

Aluminium-induced phospholipid signal transduction pathway in Coffea arabica suspension cells and its amelioration by silicic acid.

Coffee (Coffea arabica L.) is of economic importance worldwide. Its growth in organic-rich acidic soils is influenced by aluminium such that coffee yield may be impaired. Herein we have used the Al-sensitive C. arabica suspension cell line L2 to analyse the effect of two different Al species on the phosphoinositide signal transduction pathway. Our results have shown that the association of Al with coffee cells was affected by the pH and the form of Al in media. More Al was associated with cells at pH 4.3 than 5.8, whereas when Al was present as hydroxyaluminosilicates (HAS) the association was halved at pH 4.3 and unchanged at pH 5.8. Two signal transduction elements were also evaluated; phospholipase C (PLC) activity and phosphatidic acid (PA) formation. PLC was inhibited ( approximately 50%) when cells were incubated for 2 h in the presence of either AlCl(3) or Al in the form of HAS. PA formation was tested as a short-term response to Al. By way of contrast to what was found for PLC, incubation of cells for 15 min in the presence of AlCl(3) decreased the formation of PA whereas the same concentration of Al as HAS produced no effect upon its formation. These results suggest that Al is capable to exert its effects upon signal transduction as Al((aq))(3+) acting upon a mechanism linked to the phosphoinositide signal transduction pathway.

Aluminum↗

The effect of sodium chloride on the dissolution of calcium silicate hydrate gels.

The use of cement based materials will be widespread in the long-term management of radioactive materials in the United Kingdom. One of the applications could be the Nirex reference vault backfill (NRVB) as an engineered barrier within a deep geological repository. NRVB confers alkaline conditions, which would provide a robust chemical barrier through the control of the solubility of some key radionuclides, enhanced sorption and minimised corrosion of steel containers. An understanding of the dissolution of C-S-H gels in cement under the appropriate conditions (e.g., saline groundwaters) is necessary to demonstrate the expected evolution of the chemistry over time and to provide sufficient cement to buffer the porewater conditions for the required time. A programme of experimental work has been undertaken to investigate C-S-H gel dissolution behaviour in sodium chloride solutions and the effect of calcium/silicon ratio (C/S), temperature and cation type on this behaviour. Reductions in calcium concentration and pH values were observed with samples equilibrated at 45 degrees C compared to those prepared at 25 degrees C. The effect of salt cation type on salt-concentration dependence of the dissolution of C-S-H gels was investigated by the addition of lithium or potassium chloride in place of sodium chloride for gels with a C/S of 1.0 and 1.8. With a C/S of 1.0, similar increases in dissolved calcium concentration with increasing ionic strength were recorded for the different salts. However, at a C/S of 1.8, anomalously high calcium concentrations were observed in the presence of lithium.

Calcium Compounds↗

Degradation of phenol using tyrosinase immobilized on siliceous supports.

The degradation of phenol by tyrosinase immobilized on chemically modified sodium aluminosilicate (NaA), calcium aluminosilicate (CaA), and silica gel was studied. Phenol conversion by immobilized tyrosinase ranged between approximately 15% and 60%, depending upon the initial phenol concentration, pH, and enzyme loading. Tyrosinase immobilized on CaA and on NaA could be re-used repeatedly without any decrease in performance. However, in studies at pH 8.0, significant enzyme inhibition was observed, since phenol conversion was rapid for approximately 20 min, then reached a plateau. The inhibition was reversible; activity was restored upon placing the immobilized enzyme in fresh substrate. Reducing the pH to 6.8 from 8.0 led to higher conversion of phenol, and decreased the inhibition of the immobilized enzyme.

Aluminum Silicates↗

Influences of phosphate and silicate on Cr(VI) and Se(IV) accumulation in marine phytoplankton.

