Over the T-range of this work, k(T) can be expressed as k(T, P = 0) = 2.31 × 10-11 (T/300 K)-1.615 exp(-38.45/T) cm3 s-1 for T = 50-400 K k(T, P = 0) = 1.15 × 10-12 (T/300 K)0.8637 exp(892.6/T) cm3 s-1 for T = 400-1000 K k(T, P = 0) = 4.57 × 10-15 (T/300 K)3.375 exp(3477.4/T) cm3 s-1 for T = 1000-3500 K.Stabilization of multiply-charged atomic clusters in the gas phase has been a topic of great interest not only because of their potential applications as weakly-coordinating anions, but also for their ability to promote unusual reactions and serve as building blocks of materials. Recent experiments have shown that, after removing one terminal ligand from the closo-dodecacyano-borate, B12(CN)122-, the cluster can strongly bind an argon atom at room temperature. Bearing this in mind, here, we have developed more than a dozen highly stable tri- and tetra-anions using density functional theory (DFT) calculations with hybrid functional (B3LYP) and semi-empirical dispersion corrections. The interactions between the clusters and noble gas atoms, including Ne, Ar and Kr, are studied. The resulting super-electrophilic sites embedded in these charged clusters can bind noble gas atoms with binding energies up to 0.7 eV. This study enriches the database of highly-charged clusters and provides a viable design rule for super-electrophiles that can strongly bind noble gas atoms.Comprehensive investigations of the possible formation pathways of sulfate, the main composition of atmospheric aerosol in marine areas, continue to challenge atmospheric chemists. As one of the most important oxidation routes of S(iv) contributing to sulfate formation, the reaction process of S(iv) oxidized by hypobromic acid, which is ubiquitous with the gas-phase mixing ratios of ∼310 ppt and has a well-known oxidative capacity, has attracted wide attention. However, little information is available about the detailed reaction mechanism. Especially, due to the abundant species in cloud water, the potential effect of these compositions on these reaction processes and the corresponding effect mechanism are also uncertain. Using high-level quantum chemical calculations, we theoretically elucidate the two-step mechanism of Br+ transfer proposed by experiment through the verification of the key BrSO3- intermediate formation and subsequent hydrolysis reaction or the uncovered reaction of BrSO3- intermediate with OH-. Further, the novel and more competitive mechanisms (OH+ or O atom transfer pathways) that have not been considered in previous studies, leading to sulfate formation directly, have been found. Furthermore, it should be mentioned that we revealed the effect mechanism of constituents catalyzed in cloud water, especially the important H2O-catalyzed mechanism. In addition, all the above pathways follow this catalytic mechanism. This finding indicates a linkage between the complex nature of the atmospheric constituents and related atmospheric reaction, as well as the enhanced occurrence of atmospheric secondary sulfate formation in the atmosphere. Hence, this exploration of sulfate formation related to hypobromic acid could provide a better understanding about the sources of sulfate in marine areas.Type 2 diabetes mellitus (T2DM) is a prevalent chronic disease characterized by hyperglycemia and insulin resistance. Regular exercise is one of the effective lifestyle interventions for maintaining healthy weight and blood glucose levels in the normal range and lowering risk factors. Probiotics, live microorganisms that are beneficial to health, are involved in the regulation of host metabolism. We thus hypothesize that the combination of exercise training and Bifidobacterium longum OLP-01 (OLP-01) could improve insulin sensitivity, blood glucose control and body composition in db/db ****. Twenty-four C57BL/6 J db/db male **** (20-weeks old) were divided into four groups (n = 6 per group) vehicle, OLP-01 supplementation (OLP-01), exercise training (EX) and exercise training with OLP-01 supplementation (EX + OLP-01). Animals in the EX and EX + OLP-01 groups underwent strength exercise training for 6 weeks, 5 days per week. After the exercise training, we tested forelimb grip strength, exhaustive running, oral glucose tolerance test (OGTT) and serum biomarkers. Results Combined intervention of EX and OLP-01 prevented elevation of body weight and body