Multicomponent supramolecular materials, which comprise plural supramolecular architectures that exhibit distinct self-sorting behaviors, are receiving increasing attention because they can be implemented with sophisticated functions and hierarchical structures, e.g., living cells. Nevertheless, the application of supramolecular system design to engineer self-sorting behaviors among plural supramolecular architectures remains challenging. Herein, we show that the thermal annealing-induced one-pot assembly of multiple single-stranded DNAs and a single semi-artificial glycopeptide (GP) results in the emergent formation of integrative self-sorted supramolecular nanostructures (ssSNs) consisting of a GP supramolecular nanoribbon surrounded by DNA tile-nanotubes. Fluorescence imaging revealed the formation of each supramolecular nanostructure through orthogonal molecular assembling processes. Moreover, the fluorescence recovery after photobleaching (FRAP) disclosed the presence of reversible attractive interactions between the DNA tile, prior to the formation of the tile-nanotube, and the GP supramolecular nanostructures at the mesoscale level, which are crucial for the formation of the integrative ssSNs. Further, we revealed that the integrative ssSNs retain their biostimuli responsiveness so that each supramolecular nanostructure can be selectively degraded. Finally, we successfully constructed a complex soft nanomaterial composed of ternary supramolecular architectures (a GP supramolecular nanostructure, DNA tile-nanotube, and DNA microsphere) based on the present as well as previous findings.

Nature creates exquisite molecular assemblies, required for the molecular-level functions of life, via self-assembly. Understanding and harnessing these complex processes presents an immense opportunity for the design and fabrication of advanced functional materials. However, the significant industrial potential of self-assembly to fabricate highly functional materials is hampered by a lack of knowledge of critical reaction intermediates, mechanisms, and kinetics. As we move beyond the covalent synthetic regime, into the domain of non-covalent interactions occupied by self-assembly, harnessing and embracing complexity is a must, and non-targeted analyses of dynamic systems are becoming increasingly important. Coordination driven self-assembly is an important subtype of self-assembly that presents several wicked analytical challenges. These challenges are \"wicked\" due the very complexity desired confounding the analysis of products, intermediates, and pathways, therefore limiting reaction optimisation, tuning, and ultimately, utility. Ion Mobility-Mass Spectrometry solves many of the most challenging analytical problems in separating and analysing the structure of both simple and complex species formed via coordination driven self-assembly. Thus, due to the emerging importance of ion mobility mass spectrometry as an analytical technique tackling complex systems, this review highlights exciting recent applications. These include equilibrium monitoring, structural and dynamic analysis of previously analytically inaccessible complex interlinked structures and the process of self-sorting. The vast and largely untapped potential of ion mobility mass spectrometry to coordination driven self-assembly is yet to be fully realised. Therefore, we also propose where current analytical approaches can be built upon to allow for greater insight into the complexity and structural dynamics involved in self-assembly.

Nature segregates fundamental tasks such as information storage/transmission and catalysis between two different compound classes (e.g. polynucleotides for replication and folded polyamides for catalysis). This division of labor is likely a product of evolution, raising the question of how simpler systems in which replicators and folded macromolecules co-exist may emerge in the transition from chemistry to biology. In synthetic systems, achieving co-existence of replicators and foldamers in a single molecular network remains an unsolved problem. Previous work on dynamic molecular networks has given rise to either self-replicating fibers or well-defined foldamer structures (or completely un-sorted complex systems). We report a system in which two cross-reactive dithiol (nucleobase- and peptide-based) building blocks self-sort into a replicator fiber and foldamer that both emerge spontaneously and co-exist. The self-sorting behavior remains prevalent across different building block ratios as two phases of emergence occur: replicator growth followed by foldamer formation. This is attributed to the autocatalytic formation of the replicator fiber, followed by enrichment of the system in the remaining building block, which is subsequently incorporated into a foldamer.

