Rhodium catalyzed chelation-assisted C-H bond functionalization reactions

Over the last several decades, researchers have achieved remarkable progress in the field of organometallic chemistry. The development of metal-catalyzed cross-coupling reactions represents a paradigm shift in chemical synthesis, and today synthetic chemists can readily access carbon-carbon and carbon-heteroatom bonds from a vast array of starting compounds. Although we cannot understate the importance of these methods, the required prefunctionalization to carry out these reactions adds cost and reduces the availability of the starting reagents. The use of C-H bond activation in lieu of prefunctionalization has presented a tantalizing alternative to classical cross-coupling reactions. Researchers have met the challenges of selectivity and reactivity associated with the development of C-H bond functionalization reactions with an explosion of creative advances in substrate and catalyst design. Literature reports on selectivity based on steric effects, acidity, and electronic and directing group effects are now numerous. Our group has developed an array of C-H bond functionalization reactions that take advantage of a chelating directing group, and this Account surveys our progress in this area. The use of chelation control in C-H bond functionalization offers several advantages with respect to substrate scope and application to total synthesis. The predictability and decreased dependence on the inherent stereoelectronics of the substrate generally result in selective and high yielding transformations with broad applicability. The nature of the chelating moiety can be chosen to serve as a functional handle in subsequent elaborations. Our work began with the use of Rh(I) catalysts in intramolecular aromatic C-H annulations, which we further developed to include enantioselective transformations. The application of this chemistry to the simple olefinic C-H bonds found in α,β-unsaturated imines allowed access to highly substituted olefins, pyridines, and piperidines. We observed complementary reactivity with Rh(III) catalysts and developed an oxidative coupling with unactivated alkenes. Further studies on the Rh(III) catalysts led us to develop methods for the coupling of C-H bonds to polarized π bonds such as those in imines and isocyanates. In several cases the methods that we have developed for chelation-controlled C-H bond functionalization have been applied to the total synthesis of complex molecules such as natural products, highlighting the utility of these methods in organic synthesis.     

New roles for community pharmacists in modern health care systems: a challenge for pharmacy education and research

The academic activities led by the Unit of Community Pharmacy can be classified as translational. Our group is interested in person-centered pharmaceutical services aimed at a more responsible use of drugs (effectiveness, safety, efficiency) in collaboration with physicians and other health care professionals in a primary care setting. The following domains of education and research are high priorities for our group: medication therapy management, medication adherence, integrated care, individualization of therapies, care management for the elderly and e-health.     

Endotracheal tube biofilm and ventilator‐associated pneumonia with mechanical ventilation

Objective: To analyze biofilm on internal and external surfaces of endotracheal tubes after their use in critical care patients, and to produce evidence of association between use of the tube, presence of biofilm, and the occurrence of pneumonia. Methods: This was a clinical study performed at the Intensive Care Unit of an emergency hospital in the interior of São Paulo state, Brazil. Data collection involved 30 endotracheal tubes used on adult patients for a period of ≥48 h of mechanical ventilation for scanning electron microscopy. Results: Analysis of the biofilm on the 30 tubes by scanning electron microscopy showed various abiotic and biotic structures, predominately on the internal surface, such as: fibrin network, erythrocytes, leukocytes, cocci, bacilli, and molds, among others. The intubation period of the endotracheal tube for ≥8 days represented one of the risk factors for ventilator‐associated pneumonia (RR 7.41, P < 0.001). Conclusions: The presence of the endotracheal tube permits microbial colonization, overall contributing to the development of biofilm and the occurrence of pneumonia. Microsc. Res. Tech. 77:305–312, 2014. © 2014 Wiley Periodicals, Inc.     

AN EXPERIMENTAL STUDY OF THE EFFECT OF PARAFFINIC SOLVENTS ON THE ONSET AND BULK PRECIPITATION OF ASPHALTENES

ABSTRACT

Asphaltene onset concentration and bulk deposition were measured for a typical live reservoir oil titrated with n-C₆H₁₄, n-C₅H₁₂, n-C₄H₁₀, C₃H₈, C₂H₆, CH₄ and CO₂ at 100° C (212 ° F) and 29.9 MPa (4340 psia). The concentration of titrant at asphaltene onset was observed to decrease approximately in a linear fashion with decreasing molecular weight of the paraffinic solvent; CH₄ did not induce any asphaltene precipitation. Bulk deposition experiments were performed using a solvent: oil volume ratio of 10:1; the results indicated that the weight percent of asphaltenes precipitated increased exponentially with decreasing molecular weight of the paraffinic solvents. More importantly, the asphaltene molecular weight showed a maximum for n-C₄H₁₀ precipitated asphaltenes. Possible explanations for this unusual result are presented.     

Rheological Properties of Frozen Concentrated Orange Juice (FCOJ) as a Function of Concentration and Subzero Temperatures

Data on flow properties of Frozen Concentrated Orange Juice (FCOJ) produced from oranges cv. Pera-Rio (65.04 °Brix, 8.8% w/w pulp content, 2.5% w/w pectin, 3.84% citric acid, 1.293 g cm^?3) from ?18 to 0°C were fitted with appropriate predictive models. The power law model was found to be the most appropriate to fit the flow curves obtained for FCOJ between 46.56 and 65.04 °Brix. In higher concentrations, thixotropy was observed and showed more temperature dependence. A single equation combining Arrhenius and exponential relationships was applied to describe the temperature effect and shear rate on the quantity of breakdown of FCOJ.     