The influences of major nutrient additions (P, Si, or N) on the accumulation of chromate [Cr(VI)] and selenite [Se(IV)] in three species of marine phytoplankton, including two diatoms (Thalassiosira pseudonana, and Skeletonema costatum), and one green alga (Chlorella autotrophica) were examined. Accumulation rate was quantified by measurements of metal concentration factor in algal cells over a short 5-h exposure period. Our results suggested that Se(IV) was little bioavailable to C. autotrophica and S. costatum, but was highly bioavailable to diatom T. pseudonana. Se(IV) accumulation in both diatoms and green alga was inversely dependent on the ambient P and Si concentration. Concentration factor decreased by 2.4-8.1 and 1.5-4.6 times with the additions of 7.2 microM P or 105.6 microM Si, respectively, after 5 h of exposure. Bioconcentration factors of Se(IV) in these species determined under laboratory conditions, which generally employ high nutrient concentrations, may not be applicable to those prevailing in the field. In contrast to Se(IV), Cr(VI) accumulation in the green alga and two diatoms was not related to the ambient P concentrations, but was inversely dependent on the ambient Si concentrations. These data demonstrated that the influences of major nutrients on anionic metal accumulation were highly species-specific, both for metals and phytoplankton. Nutrient enrichments in many water bodies may potentially affect the accumulation of anionic metals, and thus their biological transport and fate in these environments.

Animals↗

Use of silicate sol-gels to trap the R and T quaternary conformational states of pig kidney fructose-1,6-bisphosphatase.

Encapsulation of the homotetrameric pig kidney fructose-1,6-bisphosphatase (FBPase) in tetramethyl orthosilicate sol-gels was used to dramatically reduce the rate of the allosteric transition of the enzyme between the T and R allosteric states. When assayed in the absence of the allosteric inhibitor AMP, the enzyme encapsulated in the T-state exhibited little activity. The enzyme encapsulated in the R-state exhibited a 4-fold lower k(cat) and V(max) than the enzyme in solution, and the apparent K(m) for this enzyme was 350-fold higher than the corresponding value for the enzyme in solution. The [Mg(2+)](0.5) for the encapsulated enzyme was only 0.1 mM, compared to 0.54 mM for the normal enzyme. Magnesium activation, under both sets of conditions, was cooperative with a Hill coefficient of approximately 2. The activity of enzyme encapsulated in the R-state decreased to about 70% of initial activity within 1 min of adding AMP, it then decreased slowly to about 40% of initial activity over the following 7 h. Under the conditions tested, the encapsulated enzyme never became completely inactivated and AMP inhibition was no longer cooperative. For enzyme encapsulated in the T-state, activity was restored over approximately 7 h after removal of the AMP. The biphasic and slow responses to changing AMP levels suggest that encapsulated enzyme can be used to study the effects of local conformational changes distinct from the global quaternary conformational changes by slowing down the ability of the enzyme to carry out global rotations. The response to AMP exhibited by the encapsulated enzyme is consistent with the ability of AMP, at least partially, to directly influence the activity of the active site within each subunit.

Adenosine Monophosphate↗

UraniumVI sorption behavior on silicate mineral mixtures.

UraniumVI sorption experiments involving quartz and clinoptilolite, important mineral phases at the proposed US nuclear waste repository at Yucca Mountain, NV, were conducted to evaluate the ability of surface complexation models to predict UVI sorption onto mineral mixtures based on parameters derived from single-mineral experiments. The experiments were conducted at an initial UVI aqueous concentration of approximately 2.0 x 10(-7) mol.l-1 (0.1 mol.l-1 NaNO3 matrix) and over the pH range approximately 2.5 to approximately 9.5. The UVI solutions were reacted with either quartz or clinoptilolite only, or with mixtures of the two minerals. The experiments were carried out under atmospheric pCO2(g) conditions (in loosely capped containers) or under limited pCO2(g) (in capped containers or in a glove box). Data from sorption experiments on quartz at atmospheric pCO2 conditions were used to derive UVI binding constants for a diffuse-layer surface complexation model (DLM). The DLM was then used with surface area as a scaling factor to predict sorption of UVI onto clinoptilolite and clinoptilolite/quartz mixtures under both atmospheric and low pCO2 conditions. The calculations reproduced many aspects of the pH-dependent sorption behavior. If this approach can be demonstrated for natural mineral assemblages, it may be useful as a relatively simple method for improving radionuclide transport models in performance-assessment calculations.

Adsorption↗