Optimality Conditions in Nondifferentiable G-Invex Multiobjective Programming

We consider a class of nondifferentiable multiobjective programs with inequality and equality constraints in which each component of the objective function contains a term involving the support function of a compact convex set. We introduce G-Karush-Kuhn-Tucker conditions and G-Fritz John conditions for our nondifferentiable multiobjective programs. By using suitable G-invex functions, we establish G-Karush-Kuhn-Tucker necessary and sufficient optimality conditions, and G-Fritz John necessary and sufficient optimality conditions of our nondifferentiable multiobjective programs. Our optimality conditions generalize and improve the results in Antczak (2009) to the nondifferentiable case

Blood and milk metabolites of Holstein dairy cattle for the development of objective indicators of a subacute ruminal acidosis

Objective The purpose of this study was to perform a comparative analysis of metabolite levels in serum and milk obtained from cows fed on different concentrate to forage feed ratios. Methods Eight lactating Holstein cows were divided into two groups: a high forage ratio diet (HF; 80% Italian ryegrass and 20% concentrate of daily intake of dry matter) group and a high concentrate diet (HC; 20% Italian ryegrass and 80% concentrate) group. Blood was collected from the jugular vein, and milk was sampled using a milking machine. Metabolite levels in serum and milk were estimated using proton nuclear magnetic resonance and subjected to qualitative and quantitative analyses performed using Chenomx 8.4. For statistical analysis, Student’s t-test and multivariate analysis were performed using Metaboanalyst 4.0. Results In the principal component analysis, a clear distinction between the two groups regarding milk metabolites while serum metabolites were shown in similar. In serum, 95 metabolites were identified, and 13 metabolites (include leucine, lactulose, glucose, betaine, etc.) showed significant differences between the two groups. In milk, 122 metabolites were identified, and 20 metabolites (include urea, carnitine, acetate, butyrate, arabinitol, etc.) showed significant differences. Conclusion Our results show that different concentrate to forage feed ratios impact the metabolite levels in the serum and milk of lactating Holstein cows. A higher number of metabolites in milk, including those associated with milk fat synthesis and the presence of Escherichia coli in the rumen, differed between the two groups compared to that in the serum. The results of this study provide a useful insight into the metabolites associated with different concentrate to forge feed ratios in cows and may aid in the search for potential biomarkers for subacute ruminal acidosis

Study on ATAD5-mediated PCNA Regulation in Safeguarding Genomic Integrity and Orchestrating ESC Differentiation

Department of Biological Sciencesclos

Ir(iii)-Catalysed electrooxidative intramolecular dehydrogenative C-H/N-H coupling for the synthesis of N-H indoles

Herein, an iridium(iii)-catalysed electrooxidative intramolecular dehydrogenative C-H/N-H coupling of unprotected 2-alkenyl anilines is described. The developed method allows the synthesis of a variety of 3-substituted N-H indole scaffolds under undivided electrolytic conditions. Mechanistic studies suggest that the reaction proceeds through the electro-oxidation induced reductive elimination pathway.11Nsciescopu

A Direct Access to 7-Aminoindoles via Iridium-Catalyzed Mild C-H Amidation of N-Pivaloylindoles with Organic Azides

Ir(III)-catalyzed regioselective direct C-7 amidation of indoles in reaction with organic azides has been developed. While its efficiency was varied by the choice of N-directing groups, N-pivaloylindoles were most effective in undergoing the desired amidation at room temperature over a broad range of substrates. The reaction was scalable, and deprotection of the chelation group was also facile. © 2016 American Chemical Society135371sciescopu

Transition Metal-Catalyzed C-H Amination: Scope, Mechanism, and Applications

Catalytic transformation of ubiquitous C-H bonds into valuable C-N bonds offers an efficient synthetic approach to construct N-functionalized molecules. Over the last few decades, transition metal catalysis has been repeatedly proven to be a powerful tool for the direct conversion of cheap hydrocarbons to synthetically versatile amino-containing compounds. This Review comprehensively highlights recent advances in intra- and intermolecular C-H amination reactions utilizing late transition metal-based catalysts. Initial discovery, mechanistic study, and additional applications were categorized on the basis of the mechanistic scaffolds and types of reactions. Reactivity and selectivity of novel systems are discussed in three sections, with each being defined by a proposed working mode. © 2017 American Chemical Society24727111sciescopu

