Scope and Mechanistic Study of the Ruthenium-Catalyzed \u3cem\u3eortho\u3c/em\u3e-C−H Bond Activation and Cyclization Reactions of Arylamines with Terminal Alkynes

The cationic ruthenium hydride complex [(PCy3)2(CO)(CH3CN)2RuH]+BF4- was found to be a highly effective catalyst for the C−H bond activation reaction of arylamines and terminal alkynes. The regioselective catalytic synthesis of substituted quinoline and quinoxaline derivatives was achieved from the ortho-C−H bond activation reaction of arylamines and terminal alkynes by using the catalyst Ru3(CO)12/HBF4·OEt2. The normal isotope effect (kCH/kCD = 2.5) was observed for the reaction of C6H5NH2 and C6D5NH2 with propyne. A highly negative Hammett value (ρ = −4.4) was obtained from the correlation of the relative rates from a series of meta-substituted anilines, m-XC6H4NH2, with σp in the presence of Ru3(CO)12/HBF4·OEt2 (3 mol % Ru, 1:3 molar ratio). The deuterium labeling studies from the reactions of both indoline and acyclic arylamines with DC⋮CPh showed that the alkyne C−H bond activation step is reversible. The crossover experiment from the reaction of 1-(2-amino-1-phenyl)pyrrole with DC⋮CPh and HC⋮CC6H4-p-OMe led to preferential deuterium incorporation to the phenyl-substituted quinoline product. A mechanism involving rate-determining ortho-C−H bond activation and intramolecular C−N bond formation steps via an unsaturated cationic ruthenium acetylide complex has been proposed

Simulation Analysis for in-Line Sorting-and-Washing of Reusable Pallets: A Case Study

In this study, a system constituting an integral part of a continuous sequence of operations or machines in a line is presented as a form of "in-line" system. Due to the sequential nature of the production line, the throughput rate of the line depends on the slowest process. This paper presents one example of an in-line system that is used for pallet re-use by sorting, washing, and drying in a continuous processing line. Basically, a well-structured in-line system provides high throughput because of the non-stop flow of materials in the system. However, there is a hidden loss in the system efficiency. The object of this paper is to evaluate some of the possible alternatives to solve these hidden inefficiency problems and to improve throughputs through simulated models. The three outcomes from this simulation indicate that exchanging the robotic arm with a sorter and adding additional spin-drying machines could reduce overhead costs and the average waiting time for the spin-drying machine and improve the utilization of the resources in the washing process

Tight junction Claudin proteins restrict invasive cancer cell behaviors in murine models of breast cancer

Breast cancer is the most common cancer diagnosed and second leading cause of death in women. Transcriptomic analyses have identified Claudin-low as a subtype of breast cancer, with low expression of tight junction genes Claudin 3, 4, 7, and Occludin as a key defining feature. While clinical and genomic studies have shown that Claudin-low is an aggressive subtype with poor prognosis, it remains unclear whether loss of these proteins is directly responsible for the aggressive cancer cell behaviors involved in metastatic disease. We hypothesized that Claudin proteins directly suppress invasive and metastatic cancer cell behaviors. We used a genetically engineered mouse model (GEMM) of basal breast cancer, C3(1)-Tag, to examine Claudin expression in primary tumors and in 3D organotypic assays of cancer cells derived from this mouse model. Our data revealed that Claudin 3 and Claudin 7 are heterogeneously expressed in C3(1)-TAg basal tumors, with expression lost in discrete regions within primary tumors. Using 3D ex vivo culture of tumor organoids, we also observed specific loss of Claudin expression in invading cells. To directly test our hypothesis, CRISPR gene-editing was used to deplete Claudin 3 and Claudin 7 in 3D organotypic assay. Upon individual knockout of Claudin 3 and Claudin 7 using CRISPR gene-editing, breast cancer organoids grown in 3D culture showed increased growth and collective invasion. Altogether, these findings indicate that Claudin 3 and Claudin 7 suppress collective invasion behaviors in primary breast cancer cells

Association Between Macronutrients Intake and Depression in the United States and South Korea

