Pathway-Dependent Self-Assembly for Control over Helical Nanostructures and Topochemical Photopolymerization.

Pathway-dependent self-assembly, in which a single building block forms two or more types of self-assembled nanostructures, is an important topic due to its mimic to the complexity in biology and manipulation of diverse supramolecular materials. Here, we report a pathway-dependent self-assembly using chiral glutamide derivatives (L or D-PAG), which form chiral nanotwist and nanotube through a cooperative slow cooling and an isodesmic fast cooling process, respectively. Furthermore, pathway-dependent self-assembly can be harnessed to control over the supramolecular co-assembly of PAG with a luminophore ß-DCS or a photopolymerizable PCDA. Fast cooling leads to the co-assembled PAG/ß-DCS nanotube exhibiting green circularly polarized luminescence (CPL), while slow cooling to nanofiber with blue CPL. Additionally, fast cooling process promotes the photopolymerization of PCDA into a red chiral polymer, whereas slow cooling inhibits the polymerization. This work not only demonstrates the pathway-dependent control over structural characteristics but also highlights the diverse functions emerged from the different assemblies.

Helical Nanostructures: Chirality Transfer and a Photodriven Transformation from Superhelix to Nanokebab.

Photosensitive cinnamic acid conjugated glutamides were designed to demonstrate photocontrolled hierarchical chirality transfer and switching in self-assembled systems. In methanol, the cinnamic acid derivatives self-assembled into superhelices, which could be switched into nanokebabs upon UV irradiation. These two nanostructures showed opposite helicity. The chiral nanostructures could further convey their chirality to achiral fluorescent molecules and result in the emission of circularly polarized luminescence (CPL). Remarkably, the CPL followed the helicity of the chiral nanostructure rather than the inherent molecular chirality. Photodriven dimerization of the cinnamic moiety lead to a significant change in molecular packing and subsequent switching of the helicity of the formed nanostructures.

Self-Assembly of Amphiphilic Schiff Base and Selectively Turn on Circularly Polarized Luminescence by Al3.

We designed glutamide-derived amphiphilic Schiff bases containing three different aldehyde moieties for the fabrication of circularly polarized luminescence (CPL) emitting materials. Upon self-assembly in acetonitrile, Schiff bases featuring 4-(dimethylamino)-2-hydroxylbenzaldehyde and 1-hydroxy-2-naphthaldehyde groups form supramolecular gels with twist and fiber structures, respectively, whereas Schiff bases featuring 2-hydroxy-1-naphthaldehyde groups form precipitation with flake structures. Although emission and circular dichroism signals can be detected from the supramolecular gels formed by amphiphilic Schiff bases, none of them exhibits a circularly polarized luminescence (CPL). Although Mg2+, Zn2+, and Al3+ can significantly enhance the fluorescence of the Schiff bases, interestingly, only Al3+ ion is able to turn on the CPL emission. This study on the one hand provides a simple method for the fabrication of CPL-emitting supramolecular materials and on the other hand offers a novel way for the sensing of aluminum ion with supramolecular materials.

Photoirradiation-generated radicals in two-component supramolecular gel for polymerization.

While supramolecular gels have been attracting great interest due to their easy design and fabrication, development of new applications based on these gels is always a challenging topic. Here, we report a two-component supramolecular gel that can generate and stabilize radicals through photo-irradiation, which can be subsequently used for polymerization. It has been found that the electrostatic interactions between a cationic amphiphile and anionic sulfonate could afford co-assembly into a two-component supramolecular gel. Upon photo-irradiation, the gel changed colour and produced the radicals, as verified from the EPR measurements. The radical thus formed in the supramolecular gel is relatively stable and could be used to polymerize acrylic acid directly without deoxygenation. In contrast, acrylic acid could not be polymerized in solution under the same conditions. This work expands the application scope of supramolecular gels.

Bacteria-Based Living Probes: Preparation and the Applications in Bioimaging and Diagnosis.

