Oleg Borodin

The obvious contradiction between the high local concentration‐based substrate reactivity and free diffusion‐based high reaction efficiency was still one of the important challenges in chemistry. Herein, we proposed an efficient aggregation‐induced synergism via hydrophobic‐driven self‐assembly of amphiphilic oligonucleotides to generate high local concentration and retain high reaction efficiency via hydrophobic‐based aggregation, which is important to construct the efficient DNA nanomachines for ultrasensitive strategy. With microRNA 155 as a model, it could trigger a strand displacement amplification with the DNA monomers on the 3D DNA nanomachine and generate an amplified fluorescent response for its sensitive assay. The local concentration of the substrates was increased at least a 9.0 × 10 5 fold via hydrophobic interaction‐based self‐assembly in comparison with the traditional homogeneous reaction system, performing high local concentration‐based and free diffusion‐based enhanced reaction efficiency. As expected, the aggregation‐induced synergism via hydrophobic‐driven self‐assembly of amphiphilic oligonucleotides performed excellent properties to generate 3D DNA nanomachine for microRNA 155 assay in cells. Most importantly, this approach could be easily expanded for the bioassay of various biomarkers, such as nucleotides, proteins and cells, offering a new avenue for the simple and efficient application in bioanalysis and clinical diagnosis.

Drug release: While poly(orthoester)s have many advantages, the synthesis of poly(acyclic orthoester)s has not yet been reported. Here the facile synthesis of poly(acyclic orthoester)s by polycondensation of acyclic diketene acetals and diols is developed. Poly(acyclic orthoester) nanoparticles release antigens into the cytoplasm, enhancing antigen presentation efficiency, and could serve to broaden the applications of poly(orthoester)s in protein‐ and gene‐based therapies.

Abstract

While poly(acyclic orthoester)s (PAOEs) have many appealing features for drug delivery, their application is significantly hindered by a lack of facile synthetic methods. Reported here is a simple method for synthesizing acyclic diketene acetal monomers from diols and vinyl ether, and their polymerization with a diol to first synthesize PAOEs. The PAOEs rapidly hydrolyze at lysosomal pH. With the help of a cationic lipid, ovalbumin, a model vaccine antigen was efficiently loaded into PAOEs nanoparticles using a double emulsion method. These nanoparticles efficiently delivered ovalbumin into the cytosol of dendritic cells and demonstrated enhanced antigen presentation over poly(lactic‐co‐glycolic acid) (PLGA) nanoparticles. PAOEs are promising vehicles for intracellular delivery of biopharmaceuticals and could increase the utility of poly(orthoesters) in biomedical research.

Play with Lego: A modular synthetic strategy for macrocycles with functional skeletons was demonstrated, involving one‐pot and high‐yielding condensation between bis(2,4‐dimethoxyphenyl)arene monomers and paraformaldehyde. By changing the blocks, variously functional units can be conveniently introduced into the backbone of macrocycles.

Abstract

Reported here is a molecule‐Lego synthetic strategy for macrocycles with functional skeletons, involving one‐pot and high‐yielding condensation between bis(2,4‐dimethoxyphenyl)arene monomers and paraformaldehyde. By changing the blocks, variously functional units (naphthalene, pyrene, anthraquinone, porphyrin, etc.) can be conveniently introduced into the backbone of macrocycles. Interestingly, the macrocyclization can be tuned by the geometrical configuration of monomeric blocks. Linear (180°) monomer yield cyclic trimers and pentamers, while V‐shaped (120°, 90° and 60°) monomers tend to form dimers. More significantly, even heterogeneous macrocycles are obtained in moderate yield by co‐oligomerization of different monomers. This series of macrocycles have the potential to be prosperous in the near future.

The bigger the better: Two categories of giant, lipid‐like amphiphilic molecules organize into various mesostructures, shedding new light on the underlying principles of lipid self‐assembly. The geometric parameters of these giant, lipid‐like molecules are modulated on a molecular level to understand the physiochemical driving forces behind their self‐assembly.

Abstract

How biomembranes are self‐organized to perform their functions remains a pivotal issue in biological and chemical science. Understanding the self‐assembly principles of lipid‐like molecules hence becomes crucial. Herein, we report the mesostructural evolution of amphiphilic sphere‐rod conjugates (giant lipids), and study the roles of geometric parameters (head–tail ratio and cross‐sectional area) during this course. As a prototype system, giant lipids resemble natural lipidic molecules by capturing their essential features. The self‐assembly behavior of two categories of giant lipids (I‐shape and T‐shape, a total of 8 molecules) is demonstrated. A rich variety of mesostructures is constructed in solution state and their molecular packing models are rationally understood. Giant lipids recast the phase behavior of natural lipids to a certain degree and the abundant self‐assembled morphologies reveal distinct physiochemical behaviors when geometric parameters deviate from natural analogues.

The importance of the whole picture : Aggregation‐induced emission (AIE) research demonstrates that many properties and functions that are absent in molecular species can be found in molecular aggregates. AIE research thus emphasizes the significance of aggregate science in addition to molecular science for materials development.

Abstract

Aggregation‐induced emission (AIE) describes a photophysical phenomenon in which molecular aggregates exhibit stronger emission than the single molecules. Over the course of the last 20 years, AIE research has made great strides in material development, mechanistic study and high‐tech applications. The achievements of AIE research demonstrate that molecular aggregates show many properties and functions that are absent in molecular species. In this review, we summarize the advances in the field of AIE and its related areas. We specifically focus on the new properties of materials attained by molecular aggregates beyond the microscopic molecular level. We hope this review will inspire more research into molecular ensembles at and beyond the meso level and lead to the significant progress in material and biological science.

