Temperature dependence of ultra-exothermic charge recombinations.

We measured the temperature dependence (from +32 to -50 degrees C) of charge-recombination rates between contact radical ion pairs in isopropyl ether. In the systems selected for this study, aromatic hydrocarbon cations are the electron acceptors and the fumaronitrile anion is the electron donor. Nearly quantitative electron transfers occur at all temperatures. The charge recombinations have excess exothermicities of -60 kcal mol(-1) and exhibit a very weak temperature dependence. Our observations emphasize the absence of solvent effects and the relevance of nuclear tunneling in charge recombinations.     

Ultrafast dephasing of localized surface plasmons in colloidal silver nanoparticles: the influence of stabilizing agents

Localized surface plasmon dephasing times for aqueous colloidal silver nanoparticles (NPs) stabilized with three different capping agents (trisodium citrate??TSC, poly(vinylpyrrolidone)??PVP, and poly(vinylalcohol)?? PVA) were measured using the persistent spectral hole burning technique. The results obtained by fitting a theoretical curve to the experimental data show that the dephasing times are dependent on the chosen stabilizer (3.0, 2.3, and 1.8?fs for TSC, PVP, and PVA, respectively), and the differences are attributed to changes in the electronic density of states due to the interaction between the NPs and the capping agents. The results are supported by ab initio calculations for the chemisorbate and metallic cluster interaction.     

Synthesis of chiral spiropyrazoline-β-lactams and spirocyclopropyl-β-lactams from 6-alkylidenepenicillanates

Chiral spiropyrazolinepenicillanates were obtained in a stereoselective fashion via 1,3-dipolar cycloaddition reactions of 6-alkylidenepenicillanates with diphenyldiazomethane, phenyldiazomethane, and diazomethane. Microwave-induced ring contraction of spiro-1-pyrazoline-β-lactams leading to chiral spirocyclopropylpenicillanates is also described.     

Electrochemical behavior of europium perovskites (Ca<Subscript>0.6</Subscript>Eu<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript>) in alkaline aqueous media

In this paper, the electrochemical behavior of europium perovskites (Ca_0.6Eu_0.4MnO₃) prepared by a gel combustion method followed by a thermal treatment performed at 1073 and 1473 K is compared with the pristine oxide CaMnO₃ (T = 1073 K) obtained by the same method. The experiments were performed in alkaline aqueous media via open-circuit potential, cyclic voltammetry, chronopotentiometry, and impedance spectroscopy. The data show that the electrode roughness is inversely proportional to the oxide particle size. The chronopotentiometric curves show also that the presence of europium is advantageous due to the increase of the electrode roughness for the oxides formed at the same temperature (1073 K) or by increasing the charge per unit area for the oxide formed at 1473 K. The impedance spectra, which were obtained in the capacitive behavior domain, reflect the porous morphology of the electrode surfaces according to the theory developed by Levie. This feature is particularly evident for the electrodes with an average particle diameter of 90 and 60 nm, corresponding respectively to the oxides CaMnO₃ and Ca_0.6Eu_0.4MnO₃, both formed at 1073 K.     

Monitoring the thermal efficiency of fouled heat exchangers: A simplified method

Fouling is a problem whether we are aware of it or not. In an industrial plant, it is important not only to be able to measure the buildup of unwanted deposits, but also to do it in the simplest and most economically possible way. This paper addresses the question of monitoring fouling in an oil refinery plant, where the high number of heat exchanger units and the variability of the feedstock charge pose additional problems in terms of the practicability of following the energetic performance of such equipment. In this case, the flow rates and quality of the fluids flowing through the heat exchangers do not usually correspond to the design conditions, because they change with time. Therefore, to assess the fouling level of the exchangers, the day-to-day measured thermal efficiency should not be compared with the efficiency predicted in the design calculations. The latter should be recalculated by introducing whenever necessary new values of flow rates, physical properties, and so forth, and by evaluating new heat transfer coefficients. However, the procedures are too time consuming to be applied frequently. The present work describes a simplified method for following heat exchanger performances, based on the assessment of the number of transfer units and thermal efficiencies, where the effects of changing the feedstock charge, particularly the flow rates of the fluids, are taken into account. The only data that need to be collected are the four inlet/outlet temperatures of the heat exchanger unit and one of the flow rates. Several heat exchanger units in an oil refinery were successfully monitored by means of this method, and it was found that the variations in the physical properties did not significantly affect the results obtained for the particular plant under study.     

