In situ Synthesis of Supramolecular Polymers:Finding the Right Conditions when Combining Covalent and Non-Covalent Synthesis

The combination of covalent and non-covalent synthesis is omnipresent in nature and potentially enables access to new materials. Yet, the fundamental principles that govern such a synthesis are barely understood. Here, we demonstrate how even simple reaction mixtures behave surprisingly complex when covalent reactions are coupled to self-assembly processes. Specifically, we study the reaction behavior of a system in which the in situ formation of discotic benzene-1,3,5-tricarboxamide (BTA) monomers is linked to an intertwined non-covalent reaction network including self-assembly into helical BTA polymers. This system shows an unexpected phase-separation behavior in which an interplay of reactant/product concentrations, side-products and solvent purity determines the system composition. We envision that these insights can bring us one step closer to how to design the synthesis of systems in a combined covalent/non-covalent fashion.</p

Temperature Directs the Majority-Rules Principle in Supramolecular Copolymers Driven by Triazine–Benzene Interactions

Supramolecular copolymers have typically been studied in the extreme cases, such as self-sorting or highly mixed copolymer systems, while the intermediate systems have been less understood. We have reported the temperature-dependent microstructure in copolymers of triazine- and benzene-derivatives based on charge-transfer interactions with a highly alternating microstructure at low temperatures. Here, we investigate the temperature-dependent copolymerization further and increase the complexity by combining triazine- and benzene-derivatives with opposite preferred helicities. In this case, intercalation of the benzene-derivative into the triazine-derivative assemblies causes a helical inversion. The inversion of the net helicity was rationalized by comparing the mismatch penalties of the individual monomers, which indicated that the benzene-derivative dictates the helical screw-sense of the supramolecular copolymers. Surprisingly, this was not reflected in further investigations of slightly modified triazine- and benzene-derivatives, thus highlighting that the outcome is a subtle balance between structural features, where small differences can be amplified due to the competitive nature of the interactions. Overall, these findings suggest that the temperature-dependent microstructure of triazine- and benzene-based supramolecular copolymers determines the copolymer helicity of the presented system in a similar way as the mixed majority-rules phenomenon.</p

Controlling Helical Asymmetry in Supramolecular Copolymers by In Situ Chemical Modification

Amplification of asymmetry in complex molecular systems results from a delicate interplay of chiral supramolecular structures and their chemical reactivity. In this work, we show how the helicity of supramolecular assemblies can be controlled by performing a non-stereoselective methylation reaction on comonomers. By methylating chiral glutamic acid side chains in benzene-1,3,5-tricarboxamide (BTA) derivatives to form methyl esters, the assembly properties are modulated. As reacted comonomers, the methyl ester-BTAs induce a stronger bias in the screw-sense of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers. Hence, applying the in situ methylation in a system with the glutamic acid-BTA comonomer induces asymmetry amplification. Moreover, mixing small quantities of enantiomers of glutamic acid-BTA and glutamate methyl ester-BTA in the presence of the achiral alkyl-BTAs leads to deracemization and inversion of the helical structures in solution via the in situ reaction toward a thermodynamic equilibrium. Theoretical modeling suggests that the observed effects are caused by enhanced comonomer interactions after the chemical modification. Our presented methodology enables on-demand control over asymmetry in ordered functional supramolecular materials.</p

How Subtle Changes Can Make a Difference – Reproducibility in Complex Supramolecular Systems

The desire to construct complex molecular systems is driven by the need for technological (r)evolution and our intrinsic curiosity to comprehend the origin of life. Supramolecular chemists tackle this challenge by combining covalent and noncovalent reactions leading to multicomponent systems with emerging complexity. However, this synthetic strategy often coincides with difficult preparation protocols and a narrow window of suitable conditions. Here, we report on unsuspected observations of our group that highlight the impact of subtle “irregularities” on supramolecular systems. Based on the effects of pathway complexity, minute amounts of water in organic solvents or small impurities in the supramolecular building block, we discuss potential pitfalls in the study of complex systems. This article is intended to draw attention to often overlooked details and to initiate an open discussion on the importance of reporting experimental details to increase reproducibility in supramolecular chemistry

Benzene Tetraamide:A Covalent Supramolecular Dual Motif in Dynamic Covalent Polymer Networks

In dynamic polyamide networks, 1,2,4,5-benzene tetraamide (B4A) units act simultaneously as a dynamic covalent cross-linker and as supramolecular stacking motif. This results in materials with a rubbery plateau modulus that is about 20 times higher than that of a corresponding reference network in which the supramolecular interaction is suppressed. In branched polyamides with the same B4A dynamic motif, hydrogen bonding and stacking lead to strong and reversible supramolecular networks, whereas a branched polyamide with the nonstacking reference linker is a viscous liquid under the same conditions. Wide-angle X-ray scattering and variable-temperature infrared experiments confirm that covalent cross-linking and stacking cooperatively contribute to the dynamics of the network. Stress relaxation in the reference network is dominated by a single mode related to the dynamic covalent chemistry, whereas relaxation in the B4A network has additional modes assigned to the stacking dynamics.</p

More Competitive Search Through Regulation

This paper identifies a set of possible regulations that could be used both to make the search market more competitive and simultaneously ameliorate the harms flowing from Google's current monopoly position. The purpose of this paper is to identify conceptual problems and solutions based on sound economic principles and to begin a discussion from which robust and specific policy recommendations can be drafted

Unraveling the deep learning gearbox in optical coherence tomography image segmentation towards explainable artificial intelligence

Machine learning has greatly facilitated the analysis of medical data, while the internal operations usually remain intransparent. To better comprehend these opaque procedures, a convolutional neural network for optical coherence tomography image segmentation was enhanced with a Traceable Relevance Explainability (T-REX) technique. The proposed application was based on three components: ground truth generation by multiple graders, calculation of Hamming distances among graders and the machine learning algorithm, as well as a smart data visualization ('neural recording'). An overall average variability of 1.75% between the human graders and the algorithm was found, slightly minor to 2.02% among human graders. The ambiguity in ground truth had noteworthy impact on machine learning results, which could be visualized. The convolutional neural network balanced between graders and allowed for modifiable predictions dependent on the compartment. Using the proposed T-REX setup, machine learning processes could be rendered more transparent and understandable, possibly leading to optimized applications