Abstract The stiffness of hydrogels is crucial for their application. Nature’s become stiffer as they are strained. This not constant but increases when the gel stiffening used, instance, by cells that actively strain environment to modulate function. When optimized, such strain-stiffening materials extremely sensitive and very responsive stress. Strain stiffening, however, unexplored in synthetic gels since structural design parameters unknown. Here we uncover how readily tuneable...

Abstract Organic semiconductors and organic–inorganic hybrids are promising materials for spintronic‐based memory devices. Recently, an alternative route to organic spintronic based on chiral‐induced spin selectivity (CISS) is suggested. In the CISS effect, chirality of molecular system itself acts as a filter, thus avoiding use magnets injection. Here, filtering in excess 85% helical π‐conjugated supramolecular nanofibers at room temperature reported. The high spin‐filtering efficiency can...

Interactions between solvents and solutes are a cornerstone of physical organic chemistry have been the subject investigations over last century. In recent years, renewed interest in fundamental aspects solute-solvent interactions has sparked field supramolecular general that polymers particular. Although solvent effects recognized for long time, unique opportunities offer to gain insight into become clear relatively recently. The multiple hold polymeric structure together similar strength...

Fascinating properties are displayed by synthetic multicomponent supramolecular systems that comprise a manifold of competitive interactions, thereby mimicking natural processes. We present the integration two reentrant phase transitions based on an unexpected dilution-induced assembly process using polymers and surfactants. The co-assembly water-soluble benzene-1,3,5-tricarboxamide (BTA-EG 4 ) surfactant at specific ratio yielded small-sized aggregates. These interactions were modeled...

Bacterial multimodular polyketide synthases (PKSs) are giant enzymes that generate a wide range of therapeutically important but synthetically challenging natural products. Diversification structures can be achieved by engineering these enzymes. However, notwithstanding successes made with textbook

Pathway complexity in supramolecular polymerization has recently sparked interest as a method to generate complex material behavior. The response of these systems relies on the existence metastable, kinetically trapped state. In this work, we show that strong switch-like behavior polymers can also be achieved through introduction competing aggregation pathways. This is illustrated with porphyrin-based monomer at various concentrations, solvent compositions, and temperatures. It found...

Abstract Connecting molecular-level phenomena to larger scales and, ultimately, sophisticated molecular systems that resemble living remains a considerable challenge in supramolecular chemistry. To this end, self-assembly at higher hierarchical levels has be understood and controlled. Here, we report unusual self-assembled structures formed from simple porphyrin derivative. Unexpectedly, one-dimensional (1D) polymer coiled give an Archimedean spiral. Our analysis of the polymerization by...

In general, supramolecular polymers are thermally labile in solution and easily depolymerized upon heating. This dynamic nature is beneficial many aspects but limits certain applications. Recently, we developed "thermally bisignate polymerization", through which a polymer formed heating as well cooling hydrocarbon solvent containing small amount of alcohol. Here, present detailed mechanistic picture for this polymerization based on both spectroscopic computational studies. For particular...

In polymer chemistry, modulation of sequence and control over chain length are routinely applied to alter fine-tune the properties covalent (co)polymers. For supramolecular polymers, same principles underlying this have not been fully elucidated up date. Particularly, rational molecular weight in dynamic polymers is trivial, especially when a cooperative mechanism operative. We start review by summarizing how molecular-weight has achieved seminal examples field polymerizations. Following...

By enchaining a small fraction of chiral monomer units, the helical sense dynamic polymer constructed from achiral units can be disproportionately biased. This phenomenon, known as sergeants-and-soldiers (S&S) effect, has been found to widely applicable covalent and supramolecular polymers. However, it not exemplified with that features multiple states. Herein, we demonstrate S&S effect in context temperature-controlled copolymerization biphenyl tetracarboxamides alkanes. The one-dimensional...

The combination of covalent and non-covalent synthesis is omnipresent in nature potentially enables access to new materials. Yet, the fundamental principles that govern such a are barely understood. Here, we demonstrate how even simple reaction mixtures behave surprisingly complex when reactions coupled self-assembly processes. Specifically, study behavior system which situ formation discotic benzene-1,3,5-tricarboxamide (BTA) monomers linked an intertwined network including into helical BTA...

