Synthesis of p-cymene from limonene, a renewable feedstock

Highly selective limonene conversions to p-cymene in short reaction times were achieved under “solvent free” conditions over mesoporous silica–alumina supports heated by microwave irradiation. An increase in the silica content of these mixed oxides led to increases in the specific surface area, porosity (pore size and volume) and the surface acidity. The conversion and selectivity of limonene to p-cymene under microwave irradiation was also found to rise as the silica content in these mixed oxides was increased. By careful choice of the solid and reaction parameters the activities for the conversion of limonene and selectivity to p-cymene (used as an intermediate in fine chemical syntheses) could be fine tuned. Results are presented under both dry media and reflux conditions.     

Electrochemical detection of Cd ions by a self-assembled monolayer of 1,9-nonanedithiol on gold

The application of 1,9-nonanedithiol (NDT) self-assembled monolayer (SAM) on gold for the electrochemical determination of Cd²⁺ was studied. Interestingly, we found that a NDT SAM strongly affects the stripping wave of Cd, resulting in a sharp peak that was used for electroanalytical determination of Cd²⁺ in aqueous solutions. The different parameters, such as potential and time of deposition of Cd, were examined. Furthermore, polarization-modulated infrared reflection absorption spectroscopy (PM IRRAS) and X-ray photoelectron spectroscopy (XPS) were used for exploring the interaction between the deposited Cd and the thiol groups on Au. FTIR measurements clearly indicate that NDT is assembled in a disordered liquid type monolayer interacting with the Au electrode via both thiol moieties. XPS reveals that Cd is stripped at two different potentials and that the signal of sulfur is almost unchanged by deposition and desorption of Cd. All these finding allude to the interesting conclusion that Cd is deposited on Au lifting to some extent the thiol groups.     

LLDPE with Exclusively Ethyl Branches by Tandem Catalysis with Single-Site Zr(IV)/Co(II) Catalysts

Semicrystalline linear low density polyethylenes (LLDPEs) with exclusively ethyl branching (from 7 to 56 branches per 1,000 carbon atoms) were prepared from ethylene by homogeneous tandem catalytic systems comprising (imino)pyridine cobalt(II) dichlorides as oligomerization precursors, bis(cyclopentadienyl)zirconium(IV) dichloride as copolymerization precursor and methyaluminoxane as activator. The activity of the tandem systems was evaluated by varying either the molar fraction of the cobalt precursors or the ethylene pressure. The latter parameter was of crucial importance to control both the productivity and the extent of 1-butene incorporation. In particular, increasing the ethylene pressure from 2 bar to 4 bar changed the “comonomer effect” from positive to negative.     

Compatibilization of commingled plastics with maleic anhydride modified polyethylenes and ultraviolet preirradiation

The improvement of the properties of commingled plastics was carried out with a prototype blend of Mexican municipal plastic waste with and without poly(vinyl chloride) (PVC). Compatibilizing agents such as high‐density, low‐density, and linear low‐density polyethylenes modified with maleic anhydride were used. The agents were prepared in the laboratory with peroxide, and their usefulness was compared with that of a commercially modified linear low‐density polyethylene. The blends with PVC were preirradiated with ultraviolet radiation for 12, 24, or 48 h to create oxidized groups to help in situ compatibilization during the blending step of the reactive extrusion process. Compatibilized materials showed a markedly more homogeneous morphology with improved mechanical properties: the elongation at break and impact strength increased with the compatibilization level. The presence of PVC in commingled plastics significantly reduced the beneficial effect of the maleic anhydride modified polyethylene as a compatibilizer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Catalytic properties of dendron–OMS hybrids

The synthesis and catalytic testing of several dendron–ordered mesoporous silica hybrids are reported. These materials are active in both the nitroaldol (Henry) reaction and the transesterification of glyceryl tributyrate to afford methyl esters. In both reactions it is observed that dendrons terminated with primary amines are more catalytically active than samples containing dendrons terminated with secondary amines. On a mmol nitrogen per gram of silica basis, the first generation dendrons are the most active for both chemistries, and the SBA-15 samples display a higher activity than the MCM-41 samples. The pore-size effect observed is consistent with significant diffusion resistance in the MCM-41 samples. The activity trend observed in the SBA-15 materials is consistent with decreased cooperative effects between the amines and surface silanols as the dendrons become larger. Clear trends are observed indicating that higher generation dendrons are more selective to alcohol formation in the Henry reaction. The dendron catalysts are much more active and stable than simple amines attached to silica in the transesterification of triglycerides. Preliminary results shown indicate that these materials can also catalyze more demanding chemistries, an example of which is the Aldol condensation of 5-(hydroxymethyl)furfural and acetone. The results shown indicate that dendron–OMS hybrids can serve as effective solid base catalysts for a diverse range of chemistries.     

