Chromatographic techniques for the determination of alkyl-phenols, tocopherols and other minor polar compounds in raw and roasted cold pressed cashew nut oils

Anacardium occidentale belongs to the family Anacardiaceae and is principally grown in tropical America (Mexico, Peru, Brazil, etc.) and India. Cashew nuts contain low amounts of hydroxy alkyl phenols that come from an oily liquid present in their shell and that is known as cashew-nut shell liquid. This paper reports the alkyl phenols composition of cold pressed raw and roasted cashew nut oil. First of all, cashew nut shell liquid was used for a basic fractionation of the alkyl phenol classes by preparative TLC and definitively identified by GC-MS and GC-FID. Anacardic acids were the major alkylphenols contained in both oils followed by cardol, cardanol and 2-methylcardol compounds, respectively. Raw and roasted oils did not show different compositions except for cardanols. The oil produced from roasted cashew nut reported a higher concentration of cardanols. Furthermore, tocopherols and other minor polar compounds were determined by HPLC-FLD and HPLC-DAD-MS, respectively. Tocopherol content varied in a range of 171.48-29.56mg/100g from raw to roasted cashew nut oil, being β-tocopherol the one which presented a higher decrease (93.68%). Also minor polar compounds in cashew oil decreased after roasting from 346.52 to 262.83mg/kg.     

The bargaining set for sharing the power

The evaluation of the power of the parties of a Parliament is usually carried out following a static approach, counting their numbers of seats and possible ideological relations among them. In this paper we propose a dynamic model in which parties may blackmail each other in order to increase their power at the expense of others. This model may be solved in terms of the Bargaining Set (Aumann and Maschler in Advances in game theory. Princeton University Press, Princeton, 1964), a set valued solution, in contrast to the classical power indices that are point valued; so it may be used to check the robustness of a power division taking into account possible blackmailing activities. The paper is mainly based on the idea of proposing an existing instrument, the Bargaining Set, as power index to analyze this blackmailing situation. The computational complexity limits the possibility of applying it to real-world situations, but the possibility of making the computation easier is shown using some examples.     

Stereoselective synthesis of 2,3-epoxy alcohols mediated by a remote sulfinyl group

The influence of the sulfinyl group as a chiral auxiliary in the stereoselective addition of oxiranyllithiums to (S)-2-p-tolylsulfinylbenzaldehyde has been studied. All reactions evolve with retention of configuration at the starting lithiated carbon. Completely stereoselective additions have been observed when configurations at sulfur and the lithiated carbon are different (matched pair), whereas variable dr's values (ranging between 52:48 and >99:<1%) when they are identical (mismatched pair).     

Solvent and TMEDA effects on the configurational stability of chiral lithiated aryloxiranes

The employment of hexane/N,N,N',N'-tetramethylethylenediamine (TMEDA) dramatically hinders the racemization of those lithiated styrene oxides (trifluoromethyl-, chloro-, and phenylthio-substituted) that have been proven to be configurationally unstable in THF on the timescale of their reactions. The barriers to inversion and the activation parameters, calculated (Eyring equation) for reactions performed in THF, THF/TMEDA, and hexane/TMEDA, suggest the intervention of particular enantiomerization mechanisms for each case. The role of TMEDA in both coordinating and noncoordinating solvents has also been questioned and discussed in light of the kinetic data gathered and a model for deprotonation in hexane/TMEDA has also been proposed. The synthetic benefits of our results became apparent on establishing an asymmetric synthesis of an industrially important antifungal agent.     

Thermodynamic and dynamic anomalies in a one-dimensional lattice model of liquid water

We investigate the occurrence of waterlike thermodynamic and dynamic anomalous behavior in a one dimensional lattice gas model. The system thermodynamics is obtained using the transfer matrix technique and anomalies on density and thermodynamic response functions are found. When the hydrogen bond (molecules separated by holes) is more attractive than the van der Waals interaction (molecules in contact) a transition between two fluid structures is found at null temperature and high pressure. This transition is analogous to a 'critical point' and intimately connects the anomalies in density and in thermodynamic response functions. Monte Carlo simulations were performed in the neighborhood of this transition and used to calculate the self diffusion constant, which increases with density as in liquid water.     

Synthesis of simple heparanase substrates

Heparanase degrades heparan sulfate (HS) chains on proteoglycans; elevated levels of heparanase expression correlate with tumour cell metastatic potential and vascularity, and reduced post-operative survival of cancer patients. Consequently, heparanase expression is considered a biomarker for cancer detection. Although several heparanase assays have been developed, most require the preparation of heterogeneous, (radio)labelled HS substrates and rely on the separation of enzymatically-degraded products on the basis of molecular size. In studies directed towards the development of a more direct heparanase assay, a series of glucuronides and glycosyl glucuronides were synthesised as putative heparanase substrates. These compounds were designed with various aryl aglycones that could be measured spectrophotometrically upon hydrolysis of the glycosidic linkage by heparanase. It was found that the N-sulfated 4-nitrophenyl glycosyl glucuronide 24 and the N-sulfated methylumbelliferyl glycosyl glucuronide 26 were hydrolysed by recombinant human heparanase. These compounds represent the simplest substrates of heparanase reported to date.     

Chemical composition and in vitro activity of plant extracts from Ferula communis and Dittrichia viscosa against postharvest fungi

F. communis and D. viscosa are perennial Mediterranean weeds that have been used for different therapeutic purposes in traditional pharmacopeia. Plant extracts were obtained from air dried D. viscosa young shoots (DvA) and F. communis aerial part (FcA) and roots (FcR) with n-hexane. The chemical compositions of the extracts were analyzed by HPLC-DAD, LC-MS (ESI) and LC-Q-TOF techniques. Two sesquiterpene lactones (inuviscolide, tomentosin) and three sesquiterpene acids (costic acid, hydroxycostic acid, ilicic acid) were identified from the D. viscosa extract, while in F. communis extracts three daucane sesquiterpenes (acetoxyferutinin, oxojaeskeanadioyl anisate, fertidin) and one coumarin (ferulenol) derivates were found. Biological activities of plant extracts were studied in in vitro experiments on the colonies and conidia of Botryotinia fuckeliana, Penicillium digitatum, P. expansum, Monilinia laxa, M. fructigena and Aspergillus spp. Extracts showed varying degree of antifungal activities on colony growth and conidia germination. The extract from FcA showed the least effect, while DvA extract had the strongest fungitoxic effects. FcR extract presented a fungitoxic effect on the colony growth, but it was not able to inhibit the conidia germination. These distinctions can be attributed to the differences in chemical composition of plant extracts.     

Fatigue Effects in Elastic Materials with Variational Damage Models: A Vanishing Viscosity Approach

Journal of Nonlinear Science - We study the existence of quasistatic evolutions for a family of gradient damage models which take into account fatigue, that is the process of weakening in a...     

Flow injection preconcentration by chemofiltration and spectrophotometric determination of Gd

A new on-line Gd preconcentration and determination system associated to flow injection (FI) method was developed. 2,2′-(1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid (Arsenazo III) was used as a complexing agent at pH 2.5. A reactor containing the polyamide membrane was used for the retention of the Gd complex by chemofiltration. The complex was then removed from the reactor with buffer solution pH 9. The variables affecting the combined on-line preconcentration-absorptiometric method have been evaluated and optimised. The coupling of the on-line preconcentration and spectrophotometric flow through detection led to a detection limit of 15 μg l⁻¹ for a preconcentration time of 5 min at 2 ml/min. The method was successfully applied to biological samples.