Bacteria can colonize a variety of in vivo biointerfaces, particularly the skin, nasal, and oral mucosa, the gastrointestinal tract, and the reproductive tract, but also target specific lesion sites, such as tumor and wound. By virtue of their prominent characteristics in motility, editability, and targeting ability, bacteria carrying imageable agents are widely developed as living probes for bioimaging and diagnosis of different diseases. This review first introduces the strategies used for preparing bacteria-based living probes, including biological engineering, chemical modification, intracellular loading, and optical manipulation. It then summarizes the recent progress of these living probes for fluorescence imaging, near-infrared imaging, ultrasonic imaging, photoacoustic imaging, magnetic resonance imaging, and positron emission tomography imaging. The biomedical applications of bacteria-based living probes are also reviewed particularly in the bioimaging and diagnosis of bacterial infections, cancers, and intestine-associated diseases. In addition, the advantages and challenges of bacteria-based living probes are discussed and future perspectives are also proposed. This review provides an updated overview of bacteria-based living probes, highlighting their great potential as a unique yet versatile platform for developing next-generation imageable agents for intelligent bioimaging, diagnosis, and even therapy.

Chiral-Selective Antigen-Presentation by Supramolecular Chiral Polymer Micelles.

Chirality is ubiquitous in biological systems, which is closely related to biological functions, life processes, and even the pathogenesis of diseases. However, the interface between the chirality of synthetic materials and organisms, particularly the immune system, remains poorly understood. Here, supramolecular chiral polymer micelles (SCPMs) are prepared by complexing antigenic proteins with chiral amino acid-modified polyethyleneimine. The introduction of chirality not only reduces the toxicity of cationic polymer, but also benefits cell uptake and antigen presentation. Especially, D-chirality presents the lowest cytotoxicity, while promoting the highest expression level of costimulatory molecules on dendritic cells compared to L-chirality and achirality. The superiority of D-chirality to stimulate dendritic cell maturation is supported by immunization with D-SCPMs, which achieves significant antigen-specific proliferation of T cells in the spleen, lymph nodes, and tumor of mice. Chirality-mediated antigen processing and presentation are demonstrated by D-SCPMs self-assembled from chiral alkaline histidine or neutral phenylalanine modified polyethyleneimine and tumor associated ovalbumin or severe acute respiratory syndrome coronavirus 2 spike 1 antigenic protein. Immunoactivation enabled by D-chirality opens a window to prepare potent nanotherapeutics for disease prevention and treatment.

Circularly Polarized Luminescence of Aluminum Complexes for Chiral Sensing of Amino Acid and Amino Alcohol.

Determination of the absolute configuration (AC) of chiral molecules is a key issue in many fields related to chirality such as drug development, the asymmetric reaction screening, and the structure determination of natural compounds. Although various methods, such as X-ray crystallography and NMR spectroscopy, are used to determine the AC, a simple and cheap alternative method is always anticipated. So far, electronic circular dichroism (ECD) spectroscopy has been widely used to ascertain the AC and enantiomeric excess (ee) values by applying appropriate organic probes. Here, circularly polarized luminescence (CPL) spectroscopy was applied to determine the AC and ee values of a series of amino acid and amino alcohol. The measurements were conducted by mixing the amino acids or amino alcohols with an achiral 1-hydroxy-2-naphthaldehyde. Upon in situ formation of the Schiff base complexes, the system showed emission enhancement and CPL in the presence of Al3+ , whose intensity and sign can be used to assign the chiral sense of the amino acids and amino alcohols. The authenticity of the method was further compared with the established CD spectroscopy, revealing that CPL spectra of formed Al3+ complex were effective to determine the AC of chiral species.

Chiral nanostructures self-assembled from nitrocinnamic amide amphiphiles: substituent and solvent effects.