The precise operation of molecular motion for constructing complicated mechanically interlocked molecules has received considerable attention and is still an energetic field of supramolecular chemistry. Herein, we reported the construction of two tris[2]pseudorotaxanes metallacycles with acid-base controllable molecular motion through self-sorting strategy and host-guest interaction. Firstly, two hexagonal Pt(II) metallacycles M1 and M2 decorated with different host-guest recognition sites have been constructed via coordination-driven self-assembly strategy. The binding of metallacycles M1 and M2 with dibenzo-24-crown-8 (DB24C8) to form tris[2]pseudorotaxanes complexes TPRM1 and TPRM2 have been investigated. Furthermore, by taking advantage of the strong binding affinity between the protonated metallacycle M2 and DB24C8, the addition of trifluoroacetic acid (TFA) as a stimulus successfully induces an acid-activated motion switching of DB24C8 between the discrete metallacycles M1 and M2. This research not only affords a highly efficient way to construct stimuli-responsive smart supramolecular systems but also offers prospects for precisely control multicomponent cooperative motion.

In this study, a self-sorting sensor was developed with the ability to distinguish between different pressure regimes and translate the pressure to electrical signals. Specifically, the self-sorting sensor can distinguish between soft and hard pressure like the human skin, without any software assistance and complicated circuits. To achieve the self-sorting property, Janus-like jagged structures were prepared via an all-solution process of spontaneous chemical patterning; they comprised electrically semi-insulating vertices and highly conductive valleys. This unique structure facilitates the detection and determination of the intensities and types of pressure by providing a significant gap between the current levels of two types of states, similar to the function of fibers in the human tactile system. The fabricated sensors also exhibit high sensitivity and durability as well as low power consumption, as demonstrated by the electronic skin and ternary Morse signal applications. Compared with conventional wearable pressure sensors, this sensor can detect signals without additional programming; thus, it is highly suitable for delay-sensitive, energy-efficient sensor applications such as driverless vehicles, autonomous artificial intelligence technology, and prosthetic devices.

Chiral self-sorting is intricately connected to the complicated chiral processes observed in nature and no artificial systems of comparably complexity have been generated by chemists. However, only a few examples of purely organic molecules have been reported so far, where the self-sorting process could be controlled. Herein, we describe the chiral self-sorting of large cubic [8+12] salicylimine cage compounds based on a chiral TBTQ precursor. Out of 23 possible cage isomers only the enantiopure and a meso cage were observed to be formed, which have been unambiguously characterized by single crystal X-ray diffraction. Furthermore, by careful choice of solvent the formation of meso cage could be controlled. With internal diameters of din =3.3-3.5 nm these cages are among the largest organic cage compounds characterized and show very high specific surface areas up to approx. 1500 m2  g-1 after desolvation.

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Self-sorting plays a crucial role in living systems such as the selective assembly of DNA and specific folding of proteins. However, the self-sorting of artificial helical polymers such as biomacromolecules has rarely been achieved. In this work, single-handed helical poly(phenyl isocyanide)s bearing pyrene (Py) and naphthalene (Np) probes were prepared, which exhibited interesting self-sorting properties driven by both helicity and molecular weight (Mn ) in solution, solid state, gel, and on the gel surface as well. The polymers with the same helix sense and similar Mn can self-sort and assemble into well-defined two-dimensional smectic architectures and form stable gels in organic solvents. In contrast, mixed polymers with opposite handedness or different Mn were repulsive to each other and did not aggregate. Moreover, the gels of helical polymers with the same handedness and similar Mn can recognize themselves and adhere together to form a gel.

The emerging field of molecular cybernetics has the potential to widely broaden our perception of chemistry. Chemistry will develop beyond its current focus that is mainly concerned with single transformations, pure compounds, and/or defined mixtures. On this way, chemistry will become autonomous, networked and smart through communicating molecules each of which serves a control engineering purpose, like the set of wheels in the machinery of life. The present personal account describes our latest developments in this field.

New results are presented on the multicomponent supramolecular synthesis of pseudo[1]rotaxanes, achieved by designing pairs of structurally matching N-monoalkyl-4,4\'-bipyridinium/2,7-diazapyrenium-based ligands having complementary π-donor/acceptor features, and intended to self-assemble into the targeted supramolecules by following integrative self-sorting processes. In all the studied cases, it was found that the envisioned species, characterized by NMR spectroscopy and MS spectrometry, arise as the main products of the self-assembly in aqueous media by using palladium(II)/platinum(II) metal centers as the guiding force. Crucially, we have also found that by improving the π-donor/acceptor properties of the matching pairs of ligands (L4 and L5 ), the integrative self-sorting processes prevail even in the absence of metallic ions to afford the heterodimeric species with an association constant being 756±43 M-1 .