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Dynamic combinatorial chemistry is a method widely used for generating responsive libraries of compounds, with applications ranging from chemical biology to materials science. It relies on dynamic covalent bonds that are able to form in a reversible manner in mild conditions, and therefore requires the discovery of new types of these bonds in order to progress. Amides, due to their high stability, have been scarcely used in this field and typically require an external catalyst or harsh conditions for exchange. Compounds able to undergo uncatalysed transamidation at room temperature are still rare exceptions. In this work, we describe reversible amide formation and transamidation in a class of compounds known as maleamic acids. Due to the presence of a carboxylic acid in β‐position, these compounds are in equilibrium with their anhydride and amine precursors in organic solvents at room temperature. First, we show that this equilibrium is responsive to external stimuli: by alternating the additions of a Brønsted acid and a base, we can switch between amide and anhydride several times without side‐reactions. Next, we prove that this equilibrium provides a pathway for reversible transamidation without any added catalyst, leading to thermodynamic distributions of amides at room temperature. Lastly, we use different preparation conditions and concentrations of Brønsted acid to access different library distributions, easily controlling the transition between kinetic and thermodynamic regimes. Our results show that maleamic acids can undergo transamidation in mild conditions in a reversible and tunable way, establishing them as a new addition to the toolbox of dynamic combinatorial chemistry. [ABSTRACT FROM AUTHOR]

The ability to design reaction networks with high, but addressable complexity is a necessary prerequisite to make advanced functional chemical systems. Dynamic combinatorial chemistry has proven to be a useful tool in achieving complexity, however with some limitations in controlling it. Herein we introduce the concept of antiparallel chemistries, in which the same functional group can be channeled into one of two reversible chemistries depending on a controllable parameter. Such systems allow both for achieving complexity, by combinatorial chemistry, and addressing it, by switching from one chemistry to another by controlling an external parameter. In our design the two antiparallel chemistries are thiol-disulfide exchange and thio-Michael addition, sharing the thiol as the common building block. By means of oxidation and reduction the system can be reversibly switched from predominantly thio-Michael chemistry to predominantly disulfide chemistry, as well as to any intermediate state. Both chemistries operate in water, at room temperature, and at mildly basic pH, which makes them a suitable platform for further development of systems chemistry. [ABSTRACT FROM AUTHOR]

Automated chemistry platforms have been widely explored, but many focus on fixed tasks for chemical synthesis or analysis. However, a typical synthetic chemistry workflow utilizes both, such as kinetic measurements for reaction development and optimization. Due to their repetitive and time-consuming nature, kinetic measurements are often omitted, which limits the mechanistic investigation of reactions. Herein, we present a "Chemputer" platform with on-line analytics (UV/Vis, NMR) which automates routine kinetic measurements. The system's capabilities are showcased by exploring an inverse electron-demand Diels-Alder using initial rate measurements, a metal complexation using variable time normalization analysis (VTNA), and formation of a series of tosylamide derivatives using Hammett analysis. Over 60 individual experiments are presented which required minimal intervention, highlighting the significant time savings of automation. Owing to the modular design of the platform, which facilitates rapid integration of commercial analytical tools, our approach is widely accessible and adjustable to the reaction under investigation. The platform is operated using the chemical programming language, XDL, hence experimental procedures and results are stored in a precise, computer-readable format. We propose that widespread adoption of this reporting protocol in the chemical community could build a database of validated kinetic data beneficial for Machine Learning., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Colloidal quantum dots (CQDs) are nanoscale building blocks for bottom-up fabrication of semiconducting solids with tailorable properties beyond the possibilities of bulk materials. Achieving ordered, macroscopic crystal-like assemblies has been in the focus of researchers for years, since it would allow exploitation of the quantum-confinement-based electronic properties with tunable dimensionality. Lead-chalcogenide CQDs show especially strong tendencies to self-organize into 2D superlattices with micrometer-scale order, making the array fabrication fairly simple. However, most studies concentrate on the fundamentals of the assembly process, and none have investigated the electronic properties and their dependence on the nanoscale structure induced by different ligands. Here, it is discussed how different chemical treatments on the initial superlattices affect the nanostructure, the optical, and the electronic-transport properties. Transistors with average two-terminal electron mobilities of 13 cm 2 V -1 s -1 and contactless mobility of 24 cm 2 V -1 s -1 are obtained for small-area superlattice field-effect transistors. Such mobility values are the highest reported for CQD devices wherein the quantum confinement is substantially present and are comparable to those reported for heavy sintering. The considerable mobility with the simultaneous preservation of the optical bandgap displays the vast potential of colloidal QD superlattices for optoelectronic applications., (© 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)