Trigonometric function used to formulate a multi-nodal finite tubular element

It is presented an alternative formulation to solve the problem of the deformation analysis for tubular element under pinching loads. The solution is based on a new displacement field defined from a total set of trigonometric functions. The solution is developed in a multi-nodal finite tubular ring element with a total of eight degrees of freedom per section considered. The purpose of this paper is to provide an easy alternative formulation when compared with a complex finite shell element or beam element analysis for the same application. Several case studies presented have been compared and discussed with numerical analyses results reported by other authors and the results obtained with a shell element from a Cosmos/M^® programme.     

Absolute configurations of griseorhodins A and C

The known antibiotic and cytotoxic compounds griseorhodin A (1) and griseorhodin C (2) were produced in solid culture by Streptomyces puniceus AB10, which was isolated from the leaf-cutter ant Acromyrmex rugosus rugosus. Their absolute configurations were unambiguously established as 6S,6aR,7S,8S and 6R,6aR,7S,8R, respectively, using vibrational circular dichroism (VCD) and density functional theory (DFT) calculations.     

The Fumarprotocetraric Acid Inhibits Tau Covalently,Avoiding Cytotoxicity of Aggregates in Cells

Neurodegenerative disorders, including Tauopathies that involve tau protein, base their pathological mechanism on forming proteinaceous aggregates, which has a deleterious effect on cells triggering an inflammatory response. Moreover, tau inhibitors can exert their mechanism of action through noncovalent and covalent interactions. Thus, Michael’s addition appears as a feasible type of interaction involving an α, β unsaturated carbonyl moiety to avoid pathological confirmation and further cytotoxicity. Moreover, we isolated three compounds from Antarctic lichens Cladonia cariosa and Himantormia lugubris: protolichesterinic acid (1), fumarprotocetraric acid (2), and lichesterinic acid (3). The maleimide cysteine labeling assay showed that compounds 1, 2, and 3 inhibit at 50 µM, but compounds 2 and 3 are statistically significant. Based on its inhibition capacity, we decided to test compound 2 further. Thus, our results suggest that compound 2 remodel soluble oligomers and diminish β sheet content, as demonstrated through ThT experiments. Hence, we added externally treated oligomers with compound 2 to demonstrate that they are harmless in cell culture. First, the morphology of cells in the presence of aggregates does not suffer evident changes compared to the control. Additionally, the externally added aggregates do not provoke a substantial LDH release compared to the control, indicating that treated oligomers do not provoke membrane damage in cell culture compared with aggregates alone. Thus, in the present work, we demonstrated that Michael’s acceptors found in lichens could serve as a scaffold to explore different mechanisms of action to turn tau aggregates into harmless species.     

Biofouling in water systems

The paper describes the mechanisms in the development of biofouling layers (initial surface conditioning, microbial transport and attachment, mass transfer of nutrients to the biofilm surface and through the microbial layer, cell metabolism, and detachment of cells and of larger parts of the biofilm) and summarizes the effects of several factors on the buildup and stability of biofilms (nutrient availability, fluid velocity and turbulence, temperature, surface condition, and nonliving particles). Mass transfer within biofilms is treated in more detail. A biofouling model applied to the development of biofilms in heat exchangers is presented. Finally, references are made to biofouling control methods (biocide and the proper design and operation of heat exchangers) and to future research needs in this area.