Molecular photoswitches have attracted much attention in biological and materials contexts. Despite the fact that existing classes of these highly interesting functional molecules have been heavily investigated and optimized, distinct obstacles and inherent limitations remain. Considerable synthetic efforts and complex structure-property relationships render the development and exploitation of new photoswitch families difficult. Here, we focus our attention on acylhydrazones: a novel, yet underexploited class of photochromic molecules based on the imine structural motif. We optimized the synthesis of these potent photoswitches and prepared a library of over 40 compounds, bearing different substituents in all four crucial positions of the backbone fragment, and conducted a systematic study of their photochromic properties as a function of structural variation. This modular family of organic photoswitches offers a unique combination of properties and the compounds are easily prepared on large scales within hours, through an atom-economic synthesis, from commercially available starting materials. During our thorough spectroscopic investigations, we identified photoswitches covering a wide range of thermal half-lives of their (Z)-isomers, from short-lived T-type to thermally stable P-type derivatives. By proper substitution, excellent band separation between the absorbance maxima of (E)- and (Z)-isomers in the UV or visible region could be achieved. Our library furthermore includes notable examples of rare negative photochromic systems, and we show that acylhydrazones are highly fatigue resistant and exhibit good quantum yields.
Molecular self-assembly is the basis for the formation of numerous artificial nanostructures. The self-organization of peptides, amphiphilic molecules composed of fused benzene rings and other functional molecules into nanotubes is of particular interest. However, the design of dynamic, complex self-organized systems that are responsive to external stimuli remains a significant challenge. Here, we report self-assembled, vesicle-capped nanotubes that can be selectively disassembled by irradiation. The walls of the nanotubes are 3-nm-thick bilayers and are made from amphiphilic molecules with two hydrophobic legs that interdigitate when the molecules self-assemble into bilayers. In the presence of phospholipids, a phase separation between the phospholipids and the amphiphilic molecules creates nanotubes, which are end-capped by vesicles that can be chemically altered or removed and reattached without affecting the nanotubes. The presence of a photoswitchable and fluorescent core in the amphiphilic molecules allows fast and highly controlled disassembly of the nanotubes on irradiation, and distinct disassembly processes can be observed in real time using fluorescence microscopy.
The novel concept of amphiphilic molecular motors that self-assemble into responsive supramolecular nanotubes in water is presented. The dynamic function of the molecular motor units inside the supramolecular assemblies was studied using UV-vis absorption spectroscopy and cryo-transmission electron microscopy (cryo-TEM) microscopy. Reorganization between distinct, well-defined nanotubes and vesicles can be reversibly induced by light, going through the rotation cycle of the motor, i.e. driven by alternate photochemical and thermal isomerization steps in the system. This is the first example in which a molecular rotary motor shows self-assembly in an aqueous medium with full retention of its functionality, paving the way to increasingly complex, highly dynamic artificial nanosystems in water.
The novel concept for the autoamplification of molecular chirality, wherein the amplification proceeds through the induction of supramolecular chirality, is presented. A solution of prochiral, ring-open diarylethenes is doped with a small amount of their chiral, ring-closed counterpart. The molecules co-assemble into helical fibers through hydrogen bonding and the handedness of the fibers is biased by the chiral, ring-closed diarylethene. Photochemical ring closure of the open diarylethene yields the ring-closed product, which is enriched in the template enantiomer.
Polyelectrolyte complex (PEC) films such as polyelectrolyte multilayers have demonstrated excellent oxygen barrier properties, but unfortunately, the established layer-by-layer approaches are laborious and difficult to scale up. Here, we demonstrate a novel single-step approach to produce a PEC film, based on the use of a volatile base. Ammonia was used to adjust the pH of poly(acrylic acid) (PAA) so that direct complexation was avoided when it was mixed with polyethylenimine (PEI). Different charge ratios of homogeneous PEI/PAA solutions were successfully prepared and phase diagrams varying the concentration of ammonia or polyelectrolyte were made to study the phase behavior of PEI, PAA, and ammonia in water. Transparent ∼1 μm thick films were successfully deposited on biaxially orientated polypropylene (BOPP) sheets using a Meyer rod. After casting the films, the decrease in pH, caused by the evaporation of ammonia, triggered the complexation during drying. The oxygen permeation properties of films with different ratios and single polyelectrolytes were tested. All films displayed excellent oxygen barrier properties, with an oxygen permeation below 4 cm 3 ·m –2 ·day –1 ·atm –1 (<0.002 barrer) at the optimum ratio of 2:1 PEI/PAA. This ammonia evaporation-induced complexation approach creates a new pathway to prepare PEC films in one simple step while allowing the possibility of recycling.
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