fat. https://www.selleckchem.com/products/ak-7.html Grip strength and exhaustive swimming time were significantly higher in the EX + OLP-01 group than in the other groups. We found that EX OLP-01 reduced glycolipid parameters (fasting blood glucose and hemoglobin A1c), improved insulin sensitivity (oral glucose tolerance test and HOMA-IR), relieved liver injury parameters (aspartate aminotransferase and alanine aminotransferase) and repaired pancreas damage. Based on our findings, we speculate that the positive effects of combining EX with OLP-01 on capacity for physical activity, blood glucose control and body composition suggest an integrative approach to treating type 2 diabetes. Altogether, the combination of EX with OLP-01 treatment might be a good candidate for preventing and treating diabetes.A palladium-catalyzed highly selective tetrafunctionalization of 3,6-I2-o-carborane and 4,7-I2-o-carborane has been developed, leading to the preparation of 3,6-dialkenyl-4,11-R2-o-carboranes and 4,7-dialkenyl-5,11-R2-o-carboranes (R = alkyl, allyl and aryl) in moderate to excellent yields. This represents a new strategy for selective synthesis of polyfunctionalized o-carborane derivatives via a one-pot process.Phototherapy for cancer treatment has received **** attention in recent years, and compounds with multiple anticancer mechanisms upon irradiation are particularly appealing. In this work, a nitro-anthraquinone group was attached to a biq (2,2'-biquinoline) ligand based Ru(ii) complex, endowing the resultant Ru1 compound with multiple anticancer mechanisms upon 600 nm light irradiation. Ru1 can undergo biq ligand photodissociation, showing its potential as a photoactivated chemotherapy (PACT) agent. Moreover, a Ru(iii) centre and an anthraquinone anion centre may be generated upon irradiation, which can further oxidize NADH/NADPH and generate O2˙-, successfully eliciting photoredox catalysis and photodynamic therapy (PDT). Compared to the control complex Ru2 without the nitroanthraquinone group, Ru1 exhibited **** enhanced photocytotoxicity towards a series of cancer cell lines and 3D multicellular spheroids upon red light irradiation.
Over the T-range of this work, k(T) can be expressed as k(T, P = 0) = 2.31 × 10-11 (T/300 K)-1.615 exp(-38.45/T) cm3 s-1 for T = 50-400 K k(T, P = 0) = 1.15 × 10-12 (T/300 K)0.8637 exp(892.6/T) cm3 s-1 for T = 400-1000 K k(T, P = 0) = 4.57 × 10-15 (T/300 K)3.375 exp(3477.4/T) cm3 s-1 for T = 1000-3500 K.Stabilization of multiply-charged atomic clusters in the gas phase has been a topic of great interest not only because of their potential applications as weakly-coordinating anions, but also for their ability to promote unusual reactions and serve as building blocks of materials. Recent experiments have shown that, after removing one terminal ligand from the closo-dodecacyano-borate, B12(CN)122-, the cluster can strongly bind an argon atom at room temperature. Bearing this in mind, here, we have developed more than a dozen highly stable tri- and tetra-anions using density functional theory (DFT) calculations with hybrid functional (B3LYP) and semi-empirical dispersion corrections. The interactions between the clusters and noble gas atoms, including Ne, Ar and Kr, are studied. The resulting super-electrophilic sites embedded in these charged clusters can bind noble gas atoms with binding energies up to 0.7 eV. This study enriches the database of highly-charged clusters and provides a viable design rule for super-electrophiles that can strongly bind noble gas atoms.Comprehensive investigations of the possible formation pathways of sulfate, the main composition of atmospheric aerosol in marine areas, continue to challenge atmospheric chemists. As one of the most important oxidation routes of S(iv) contributing to sulfate formation, the reaction process of S(iv) oxidized by hypobromic acid, which is ubiquitous with the gas-phase mixing ratios of ∼310 ppt and has a well-known oxidative capacity, has attracted wide attention. However, little information is available about the detailed reaction mechanism. Especially, due to the abundant species in cloud water, the potential effect of these compositions on these reaction processes and the corresponding effect mechanism are also uncertain. Using high-level quantum chemical calculations, we theoretically elucidate the two-step mechanism of Br+ transfer proposed by experiment through the verification of the key BrSO3- intermediate formation and subsequent hydrolysis reaction or the uncovered reaction of BrSO3- intermediate with OH-. Further, the novel and more competitive mechanisms (OH+ or O atom transfer pathways) that have not been considered in previous studies, leading to sulfate formation directly, have been found. Furthermore, it should be mentioned that we revealed the effect mechanism of constituents catalyzed in cloud water, especially the important H2O-catalyzed mechanism. In addition, all the above pathways follow this catalytic mechanism. This finding indicates a linkage between the complex nature of the atmospheric constituents and related atmospheric reaction, as well as the enhanced occurrence of atmospheric secondary sulfate formation in the atmosphere. Hence, this exploration of sulfate formation related to hypobromic acid could provide a better understanding about the sources of sulfate in marine areas.Type 2 diabetes mellitus (T2DM) is a prevalent chronic disease characterized by hyperglycemia and insulin resistance. Regular exercise is one of the effective lifestyle interventions for maintaining healthy weight and blood glucose levels in the normal range and lowering risk factors. Probiotics, live microorganisms that are beneficial to health, are involved in the regulation of host metabolism. We thus hypothesize that the combination of exercise training and Bifidobacterium longum OLP-01 (OLP-01) could improve insulin sensitivity, blood glucose control and body composition in db/db mice. Twenty-four C57BL/6 J db/db male mice (20-weeks old) were divided into four groups (n = 6 per group) vehicle, OLP-01 supplementation (OLP-01), exercise training (EX) and exercise training with OLP-01 supplementation (EX + OLP-01). Animals in the EX and EX + OLP-01 groups underwent strength exercise training for 6 weeks, 5 days per week. After the exercise training, we tested forelimb grip strength, exhaustive running, oral glucose tolerance test (OGTT) and serum biomarkers. Results Combined intervention of EX and OLP-01 prevented elevation of body weight and body fat. https://www.selleckchem.com/products/ak-7.html Grip strength and exhaustive swimming time were significantly higher in the EX + OLP-01 group than in the other groups. We found that EX OLP-01 reduced glycolipid parameters (fasting blood glucose and hemoglobin A1c), improved insulin sensitivity (oral glucose tolerance test and HOMA-IR), relieved liver injury parameters (aspartate aminotransferase and alanine aminotransferase) and repaired pancreas damage. Based on our findings, we speculate that the positive effects of combining EX with OLP-01 on capacity for physical activity, blood glucose control and body composition suggest an integrative approach to treating type 2 diabetes. Altogether, the combination of EX with OLP-01 treatment might be a good candidate for preventing and treating diabetes.A palladium-catalyzed highly selective tetrafunctionalization of 3,6-I2-o-carborane and 4,7-I2-o-carborane has been developed, leading to the preparation of 3,6-dialkenyl-4,11-R2-o-carboranes and 4,7-dialkenyl-5,11-R2-o-carboranes (R = alkyl, allyl and aryl) in moderate to excellent yields. This represents a new strategy for selective synthesis of polyfunctionalized o-carborane derivatives via a one-pot process.Phototherapy for cancer treatment has received much attention in recent years, and compounds with multiple anticancer mechanisms upon irradiation are particularly appealing. In this work, a nitro-anthraquinone group was attached to a biq (2,2'-biquinoline) ligand based Ru(ii) complex, endowing the resultant Ru1 compound with multiple anticancer mechanisms upon 600 nm light irradiation. Ru1 can undergo biq ligand photodissociation, showing its potential as a photoactivated chemotherapy (PACT) agent. Moreover, a Ru(iii) centre and an anthraquinone anion centre may be generated upon irradiation, which can further oxidize NADH/NADPH and generate O2˙-, successfully eliciting photoredox catalysis and photodynamic therapy (PDT). Compared to the control complex Ru2 without the nitroanthraquinone group, Ru1 exhibited much enhanced photocytotoxicity towards a series of cancer cell lines and 3D multicellular spheroids upon red light irradiation.
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