Size-dependent direct electrochemical detection of gold nanoparticles: application in magnetoimmunoassays

The effect of the AuNPs size, ranging from 5 nm to 80 nm, on the electrochemical response of screen-printed carbon electrodes (SPCEs) used as electrochemical transducers is investigated for the first time. A simple hydrodynamic modelling and calculation at the nanoscale level is applied so as to find the effect of the size of AuNP upon the electrochemical response. The results show that the best electrochemical response for AuNP suspension for the same concentration of total gold is obtained for the 20 nm sized nanoparticles. It is concluded that the Brownian motions avoid a better response for smaller AuNPs that should in fact be related with the best electrochemical signal due to their higher surface area. Finally, the size effect is studied for AuNPs acting as electroactive labels in an immunosensor that employs magnetic beads as platforms of the bioreactions. The best response for the 5 nm AuNPs in this case is due to the fact that in the immunosensing conditions the Brownian motions are minimized because the AuNPs contact with the electrotransducer surface is induced by the immunoreaction and the fast magnetic collection of the nanoparticles used as antibody labels upon application of a magnetic field.     

Effect of gold addition on Pt and Pd catalysts in liquid phase oxidations

Single phase Au–Pd and Au–Pt on carbon catalysts have been compared in the liquid phase oxidation of glycerol (representative for polyols) and n-octanol (representative for long chain aliphatic alcohol). The observed overall enhancement of catalytic activity appeared to be function of support, substrate and reaction conditions. Effect of substrate structure has been disentangled: synergistic effect between Au and Pt was maximized when polyol-like substrates were oxidized whereas Au–Pd based catalyst showed a more general match.     

Tensile mechanical behavior of linear high‐density polyethylenes modified with organic peroxide

The molecular structure of several high‐density polyethylenes of different molecular weights and vinyl contents was modified without altering their thermoplastic character using an organic peroxide. Chain linking was the main chemical event that occurred during the modification process. Samples of these polymers were crystallized from the melt, generating materials with different morphologies. Two crystallization procedures were followed: slow cooling and quenching. The density and crystallinity of the polymers were found to be slightly dependent on the molecular structures generated by the modification process. Tensile tests were performed at room temperature to evaluate the mechanical behavior of the polymers. The mechanical response of some of the slowly cooled samples changed from brittle to ductile when increasing concentrations of peroxide were added to the formulation. All the quenched samples displayed ductile behavior. The elastic modulus and yield stress were found to increase linearly with the crystallinity of the polymers independently of the molecular structure generated by the modification process. The molecular weight of the modified polymers appears to be the main structural property that influences the draw ratio after break and the ultimate tensile stress of the samples. The draw ratio diminishes, while the ultimate tensile stress increases with the molecular weight of the polymers, irrespective of the evolution of other molecular parameters.     

Chromatic evolution of virgin olive oils submitted to an accelerated oxidation test

Six samples of virgin olive oil obtained from several varieties of olive fruits (Picual, Manzanilla, Lechín, and Arbequina) were submitted to an accelerated oxidation process during a 63-h period under the conditions of the oil stability index (OSI), as measured by a Rancimat (100°C) apparatus. Spectra were measured every 3 h, and chlorophyll and carotenoid indexes and CIFLAB color ordinates were calculated. As oxidation time increased, remarkable changes in the spectral characteristics and color ordinates were observed. Oxidation provoked less vivid colors (lower values for chroma, C _* ^ab ) in all the samples; however, only some varieties became darker (lower values for lightness, L^*). The pigment loss calculated for oxidized oils was 67% for the carotenoid index and 58% for the chlorophyll index. Mathematical models are offered to predict color changes with time of storage at 20°C.     

Linear and Cyclic Depsipeptidomimetics with β‐Lactam Cores: A Class of New αvβ3 Integrin Receptor Inhibitors

The α_vβ₃ integrin receptor plays an important role in tumor metastasis and tumor‐induced angiogenesis. The inhibition of this receptor with diverse ligands, antibodies, or cyclic peptides is a promising research field for the treatment of a variety of tumors. The replacement of Phe‐(Me)Val dipeptide by a β‐lactam ring in Cilengitide has led to new products that show higher inhibitory activity than the parent cyclopeptide. In particular, substitution of a peptide bond β‐lactam‐NH‐Asp linkage by a β‐lactam‐O‐Asp ester linkage increases the activity of the new cyclodepsipeptide. In the same way it has been found that open‐chain compounds of the form Asp‐β‐lactam‐Arg can interact with the receptor and inhibit its activity moderately. The integrin inhibitory activity of the synthesized compounds has been established by using the CGH array, a method that appears to be a more reliable trial than the classical adhesion test.     

