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Reductive electrosynthesis has faced long-standing challenges in applications to complex organic substrates at scale. Here, we show how decades of research in lithium-ion battery materials, electrolytes, and additives can serve as an inspiration for achieving practically scalable reductive electrosynthetic conditions for the Birch reduction. Specifically, we demonstrate that using a sacrificial anode material (magnesium or aluminum), combined with a cheap, nontoxic, and water-soluble proton source (dimethylurea), and an overcharge protectant inspired by battery technology [tris(pyrrolidino)phosphoramide] can allow for multigram-scale synthesis of pharmaceutically relevant building blocks. We show how these conditions have a very high level of functional-group tolerance relative to classical electrochemical and chemical dissolving-metal reductions. Finally, we demonstrate that the same electrochemical conditions can be applied to other dissolving metal–type reductive transformations, including McMurry couplings, reductive ketone deoxygenations, and epoxide openings.

The study and application of transition metal hydrides (TMHs) has been an active area of chemical research since the early 1960s 1 , for energy storage, through the reduction of protons to generate hydrogen 2 , 3 , and for organic synthesis, for the functionalization of unsaturated C–C, C–O and C–N bonds 4 , 5 . In the former instance, electrochemical means for driving such reactivity has been common place since the 1950s 6 but the use of stoichiometric exogenous organic- and metal-based reductants to harness the power of TMHs in synthetic chemistry remains the norm. In particular, cobalt-based TMHs have found widespread use for the derivatization of olefins and alkynes in complex molecule construction, often by a net hydrogen atom transfer (HAT) 7 . Here we show how an electrocatalytic approach inspired by decades of energy storage research can be made use of in the context of modern organic synthesis. This strategy not only offers benefits in terms of sustainability and efficiency but also enables enhanced chemoselectivity and distinct, tunable reactivity. Ten different reaction manifolds across dozens of substrates are exemplified, along with detailed mechanistic insights into this scalable electrochemical entry into Co–H generation that takes place through a low-valent intermediate. A perspective is given on how an electrocatalytic approach, inspired by decades of energy storage studies, can be used in the context of efficient cobalt-hydride generation with a variety of applications in modern organic synthesis.

A simple electrochemically mediated method for the conversion of alkyl carboxylic acids to their borylated congeners is presented. This protocol features an undivided cell setup with inexpensive carbon-based electrodes and exhibits a broad substrate scope and scalability in both flow and batch reactors. The use of this method in challenging contexts is exemplified with a modular formal synthesis of jawsamycin, a natural product harboring five cyclopropane rings.

Chemical waste has become a major problem for the chemical industry. For centuries, scientists desperately sought ways to reduce chemical waste including developing new methods and materials, especially in the field of synthetic organic chemistry due to the massive amount of solvent waste generated during the reaction process. The Mack group successfully utilized high speed ball milling (HSBM), a solvent-free mechanochemical technique to facilitate and conduct chemical reactions. In ball milling, the ball bearings grind reactants to small size of particles, mixing them in a reaction vial, and during the fierce shaken process, the ball hits the wall and provides energy for reactants to overcome the energy barrier to form products. After two decades of development, more and more studies and research revealed this new world and now ball milling has been recognized as a potential sustainable method for conducting various organic reactions. In this dissertation, I have developed sustainable catalysis for coupling reactions and cycloaddition reactions under mechanochemical conditions. In the first chapter, I introduce the concept of green chemistry and mechanochemistry, elaborate on the solvent selection problem and ball milling applications in recent organic chemistry. In chapter 2 and chapter 3, I will discuss the details about using simple catalyst and polymer supported catalyst to perform dimerization of terminal alkynes in a ball mill, which was not only a sustainable method to form products but also enable to tune either product. The new solvent-free surface catalysis for cycloaddition reactions will discuss in chapter 4 and chapter 5, there I will introduce a novel approach by using metal foil as a cheap, recyclable catalyst to catalyze cyclopropanation and cyclopropenation through reactive carbenoid reagent. The last chapter will introduce a versatile approach for X-H insertion reactions catalyzed by cooper surface via ball milling.

Pedestrians' safety is a crucial factor in assessing autonomous driving scenarios. However, pedestrian safety evaluation is rarely considered by existing autonomous driving simulation platforms. This paper proposes a pedestrian safety evaluation method for autonomous driving, in which not only the collision events but also the conflict events together with the characteristics of pedestrians are fully considered. Moreover, to apply the pedestrian safety evaluation system, we construct a high-fidelity simulation framework embedded with pedestrian safety-critical characteristics. We demonstrate our simulation framework and pedestrian safety evaluation with a comparative experiment with two kinds of autonomous driving perception algorithms -- single-vehicle perception and vehicle-to-infrastructure (V2I) cooperative perception. The results show that our framework can evaluate different autonomous driving algorithms with detailed and quantitative pedestrian safety indexes. To this end, the proposed simulation method and framework can be used to access different autonomous driving algorithms and evaluate pedestrians' safety performance in future autonomous driving simulations, which can inspire more pedestrian-friendly autonomous driving algorithms.

Background Alternative splicing not only expands the genetic encoding of genes but also determines cellular activities. This study aimed to elucidate the regulation mechanism and biological functions of lincRNA-ASAO in the process of odontogenesis-related genes alternative splicing mediated odontogenic differentiation of hDPSCs. Methods RACE, RNA-seq, FISH and bioinformatics techniques were used to identify novel lincRNA-ASAO. ALP staining, alizarin red staining, qRT-PCR and western blot were used to identify the role of lincRNA-ASAO in regulating the odontoblast differentiation of hDPSCs. The binding protein PTBP1 of lincRNA-ASAO was screened by RNA-Pulldown, protein profiling and bioinformatics. The target gene ALPL of lincRNA-ASAO/PTBP1 was identified by RNA-seq, bioinformatics technology and DNA agarose gel electrophoresis. FISH, IF, PAR-CLIP and bioinformatics techniques were used to determine the roles of lincRNA-ASAO, PTBP1 and ALPL pre-mRNA in the odontoblast differentiation of hDPSCs. Results We identified a novel lincRNA-ASAO that could promote the odontogenic differentiation of human Dental Pulp Stem Cells (hDPSCs). And, the interaction between lincRNA-ASAO and alternative splicing factor PTBP1 promoted the odontoblast differentiation of hDPSCs. In addition, lincRNA-ASAO forms duplexes with ALPL pre-mRNA, targeting PTBP1 to exonic splicing silencer (ESS) of ALPL and regulating exon 2 skipping. Notably, lincRNA-ASAO/PTBP1 regulated ALPL production to increase the type 2 splice variant, which promoted the odontoblast differentiation of hDPSCs. Conclusions We have identified the novel lincRNA-ASAO, which can promote the odontoblast differentiation of hDPSCs. The mechanism study found that lincRNA-ASAO/PTBP1 mediated the exon 2 skipping of ALPL pre-mRNA, resulting in the type 2 splice variant of ALPL. Our results enrich the understanding of lncRNAs and alternative splicing in regulating the odontoblast differentiation of hDPSCs, and provide clues to improve the clinical therapeutic potential of hDPSCs for dental pulp restoration.