The poorly understood mode of activation and catalysis of bidentate iodine(III)-based halogen donors have been quantitatively explored in detail by means of state-of-the-art computational methods. To this end, the uncatalyzed Diels-Alder cycloaddition reaction between cyclohexadiene and methyl vinyl ketone is compared to the analogous process mediated by a bidentate iodine(III)-organocatalyst and by related, highly active iodine(I) species. It is found that the bidentate iodine(III)-catalyst accelerates the cycloaddition by lowering the reaction barrier up to 10 kcal mol-1 compared to the parent uncatalyzed reaction. Our quantitative analyses reveal that the origin of the catalysis is found in a significant reduction of the steric (Pauli) repulsion between the diene and dienophile, which originates from both a more asynchronous reaction mode and a significant polarization of the π-system of the dienophile away from the incoming diene. Notably, the activity of the iodine(III)-catalyst can be further enhanced by increasing the electrophilic nature of the system. Thus, novel systems are designed whose activity actually surpasses that of strong Lewis acids such as BF3.High contact resistance of transition-metal dichalcogenide (TMD)-based devices is one of the bottlenecks that limit the application of TMDs in various domains. Contact resistance of TMD-based devices is strongly related to the interface chemistry and band alignment at the contact metal/TMD interfaces. To understand the metal/MoS2 interface chemistry and band alignment, Ni and Ag metal contacts are deposited on MoS2 bulk and chemical vapor deposition bilayer MoS2 (2L-MoS2) film samples under ultrahigh vacuum (∼3 × 10-11 mbar) and high vacuum (∼3 × 10-6 mbar) conditions. X-ray photoelectron spectroscopy is used to characterize the interface chemistry and band alignment of the metal/MoS2 stacks. Ni forms covalent contact on MoS2 bulk and 2L-MoS2 film by reducing MoS2 to form interfacial metal sulfides. In contrast, van der Waals gaps form at the Ag/MoS2 bulk and Ag/2L-MoS2 film interfaces, proved by the absence of an additional metal sulfide chemical state and the detection of Ag islands on the surface. Different from other metal/MoS2 systems studied in this work, Ag shows potential to form an Ohmic contact on MoS2 bulk regardless of the deposition ambient. CB-5083 mouse Fermi levels (EF's) are pinned near the intrinsic EF of the 2L-MoS2 film with high defect density regardless of the work function of the metal, which highlights the impact of substrate defect density on the EF pinning effect and contact resistance.A catalyst-free and transition-metal-free method for the synthesis of 1,2-diketones from aerobic alkyne oxidation was reported. The oxidation of various internal alkynes, especially more challenging aryl-alkyl acetylenes, proceeded smoothly with inexpensive, easily handled, and commercially available potassium persulfate and an ambient air balloon, achieving the corresponding 1,2-diketones with up to 85% yields. Meanwhile, mechanistic studies indicated a radical process, and the two oxygen atoms in the 1,2-diketons were most likely from persulfate salts and molecular oxygen, respectively, rather than water.Noble metals manifest themselves with unique electronic structures and irreplaceable activity toward a wide range of catalytic applications but are unfortunately restricted by limited choice of geometric structures spanning single atoms, clusters, nanoparticles, and bulk crystals. Herein, we propose how to overcome this limitation by integrating noble metal atoms into the lattice of transition metal oxides to create a new type of hybrid structure. This study shows that iridium single atoms can be accommodated into the cationic sites of cobalt spinel oxide with short-range order and an identical spatial correlation as the host lattice. The resultant Ir0.06Co2.94O4 catalyst exhibits much higher electrocatalytic activity than the parent oxide by 2 orders of magnitude toward the challenging oxygen evolution reaction under acidic conditions. Because of the strong interaction between iridium and cobalt oxide support, the Ir0.06Co2.94O4 catalyst shows significantly improved corrosion resistance under acidic conditions and oxidative potentials. This work eliminates the "close-packing" limitation of noble metals and offers promising opportunity to create analogues with desired topologies for various catalytic applications.In the enzymatic cascade catalysis, it is a big challenge to construct a stable and reusable catalyst with targeted enzymes. The artificial multienzyme reactor has attracted great attention due to its potential for facilitating the performance of enzyme catalysis. In this study, we set up a reliable system that could assemble polyphosphate kinase (PPK) with bifunctional glutathione synthetase (GshF) via SpyCatcher/SpyTag to form multienzyme systems (MESs). Furthermore, MESs could assemble into nanoaggregates by altering the ionic strength, and the larger nanoaggregates could be applied in robust and reusable synthesis of glutathione (GSH). To enhance MES levels in vivo, gene duplication and different coexpression modes were performed. Finally, the optimized production of GSH and oxidized glutathione (GSSG) reached 102.6 and 6.7 mM within 2 h. Compared with the first round, the total yield only decreased by 9.4% after five continuous rounds of biocatalysis.Selective and potent inhibitors of activated thrombin activatable fibrinolysis inhibitor (TAFIa) have the potential to increase endogenous and therapeutic fibrinolysis and to behave like profibrinolytic agents without the risk of major hemorrhage, since they do not interfere either with platelet activation or with coagulation during blood hemostasis. Therefore, TAFIa inhibitors could be used in at-risk patients for the treatment, prevention, and secondary prevention of stroke, venous thrombosis, and pulmonary embolisms. In this paper, we describe the design, the structure-activity relationship (SAR), and the synthesis of novel, potent, and selective phosphinanes and azaphosphinanes as TAFIa inhibitors. Several highly active azaphosphinanes display attractive properties suitable for further in vivo efficacy studies in thrombosis models.