Chiral nanostructures, such as α-helical proteins and double helix DNA, are widely found in biological systems and play a significant role in the biofunction of life. These structures are essentially fabricated through the covalent or noncovalent bonds between small chiral molecules. It is thus an important issue to understand how small chiral molecules can form chiral nanostructures. Here, using a series of isomeric nitrocinnamic amide derivatives, we have investigated the self-assembly behavior and the effect of the substituent position as well as the solvent on the formation of chiral nanostructures. It was found that totally different chiral nanostructures were formed due to the different positions of the nitro group on the cinnamic amide. Moreover, it was found that the chiral sense of the self-assembled nanostructures can be regulated by the solvent whereby helicity inversion was observed. This work provides a simple way to regulate the self-assembly pathway via molecular design and choice of solvent for the controlled creation of chiral nanostructures.

Switchable circularly polarized luminescence from a photoacid co-assembled organic nanotube.

Materials with circularly polarized luminescence (CPL) are currently attracting great interest in view of their potential applications. Here, we reported self-assembled organic nanotubes with switchable CPL performance. A photoacid, 8-hydroxy-1,3,6-pyrenetrisulfonate (HPTS), was co-assembled with an amino-terminated dialkyl glutamide (LG or DG) in mixed solvents of DMF and water. The complex of LG (DG)/HPTS self-assembled into nanotube structures in the tested range of mixed solvents and showed CPL emission. Different mixing ratios of DMF to water in the solvent triggered CPL switching between different wavelengths. It was revealed that the switching of CPL resulted from the different emissions of the protonated (ROH) and deprotonated (RO-) forms of HPTS, which could be regulated by the solvent polarity. Interestingly, the addition of an acid or base could also switch the fluorescence of LG (DG)/HPTS co-assemblies and the corresponding CPL, leading to an acidity-regulated CPL switch. Thus, through a simple co-assembly strategy, switchable CPL was realized in the self-assembled organic nanotubes via both solvent polarity and acidity.

Enantioselective Activity of Hemin in Supramolecular Gels Formed by Co-Assembly with a Chiral Gelator.

Supramolecular co-assembly provides an efficient way to combine structural and functional units through noncovalent interactions and produce materials with enhanced performance. Here, using a chiral amphiphilic histidine derivative (LHC18 or DHC18) as a gelator, we have successfully co-assembled the gelator and hemin through gelation. During the co-assembly, the chiral information of the gelator was transcribed into the assemblies, and thus right- and left-handed helical ribbons from LHC18-Hemin and DHC18-Hemin co-assemblies were obtained, respectively, which were confirmed by CD spectra and SEM observations. These helical ribbons were used as artificial enzymes to catalyse the oxidation reaction of 3,4-dihydroxy-L-phenylalanine (L-DOPA). The catalytic activity of hemin in supramolecular gels can be effectively enhanced over that of free hemin. Moreover, by virtue of induced chirality, the supramolecular gels of LHC18-Hemin and DHC18-Hemin exhibited obvious enantioselective activity. This work provides a way to combine chirality transfer and supramolecular asymmetric catalysis.

Hierarchical Self-Assembly of a Porphyrin into Chiral Macroscopic Flowers with Superhydrophobic and Enantioselective Property.

Supramolecular self-assembly provides an efficient way to fabricate simple units into various hierarchical nano/microstructures, which could mimic the bioself-assembly and develop functional materials. Since chiral molecules and chiral nanostructures are widely adopted by biological systems, an introduction of the chiral factor into the self-assembly process will provide better understanding of the biological systems. Here, using a chiral amphiphilic histidine to assist the self-assembly of a porphyrin with four carboxylic acids, we obtained hierarchical chiral nano- to microstructures. We have found that through the hydrogen bonds/electrostatic interactions between the porphyrin and histidine derivatives, the π-π stacking between the porphyrins, and hydrophobic interactions between the amphiphilic histidine, the two components could self-assemble into chiral nanohelices and microflowers. The supramolecular chirality of these structures was confirmed by scanning electron microscopy images as well as the circular dichroism spectra, which was found to follow the molecular chirality of the histidine derivative. More interestingly, the microflower structures formed a superhydrophobic and chiral surface, which exhibited macroscopic enantioselective recognition of some l- and d-amino acids via contact angle measurements.