Microwave irradiation has been successfully applied in organic chemistry. Spectacular accelerations, higher yields under milder reaction conditions and higher product purities have all been reported. Indeed, a number of authors have described success in reactions that do not occur by conventional heating and even modifications of selectivity (chemo-, regio- and stereoselectivity). The effect of microwave irradiation in organic synthesis is a combination of thermal effects, arising from the heating rate, superheating or "hot spots" and the selective absorption of radiation by polar substances. Such phenomena are not usually accessible by classical heating and the existence of non-thermal effects of highly polarizing radiation--the "specific microwave effect"--is still a controversial topic. An overview of the thermal effects and the current state of non-thermal microwave effects is presented in this critical review along with a view on how these phenomena can be effectively used in organic synthesis.
Anaplasma phagocytophilum is an emerging zoonotic pathogen that causes human granulocytic anaplasmosis. These intracellular bacteria establish infection by affecting cell function in both the vertebrate host and the tick vector, Ixodes scapularis. Previous studies have characterized the tick transcriptome and proteome in response to A. phagocytophilum infection. However, in the postgenomic era, the integration of omics datasets through a systems biology approach allows network-based analyses to describe the complexity and functionality of biological systems such as host-pathogen interactions and the discovery of new targets for prevention and control of infectious diseases. This study reports the first systems biology integration of metabolomics, transcriptomics, and proteomics data to characterize essential metabolic pathways involved in the tick response to A. phagocytophilum infection. The ISE6 tick cells used in this study constitute a model for hemocytes involved in pathogen infection and immune response. The results showed that infection affected protein processing in endoplasmic reticulum and glucose metabolic pathways in tick cells. These results supported tick-Anaplasma co-evolution by providing new evidence of how tick cells limit pathogen infection, while the pathogen benefits from the tick cell response to establish infection. Additionally, ticks benefit from A. phagocytophilum infection by increasing survival while pathogens guarantee transmission. The results suggested that A. phagocytophilum induces protein misfolding to limit the tick cell response and facilitate infection but requires protein degradation to prevent ER stress and cell apoptosis to survive in infected cells. Additionally, A. phagocytophilum may benefit from the tick cell's ability to limit bacterial infection through PEPCK inhibition leading to decreased glucose metabolism, which also results in the inhibition of cell apoptosis that increases infection of tick cells. These results support the use of this experimental approach to systematically identify cell pathways and molecular mechanisms involved in tick-pathogen interactions. Data are available via ProteomeXchange with identifier PXD002181. Molecular & Cellular
Microwave irradiation has been applied with success to cycloaddition reactions. The special characteristics of such irradiation entails the use of new methodologies, including equipment, glassware, solvents, and solid supports. All of these aspects are described in this review. Under classical heating conditions, these reactions usually require long reaction times, high temperatures, and/or Lewis acid catalysts, resulting in partial or total decomposition of sensitive compounds. This is a particularly significant problem in the synthesis of natural products. These problems have been conveniently overcome by the use of microwave irradiation. The short reaction time associated with microwave activation avoids decomposition of reagents and products, and prevents polymerization of the diene or dienophile. Heterocyclic compounds have been synthesized by cycloaddition reactions, or have been observed to react as dienes and dipoles under microwave irradiation conditions. Even those heterocyclic systems that are very reluctant to participate in cycloaddition reactions, such as pyrazoles, can be induced to react under microwave irradiation conditions. The application of this method to the chemistry of [60]fullerene has permitted derivatization of this system while avoiding the problems of polycycloaddition and cycloreversion. In most cases, spectacular accelerations and great improvements in yields and reaction conditions are observed. Finally, in some cases, changes in the chemo‐, regio‐, or stereoselectivity have been observed. These changes have been connected with the absolute hardness of the transition state, with the harder state being favored under microwave irradiation conditions. Microwave chemistry thus opens new possibilities for modifying the result of competitive reactions by considering the relative hardness of the transition states.
Mango is the second most consumed tropical fruit after banana and the by-products of mango processing (peel, kernel and seed) roughly comprise 35 -60% of the total fruit weight, thus representing a potentially high volume resource of exploitable biobased chemicals and materials. Herein, conversion and characterisation of waste mango peels from three different cultivars (Alphonso, Honey and Tommy Atkins) into pectin and porous cellulose using low temperature microwave-assisted acid-free hydrolytic conditions is reported. Microwave-assisted acid-free extraction yielded up to 11.63% (dry weight basis) of pectin which was characterised by IR, NMR (both solution and solid phase) and TGA which showed close similarity to commercial (acid extracted) pectin. The degree of esterification of pectin was determined by 13C NMR (75.6 -86.2%) and titrimetry (79.3-87.7%) and the pectin showed excellent gelling ability. The molecular weight as determined by GPC was in the range 14130 (Honey) -25540 (Tommy Atkins). Porosity measurements on the depectinated residue, i.e., residual cellulosic matter showed mesoporous characteristics: average pore diameter, 9.3 nm (Alphonso) -10.5 nm (Honey), however with poor surface area 16.3 m 2 g -1 (Honey) -26.0 m 2 g -1 . Interestingly, a second microwave hydrothermal treatment on these residues retained mesoporosity whilst significantly increasing surface area (88.8 m 2 g -1 (Honey) -124.0 m 2 g -1 (Alphonso)) and pore volume by approximately six-fold. This is the first detailed combined study of microwave-assisted extraction to yield pectin and mesoporous cellulose towards a potential zero waste mango biorefinery.
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