Preparation of stearidonic acid‐enriched triacylglycerols from Echium plantagineum seed oil

HPLC analysis of Echium plantagineum seed oil shows a complex triacylglycerol (TAG) profile. TAG species were separated on an analytical scale by HPLC and their fatty acid (FA) composition is reported. GLC analyses showed that some TAG fractions reached a stearidonic acid (SDA, 18:4n‐3) percentage significantly higher than that in the original oil. TAG separation on a bigger scale was also essayed, by means of a gravimetric normal‐phase chromatographic column, using silver ion‐silica gel as stationary phase. Gradient elution with solvents of increasing polarity was applied, allowing the separation of valuable TAG species containing γ‐linolenic acid (GLA, 18:3n‐6), α‐linolenic acid (ALA, 18:3n‐3) and SDA as the main constituents (more than 85% of the total FA). An enzymatic hydrolysis reaction showed the distribution of FA in the isolated species of TAG. SDA was the major FA in the sn‐2 position (more than 50% of total FA), followed by ALA (19%) and GLA (18.5%).     

Nonlinear dynamics of potassium iodide adsorption on the interface of carbon steel in acidic medium

The development of inhibitors for hydrochloric acidic media is very common. Potassium iodide, in combination with some organic inhibitors, may transform a mediocre inhibitor into an excellent corrosion inhibitor based on a synergetic effect. There is a need to study what happens at the interface in the presence of this compound. The dynamics of the metal electrolyte interface when KI concentration increases has been characterized. The present study has been carried out based on electrochemical impedance spectroscopy and electrochemical noise analysis in the light of nonlinear phenomena by applying recurrence plots and fractal geometry. The fractal dimension of the current–time series shows a direct relationship with the fractal dimension of the surface of steel. The phenomenon of self-organization has been observed on the metal surface. The nonlinear analysis carried out by means of recurrence plots showed that the iodide ions' inhibitory effect is not only simple adsorption but also a nonlinear phenomenon that auto-organizes. The degree of complexity increases, consequently causing an interaction between the microcells and resulting in a lower charge-transfer rate.     

Capacitance properties of electrochemically deposited polyazulene films

Polyazulene films formed by electrochemical oxidation of azulene have been studied as active components in electrochemical capacitors. The film shows reversible electrochemical behavior in the positive potential range and exhibits p-doping properties. The influence of film formation conditions on the films electrochemical properties has been investigated. A strong effect of solvent on the polyazulene deposition has been observed. The highest yield of film deposition was found for dichloromethane. Polyazulene films also exhibit stable voltammetric properties in aprotic solvents. The voltammetric response of the film is affected by the size of the anion of the supporting electrolyte. In solutions containing tetra(alkyl)ammonium perchlorates, tetrafluoroborates or hexafluorophosphates, reversible oxidation of polyazulene is obtained. In the presence of large tetra(phenyl)borate anions, polyazulene is irreversibly oxidized upon electrochemical oxidation. The capacitance properties of these materials have been investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The polyazulene film displays a relatively high specific capacitance close to 400 F g⁻¹. Such high value of C_s locates this material among very good polymeric redox pseudo-capacitors.     

A Potent N-(piperidin-4-yl)-1H-pyrrole-2-carboxamide Inhibitor of Adenylyl Cyclase of G. lamblia: Biological Evaluation and Molecular Modelling Studies

In this work, we report a derivative of N-(piperidin-4-yl)-1H-pyrrole-2-carboxamide as a new inhibitor for adenylyl cyclase of Giardia lamblia which was obtained from a study using structural data of the nucleotidyl cyclase 1 (gNC1) of this parasite. For such a study, we developed a model for this specific enzyme by using homology techniques, which is the first model reported for gNC1 of G. lamblia. Our studies show that the new inhibitor has a competitive mechanism of action against this enzyme. 2-Hydroxyestradiol was used as the reference compound for comparative studies. Results in this work are important from two points of view. on the one hand, an experimentally corroborated model for gNC1 of G. lamblia obtained by molecular modelling is presented; on the other hand, the new inhibitor obtained is an undoubtedly excellent starting structure for the development of new metabolic inhibitors for G. lamblia.