Effect of brominated vegetable oils on heart lipid metabolism

Normal rats fed for 105 days on an experimental diet made up of standard laboratory chow supplemented with 0.5% of a mixture of brominated sunflower-olive oil (BVO) developed a significant increase in the triacylglycerol content of the heart, liver and soleus muscle compared to controls. In addition, BVO-treated rats had a decrease in plasma levels of triacylglycerol and total and HDL cholesterol. Plasma fatty acid levels and plasma post-heparin lipolytic activities, such as H-TGL, LPL, T-TGL and MGH were similar to those of control animals fed the standard chow alone. Heart PDH_a (active portion of pyruvate dehydrogenase) was dramatically decreased in the BVO-fed rats. A faster rate of spontaneous lipolysis was recorded in the isolated perfused preparation of hearts from the experimental animals. The addition of 10⁻⁷ M of glucagon to the perfusate, however, revealed a lipolytic effect comparable to the one observed in the control rats. In summary, our findings of normal fatty acids and low triacylglycerol plasma levels associated with normal activities of the various PHLA (post-heparin lipolytic activity) enzymes suggest that accumulation of triacylglycerol in heart muscle may not be explained essentially in terms of an elevated uptake and/or increased delivery of plasma fatty acids or plasma triacylglycerol. A decreased in situ catabolism of tissue triacylglycerol also appears unlikely because the spontaneous as well as the glucagon induced lipolysis in the heart both were found to be unimpaired. Our results suggest that the mechanisms involved in the toxicologic effects of a BVO diet on heart lipid metabolism could be exerted mainly at the level of triacylglycerol biosynthesis rather than a derangement in some known step of their catabolic pathway. Additional studies are necessary to clarify this matter. An abstract pertaining to this work was presented in November 1984 at the IV Congress of the Pan American Association of Biochemical Societies (PAABS), Buenos Aires, Argentina.     

Heat recovery from Diesel engines: A thermodynamic comparison between Kalina and ORC cycles

In the context of heat recovery for electric power generation, Kalina cycle (a thermodynamic cycle using as working fluid a mixture of water and ammonia) and Organic Rankine Cycle (ORC) represent two different eligible technologies. In this work a comparison between the thermodynamic performances of Kalina cycle and an ORC cycle, using hexamethyldisiloxane as working fluid, was conducted for the case of heat recovery from two Diesel engines, each one with an electrical power of 8900 kWe. The maximum net electric power that can be produced exploiting the heat source constituted by the exhaust gases mass flow (35 kg/s for both engines, at 346 °C) was calculated for the two thermodynamic cycles. Owing to the relatively low useful power, for the Kalina cycle a relatively simple plant layout was assumed. Supposing reasonable design parameters and a logarithmic mean temperature difference in the heat recovery exchanger of 50 °C, a net electric power of 1615 kW and of 1603 kW respectively for the Kalina and for the ORC cycle was calculated.Although the obtained useful powers are actually equal in value, the Kalina cycle requires a very high maximum pressure in order to obtain high thermodynamic performances (in our case, 100 bar against about 10 bar for the ORC cycle). So, the adoption of Kalina cycle, at least for low power level and medium–high temperature thermal sources, seems not to be justified because the gain in performance with respect to a properly optimized ORC is very small and must be obtained with a complicated plant scheme, large surface heat exchangers and particular high pressure resistant and no-corrosion materials.     

In-situ neutron diffraction study of magnesium amide/lithium hydride stoichiometric mixtures with lithium hydride excess

The hydrogen sorption of mixtures of magnesium amide (Mg(NH₂)₂) and lithium hydride (LiH) with different molecular ratios have been investigated using in-situ neutron diffraction; the experiments were performed at D20/ILL and SPODI/FRMII. The results reveal a common reaction pathway for 1:2, 3:8 and 1:4 magnesium amide: lithium hydride mixtures. Intermediate reaction steps are observed in both ab- and desorption. The thermodynamic properties of the system at 200 °C are not changed by the addition of excess lithium hydride. This finding has important implications for the tailoring the characteristics of this promising hydrogen storage material.