Electron Impact Mass Spectra With Supercritical Fluid Chromatography/Mass Spectrometry

ABSTRACT

An SFC/MS system has been constructed through additions and appropriate modifications to a GC/MS instrument. Supercritical fluid conditions were effected by transport of liquid carbon dioxide mobile phase through a micro pump to the injector and then into a fused silica capillary column. Two approaches to a successful coupling of the resultant effluent to the GC/MS system in order to yield EI mass spectra have been demonstrated. In one configuration, an open-split GC/MS interface was used to eliminate excess mobile phase. Inside the heated interface was a frit restrictor connected to a deactivated, uncoated fused silica capillary column (also heated) which functioned as a transfer line into the ion source. An alternate configuration omitted the open-split interface and located the frit restrictor inside the ion source. A specially fabricated stainless steel rod, heated by the ion source heater, had a conical opening into which the restrictor tip was positioned and also heated. In both configurations, a turbomolecular pump was used in the ion source. In the above systems, EI mass spectra were satisfactorily produced without ion-molecule contributions or carbon dioxide clusters. The resulting spectra can thus be searched against a conventional mass spectral library for the identification of compounds separated by supercritical fluid chromatography.     

A potential biodegradable lubricant from castor biodiesel esters

Worldwide, 12 million tonnes per year of lubricants are disposed of in the environment through leakages, exhausted gas, incorrect disposal, water–oil emulsions and so on. Some are resistant to biodegradation, representing an environmental threat. One solution to modify this situation is the replacement of mineral oils by biodegradable synthetic lubricants. Esters, whose chemical structures are similar to natural triglycerides, are excellent substitutes for mineral oils. Castor oil contains around 90% ricinoleic acid, and as a result, castor oil has a higher viscosity and a lower viscosity index, compared with other vegetable oils. This work was based on the production of biodegradable lubricant base fluids from castor biodiesel esters, using various chemical catalysts to yield products with interesting properties, such as high viscosity index and good oxidation stability, compared with mineral oils. This route to lubricants is safer, more economical and more efficient. Copyright © 2012 John Wiley & Sons, Ltd.     

Who pays for the ‘beer fridge’? Evidence from Canada

The energy intensity of refrigerators varies widely across vintages. Recent improvements in the energy efficiency of refrigerators have the potential to decrease residential energy use, and in some locations this could have a significant impact on a typical household's greenhouse gas (GHG) emissions. Among the impediments to the realization of the energy use and environmental benefits from the technological energy-efficiency gains in Canada is the fact that a large proportion of households continue to use their old refrigerators as ‘beer fridges’ after the purchase of a new refrigerator. In this paper, we use information from the Survey of Household Energy Use (SHEU-2003) to examine this phenomenon. The empirical results are discussed in the context of existing Canadian programs that target purchases of new refrigerators and the disposal of old ones.     

The high-speed deformation behavior of TRIP steels

The high-speed deformation behavior of TRIP steel was investigated at strain rates ranging from 10⁻² s⁻¹ to 10³ s⁻¹. The effects of metallurgical factors, such as the rolling direction, thickness, and gage length, on the tensile properties at various strain rates were evaluated. The ultimate tensile strength, uniform elongation, strain rate sensitivity, absorbed energy, and strain-hardening exponent are reported. In general, the strength increases and the ductility decreases as the strain rate increases. The samples with a high amount of retained austenite had two distinct regions of strain rate sensitivity, showing high strain rate sensitivity over a strain rate of 10² s⁻¹. The tensile properties were not affected by the gage length and thickness of the tensile samples; however, the rolling direction of the tensile samples affected the UTS values slightly. The absorbed energy of the TRIP steel greatly exceeded that of HSLA steel.     

Mobilisation of bacteria in a fine-grained residual soil by electrophoresis

An investigation of electrokinetic bacterial mobilisation in a residual soil from gneiss is presented here. The experimental program aimed at assessing the efficacy of electrophoresis against the electro-osmotic flow to transport endospores of Bacillus subtilis LBBMA 155 and nitrogen-starved cells of Pseudomonas sp. LBBMA 81. Electrokinesis was performed on a low hydraulic reconstituted clayey soil column submitted to a 5mA electrical current for 24h. Cells were coccoid-shaped and characterised as possessing low surface hydrophobicity and less than 1microm in diameter. Distribution coefficient for B. subtilis in the soil was between 16.8 and 19.9 times higher than that for Pseudomonas sp. Distribution coefficient for B. subtilis between eluate and anionic exchange column was 11.8 times higher than that for Pseudomonas sp. After the electrokinesis, it was shown that cells and endospores were distributed hyperbolically through the soil probe and moved against the electro-osmotic flow; however, endospores were transported throughout all soil core and starved cells only till half of its length. The higher transport efficiency of B. subtilis endospores was attributed to their higher negative charge on cell surface. These results demonstrate that electrokinesis can be used for bacteria transport in soils with low hydraulic conductivity, even against the electro-osmotic flow.