Dubins Path-Oriented Rapidly Exploring Random Tree* for Three-Dimensional Path Planning of Unmanned Aerial Vehicles

Unmanned aerial vehicles (UAVs) do not collide with obstacles, generate a path in real-time, and must fly to the target point. The sampling-based rapidly exploring random tree (RRT) algorithm has the advantages of fast computation and low computational complexity. It is suitable for real-time path generation, but the optimal path cannot be guaranteed. Further, the direction of the flight and the minimum radius of rotation have not been taken into account for the characteristics of the UAVs. This work proposes a Dubins path-oriented RRT* algorithm, which applies the Dubins path to the RRT algorithm to consider the direction of flight and the minimum radius of rotation and improves optimality and convergence. The proposed algorithm sets the sample node as the target point, orients toward the Dubins path, and then generates a tree. To verify the performance of the proposed algorithm, it is compared with existing RRT algorithms. As a result of performance analysis, the proposed algorithm improved the path length by 14.87% and the calculation time by 82.36%. Finally, the algorithm’s performance is verified by applying the proposed algorithm to a fixed-wing UAV and performing a numerical analysis of the generated path

Ring-opening functionalizations of unstrained cyclic amines enabled by difluorocarbene transfer

Chemical synthesis based on the skeletal variation has been prolifically utilized as an attractive approach for modification of molecular properties. Given the ubiquity of unstrained cyclic amines, the ability to directly alter such motifs would grant an efficient platform to access unique chemical space. Here, we report a highly efficient and practical strategy that enables the selective ring-opening functionalization of unstrained cyclic amines. The use of difluorocarbene leads to a wide variety of multifaceted acyclic architectures, which can be further diversified to a range of distinctive homologative cyclic scaffolds. The virtue of this deconstructive strategy is demonstrated by successful modification of several natural products and pharmaceutical analogues. Cyclic amines are commonly present in natural products and synthetic compounds, but methods for their skeletal diversification are limited. Here, the authors report a strategy for selective ring-opening functionalization of unstrained cyclic amines to pluripotent products that can be further diversified.11sciescopu

Selective Synthesis of Silacycles by Borane-Catalyzed Domino Hydrosilylation of Proximal Unsaturated Bonds: Tunable Approach to 1,n-Diols

The tris(pentafluorophenyl)boron-catalyzed domino hydrosilylation of substrates carrying unsaturated functionalities in a proximal arrangement is presented to produce silacycles. Excellent levels of efficiency and selectivity were achieved in the cyclization by the deliberate choice of the hydrosilane reagents. The key to successful cyclic hydrosilylation is the reactivity enhancement of the second intramolecular hydrosilylation by a proximity effect. Not only dienes but also enones, enynes, ynones and enimines readily afford medium-sized silacycles under convenient and mild conditions. The cyclization proceeds with acceptable diastereoselectivity mainly controlled by the conformational bias towards inducing additional stereogenic centers. The silacycles obtained from this reaction were converted to 1,n-diols or 1,n-amino alcohols upon oxidation, thus rendering the present cyclization a powerful tool for accessing synthetically valuable building blocks. (Figure presented.). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinhei1

Delineating Physical Organic Parameters in Site-Selective C–H Functionalization of Indoles

Site-selective C–H functionalization is a great challenge in homogeneous transition-metal catalysis. Herein, we present a physical organic approach to delineate the origin of regioselective amidation of <i>N</i>-acylindoles through Ir­(III) catalysis. Bulkiness of <i>N</i>-directing groups of indole substrates and electronics of carboxylate additives were identified as two major factors in controlling C2 and C7 selectivity, and their microscopic mechanisms were studied with DFT-based transition state analysis. Computational insights led us to interrogate a linear free energy relationship, and parametrization of molecular determinants enabled the establishment of an intuitive yet robust statistical model that correlates an extensive number of validation data points in high accuracy. This mechanistic investigation eventually allowed the development of a new C2 amidation and alkenylation protocol of indoles, which affords the exclusive functionalization at the C2 position with up to >70:1 selectivity