Two kinds of soft devices have been fabricated through spatial manipulation and integration of micellar filaments on the surface of hydrogels. They include a freely suspended fibrous net that can trap and release micro‐particles and the one that is capable of morphing shapes with controlled rolling directionality.

Abstract

Supramolecular assemblies are promising building blocks for the fabrication of functional soft devices for high‐tech applications. However, there is a lack of effective methods for large‐scale manipulation and integration of nano‐sized supramolecular structures on soft substrate. Now, functional soft devices composed of micellar filaments and hydrogels can be created through a versatile approach involving guided dewetting, transfer‐printing, and laser‐assisted patterning. Such an approach enables unprecedented control over the location and alignment of the micellar filaments on hydrogel substrates. As examples, freely suspended micellar fishnets immobilized on hydrogels are formed, showing the capability of trapping and releasing micro‐objects and the piconewton force sensitivity. By incorporating responsive moieties into hydrogels, shape‐morphing actuators with micelle‐controlled rolling directionality are constructed.

Hierarchical supramolecular self‐assembly of a cyclic peptide functional amphiphilic diblock copolymer into photo‐responsive tubisomes in water was investigated. These tubisomes are employed as photo‐controlled drug delivery vehicles for anticancer drug Doxorubicin to achieve enhanced intracellular DOX release and improved anticancer activity.

Abstract

Typically, the morphologies of the self‐assembled nanostructures from block copolymers are limited to spherical micelles, wormlike micelles and vesicles. Now, a new generation of materials with unique shape and structures, cylindrical soft matter particles (tubisomes), are obtained from the hierarchical self‐assembly of cyclic peptide‐bridged amphiphilic diblock copolymers. The capacity of obtained photo‐responsive tubisomes as potential drug carriers is evaluated. The supramolecular tubisomes pave an alternative way for fabricating polymeric tubular structures, and will expand the toolbox for the rational design of functional hierarchical nanostructures.

Chemistry brought to life? Between vitalism and romanticism, often‐forgotten naturalists believed in the spontaneous creation of matter, essential for biological activity to occur. Yet flawed, they opened the door to understanding shape and pattern in nature. That knowledge gives clues to the origin of primitive life and notably fuels our efforts in designing artificial cells.

Abstract

This Essay focuses briefly on early studies elaborated by natural and chemical philosophers, and the once‐called synthetic biologists, who postulated the transition from inanimate to animate matter and even foresaw the possibility of creating artificial life on the basis of physical and chemical principles only. Such ideas and speculations, ranging from soundness to weirdness, paved however the way to current developments in areas like abiotic pattern formation, cell compartmentalization, biomineralization, or the origin of life itself. In particular, the generation of biomorphs and their relationship to microfossils represents an active research domain and seems to be the logical way to bring the historical work up to the future, as some scientists are trying to make artificial cells. The last sections of this essay will also highlight modern science aimed at understanding what life is and, whether or not, it can be redefined in chemical terms.

We present here a synergy between organic electronics and supramolecular chemistry, in which a host–guest complex is designed to function as an efficacious electronic material. Specifically, the non‐covalent recognition of a fullerene, phenyl‐C 61 ‐butyric acid methyl ester ( PC 61 BM ), by our alternating perylene diimide ( P )–bithiophene ( B ) conjugated macrocycle ( PBPB ) results in a greater than five‐fold enhancement in electron mobility, relative to the macrocycle material alone. Characterisation and quantification of the binding of a number of PC 61 BM and other fullerene guests by host PBPB is provided by multi‐nuclear NMR spectroscopy and mass spectrometry. Electrochemical and photophysical studies provide evidence for intermolecular electronic communication within the [ PBPB ] ⊃ [ Fullerene ] complexes. Supramolecular self‐assembly generates a superior electron‐transporting material for the fabrication of more efficient electronic devices, such as organic field effect transistors.

Nature Chemistry, Published online: 10 February 2020; doi:10.1038/s41557-020-0419-2

Nature, Published online: 06 February 2020; doi:10.1038/d41586-020-00351-7

Nature Communications, Published online: 07 February 2020; doi:10.1038/s41467-020-14607-3

Nature, Published online: 06 February 2020; doi:10.1038/d41586-020-00326-8

Nature, Published online: 05 February 2020; doi:10.1038/d41586-020-00271-6

Linking cages: Molecular dumbbells with organic cage capping units were synthesised via a multi‐component imine condensation between a tri‐topic amine and di‐ and tetra‐topic aldehydes. This is an example of self‐sorting, which can be rationalised by computational modelling.

Abstract

Molecular dumbbells with organic cage capping units were synthesised via a multi‐component imine condensation between a tri‐topic amine and di‐ and tetra‐topic aldehydes. This is an example of self‐sorting, which can be rationalised by computational modelling.

Spatially regulated assembly of synthetic supramolecular fibers is controlled in a microfluidic device. Modulation of chemical triggers such as pH or ionic strength allowed the spatial organization of supramolecular fibers confined in water droplets. 2D suprastructures can be assembled by controlling the organization of droplet and fibrillar assembly.

Abstract

Despite the importance of spatially resolved self‐assembly for molecular machines, the spatial control of supramolecular polymerization with synthetic monomers had not been experimentally established. Now, a microfluidic‐regulated tandem process of supramolecular polymerization and droplet encapsulation is used to control the position of self‐assembled microfibrillar bundles of cyclic peptide nanotubes in water droplets. This method allows the precise preferential localization of fibers either at the interface or into the core of the droplets. UV absorbance, circular dichroism and fluorescence microscopy indicated that the microfluidic control of the stimuli (changes in pH or ionic strength) can be employed to adjust the packing degree and the spatial position of microfibrillar bundles of cyclic peptide nanotubes. Additionally, this spatially organized supramolecular polymerization of peptide nanotubes was applied in the assembly of highly ordered two‐dimensional droplet networks.