Well-defined microgel particles were prepared by combining coacervate-driven cross-linking of ionic triblock copolymers with the ability to control particle size and encapsulate functional cargos inherent in microfluidic devices. In this approach, efficient assembly PEO-based oppositely charged end-blocks allows for bioinspired under mild conditions dispersed aqueous droplets. This strategy enables integration into coacervate domains (e.g., loading anionic model compounds through...

Abstract Solvents are fundamentally essential for the synthesis and processing of soft materials. Supramolecular polymers (SPs), an emerging class materials, usually stable in single mixtures poor solvents. In contrast to these preconceived notions, here we report depolymerization SPs mixture two This surprising behavior was observed well‐known cationic perylene diimides ( c PDIs ) water amphiphilic organic solvents such as isopropanol (IPA). form IPA but readily depolymerize into monomers...

We report the synthesis and self-assembly behavior of a chiral C3-symmetrical benzene-tricarboselenoamide. The introduction selenoamide moiety enhances dipolar character supramolecular interaction confers remarkable thermal stability to polymers obtained.

Water is typically considered to be insoluble in alkanes. Recently, however, monomerically dissolved water alkanes has been shown dramatically impact the structure of hydrogen-bonded supramolecular polymers. Here, we report that methylcyclohexane (MCH) also determines outcome combining a Michael reaction with porphyrin-based system. In dry conditions, components do not affect or destabilize polymer, whereas ambient wet conditions polymers are rapidly destabilized. Although spectroscopic...

Supramolecular copolymerizations offer attractive options to introduce structural and functional diversity in supramolecular polymer materials. Yet, general principles structure-property relationships for rational comonomer design remain lacking. Here, we report on the (co)aggregation of a phenylpyridine bipyridine derivative recently reported biphenyl tetracarboxamide-based monomer. We show that both arylpyridines are poor monomers homopolymerizations. However, two efficiently influence...

Abstract The idea to synthesize and self‐assemble nano‐graphenes with structural precision into supramolecular polymers is just one of Klaus Müllen's many pioneering contributions the chemical sciences. To honor his impact in field polymer science, we here describe a study that combines experimental computational methods studying stability kinetically trapped states polymers. We show introduction stereocenters sidechains allow helical based on chiral triphenylene‐2,6,10‐tricarboxamide...

Abstract The combination of covalent and non‐covalent synthesis is omnipresent in nature potentially enables access to new materials. Yet, the fundamental principles that govern such a are barely understood. Here, we demonstrate how even simple reaction mixtures behave surprisingly complex when reactions coupled self‐assembly processes. Specifically, study behavior system which situ formation discotic benzene‐1,3,5‐tricarboxamide (BTA) monomers linked an intertwined network including into...

Abstract Solvents are fundamentally essential for the synthesis and processing of soft materials. Supramolecular polymers (SPs), an emerging class materials, usually stable in single mixtures poor solvents. In contrast to these preconceived notions, here we report depolymerization SPs mixture two This surprising behavior was observed well‐known cationic perylene diimides ( c PDIs ) water amphiphilic organic solvents such as isopropanol (IPA). form IPA but readily depolymerize into monomers...

Thioesterases (TEs) are fundamentally important enzymes present in all bacteria and eukaryotes, where they have conserved functions fatty acid biosynthesis secondary metabolism. This work provides the first structural insights into a functionally distinct group of TEs that perform diverse acylations polyketide peptide (TEB s). Structural analysis oocydin (OocS) TEB domain facilitated identification engineering active site to modulate acyl-group acceptance. In this way, we achieved higher...

Competition between supramolecular polymers for the same monomers can lead to strong responses in these systems. Using numerical simulations, we show that sharpness and asymmetry of transition from one thermodynamically stable polymer another upon changing temperature is determined by most unstable rather than polymer. The width transitions are shown depend on relative absolute nucleation penalties competing polymerizations. performance molecular polymeric materials various applications,...

Discrete block co-oligomers (BCOs) assemble into highly ordered nanostructures, which adopt a variety of morphologies depending on their environment. Here, we present series discrete oligodimethylsiloxane-oligoproline (oDMS-oPro) BCOs with varying oligomer lengths and proline end-groups, study the nanostructures formed in both bulk solution. The conjugation oligoprolines to apolar siloxanes permits aggregation behavior oligoproline moieties solvents, including solvent like methylcyclohexane....