Although the risk for depression appears to be related to daily dietary habits, how the proportion of major macronutrients affects the occurrence of depression remains largely unknown. This study aims to estimate the association between macronutrients (i.e., carbohydrate, protein, fat) and depression through national survey datasets from the United States and South Korea. Association between the prevalence of depression and each macronutrient was measured from 60,935 participants from the National Health and Nutrition Examination Survey (NHANES) and 15,700 participants from the South Korea NHANES (K-NHANES) databases. When the proportion of calories intake by protein increased by 10%, the prevalence of depression was significantly reduced both in the United States [Odds Ratio, OR (95% CI), 0.621 (0.530–0.728)] and South Korea [0.703 (0.397–0.994)]. An association between carbohydrate intake and the prevalence of depression was seen in the United States [1.194 (1.116–1.277)], but not in South Korea. Fat intake was not significantly associated with depression in either country. Subsequent analysis showed that the low protein intake groups had significantly higher risk for depression than the normal protein intake groups in both the United States [1.648 (1.179–2.304)] and South Korea [3.169 (1.598–6.286)]. In the daily diet of macronutrients, the proportion of protein intake is significantly associated with the prevalence of depression. These associations were more prominent in adults with insufficient protein intake, and the pattern of association between macronutrients and depression in Asian American and South Korean populations were similar. Our findings suggest that the proportion of macronutrients intake in everyday life may be related to the occurrence of depression

Association Between Macronutrients Intake and Depression in the United States and South Korea

Although the risk for depression appears to be related to daily dietary habits, how the proportion of major macronutrients affects the occurrence of depression remains largely unknown. This study aims to estimate the association between macronutrients (i.e., carbohydrate, protein, fat) and depression through national survey datasets from the United States and South Korea. Association between the prevalence of depression and each macronutrient was measured from 60,935 participants from the National Health and Nutrition Examination Survey (NHANES) and 15,700 participants from the South Korea NHANES (K-NHANES) databases. When the proportion of calories intake by protein increased by 10%, the prevalence of depression was significantly reduced both in the United States [Odds Ratio, OR (95% CI), 0.621 (0.530–0.728)] and South Korea [0.703 (0.397–0.994)]. An association between carbohydrate intake and the prevalence of depression was seen in the United States [1.194 (1.116–1.277)], but not in South Korea. Fat intake was not significantly associated with depression in either country. Subsequent analysis showed that the low protein intake groups had significantly higher risk for depression than the normal protein intake groups in both the United States [1.648 (1.179–2.304)] and South Korea [3.169 (1.598–6.286)]. In the daily diet of macronutrients, the proportion of protein intake is significantly associated with the prevalence of depression. These associations were more prominent in adults with insufficient protein intake, and the pattern of association between macronutrients and depression in Asian American and South Korean populations were similar. Our findings suggest that the proportion of macronutrients intake in everyday life may be related to the occurrence of depression

An exact solution of the higher-order gravity in standard radiation-dominated era

We report that the standard evolution of radiation-dominated era (RDE) universe $a \propto t^{1/2}$ is a sufficient condition for solving a sixth order gravitational field equation derived from the Lagrangian containing $B R^{ab}R_{ab} + C R {R^{;c}}_{c}$ as well as a polynomial $f(R)$ for a spatially flat radiation FLRW universe. By virtue of the similarity between $R^{ab}R_{ab}$ and $R^2$ models up to the background order and of the vanishing property of ${R^{;c}}_{c}$ for $H = 1/(2t)$, the analytical solution can be obtained from a special case to general one. This proves that the standard cosmic evolution is valid even within modified gravitational theory involving higher-order terms. An application of this background solution to the tensor-type perturbation reduces the complicated equation to the standard second order equation of gravitational wave. We discuss the possible ways to discriminate the modified gravity model on the observations such as the gravitational wave from the disturbed universe and primordial abundances

Temperature dependence of Mott transition in VO_2 and programmable critical temperature sensor

The temperature dependence of the Mott metal-insulator transition (MIT) is studied with a VO_2-based two-terminal device. When a constant voltage is applied to the device, an abrupt current jump is observed with temperature. With increasing applied voltages, the transition temperature of the MIT current jump decreases. We find a monoclinic and electronically correlated metal (MCM) phase between the abrupt current jump and the structural phase transition (SPT). After the transition from insulator to metal, a linear increase in current (or conductivity) is shown with temperature until the current becomes a constant maximum value above T_{SPT}=68^oC. The SPT is confirmed by micro-Raman spectroscopy measurements. Optical microscopy analysis reveals the absence of the local current path in micro scale in the VO_2 device. The current uniformly flows throughout the surface of the VO_2 film when the MIT occurs. This device can be used as a programmable critical temperature sensor.Comment: 4 pages, 3 figure