Dimensionally controlled and hierarchically assembled supramolecular architectures in nano/micro/bulk length scales are formed by self-organization of alkyl-conjugated fullerenes. The simple ...molecular design of covalently attaching hydrophobic long alkyl chains to fullerene (C(60)) is different from the conventional (hydrophobic-hydrophilic) amphiphilic molecular designs. The two different units of the alkyl-conjugated C(60) are incompatible but both are soluble in organic solvents. The van der Waals intermolecular forces among long hydrocarbon chains and the pi-pi interaction between C(60) moieties govern the self-organization of the alkyl-conjugated C(60) derivatives. A delicate balance between the pi-pi and van der Waals forces in the assemblies leads to a wide variety of supramolecular architectures and paves the way for developing supramolecular soft materials possessing various morphologies and functions. For instance, superhydrophobic films, electron-transporting thermotropic liquid crystals and room-temperature liquids have been demonstrated. Furthermore, the unique morphologies of the assemblies can be utilised as a template for the fabrication of nanostructured metallic surfaces in a highly reproducible and sustainable way. The resulting metallic surfaces can serve as excellent active substrates for surface-enhanced Raman scattering (SERS) owing to their plasmon enhancing characteristics. The use of self-assembling supramolecular objects as a structural template to fabricate innovative well-defined metal nanomaterials links soft matter chemistry to hard matter sciences.
Solvent‐free luminous molecular liquids (LMLs) are a new generation of soft matter which exhibit uncharged, nonvolatile, and fluidic nature and emit intense and homogeneous luminescence in the ...condensed state. They can be produced readily on the gram scale by modifying luminophores with bulky, flexible, and low‐melting side chains. Their performance can be facilely enriched by blending them with commercially available functional substances. Therefore, since their active optoelectronic properties were perceived a decade ago, LMLs have been regarded as promising contributing components in the burgeoning field of flexible and wearable light‐emitting devices. Recently, richer insights into LMLs have triggered various new applications. Additionally, unexpected phase behavior and photophysical properties have been discovered coincidentally. Therefore, the sensible and sophisticated molecular design principles of LMLs are still being augmented to guarantee predictable, steady, and consistent end‐use performance. This review summarizes the latest developments in LMLs, including molecular design principles, regulation and enrichment of their photophysical properties, and their versatile applications. Additionally, a prediction of the perspectives of LMLs in the near future is presented at the end.
The history, molecular design principles, function enrichment, and versatile applications of luminous molecular liquids are reviewed. As a newly emerging nonvolatile soft luminescent material, luminous molecular liquids are uncharged, nonvolatile, fluidic, and highly luminescent. Their effortless preparation, superior stability, high processability, facile refillability, and unlimited deformability facilitate wide applications in various research fields, in particular, the burgeoning flexible light‐emitting devices.
Self-organisation is an elegant tool for the creation of assemblies controlled in all dimensions with tunable properties in natural as well as artificial supramolecular systems. Especially, the ...supramolecular organisation of fullerene (C(60)) using π-stacking interaction to form various functional assemblies is of particular importance as it can provide excellent optoelectronic properties. Interestingly, the insufficient solubility of C(60) has been overcome through the noncovalent interaction with other hosts and covalent functionalisation with organic moieties. This has resulted in supramolecular assemblies at the nano/micro/macro scales under different preparation conditions. The developments in the area of fullerene self-assembly during the last few decades have significantly contributed to the sensible design and fabrication of organic electronic devices. A summary of the very recent reports regarding the organisation of pristine C(60), its coassembly with other hosts, unique polymorphs of fullerene derivatives, functional liquid crystalline assemblies, donor/acceptor heterojunctions and its applications will be presented in this tutorial review. Future research directions in which the supramolecular fullerene assembly may achieve more precision and improve the efficiency of the photovoltaic devices are also discussed.
The development of optoelectronically‐active soft materials is drawing attention to the application of soft electronics. A room‐temperature solvent‐free liquid obtained by modifying a π‐conjugated ...moiety with flexible yet bulky alkyl chains is a promising functional soft material. Tuning the elastic modulus (G′) is essential for employing optoelectronically‐active alkyl–π liquids in deformable devices. However, the range of G′ achieved through the molecular design of alkyl–π liquids is limited. We report herein a method for controlling G′ of alkyl–π liquids by gelation. Adding 1 wt % low‐molecular‐weight gelator formed the alkyl–π functional molecular gel (FMG) and increased G′ of alkyl–π liquids by up to seven orders of magnitude while retaining the optical properties. Because alkyl–π FMGs have functional π‐moieties in the gel medium, this new class of gels has a much higher content of π‐moieties of up to 59 wt % compared to conventional π‐gels of only a few wt %. More importantly, the gel state has a 23 % higher charge‐retention capacity than the liquid, providing better performance in deformable mechanoelectric generator‐electret devices. The strategy used in this study is a novel approach for developing next‐generation optoelectronically‐active FMG materials.
We report the development of alkyl–π functional molecular gels (FMGs), in which the addition of a 1 wt % low‐molecular‐weight gelator can increase the elastic modulus of alkyl–π liquids by up to seven orders of magnitude while retaining the optical properties. Furthermore, gelation improved the performance of mechanoelectric generator‐electret devices compared to liquid‐based ones.
The water flea Daphnia magna has been used as an animal model in ecology, evolution, and environmental sciences. Thanks to the recent progress in Daphnia genomics, genetic information such as the ...draft genome sequence and expressed sequence tags (ESTs) is now available. To investigate the relationship between phenotypes and the available genetic information about Daphnia, some gene manipulation methods have been developed. However, a technique to induce targeted mutagenesis into Daphnia genome remains elusive. To overcome this problem, we focused on an emerging genome editing technique mediated by the clustered regularly interspaced short palindromic repeats/CRISPR-associated (CRISPR/Cas) system to introduce genomic mutations. In this study, we targeted a functionally conserved regulator of eye development, the eyeless gene in D. magna. When we injected Cas9 mRNAs and eyeless-targeting guide RNAs into eggs, 18-47% of the survived juveniles exhibited abnormal eye morphology. After maturation, up to 8.2% of the adults produced progenies with deformed eyes, which carried mutations in the eyeless loci. These results showed that CRISPR/Cas system could introduce heritable mutations into the endogenous eyeless gene in D. magna. This is the first report of a targeted gene knockout technique in Daphnia and will be useful in uncovering Daphnia gene functions.
Organic phosphors have been widely explored with an understanding that crystalline molecular ordering is a requisite for enhanced intersystem crossing. In this context, we explored the ...room‐temperature phosphorescence features of a solvent‐free organic liquid phosphor in air. While alkyl chain substitution varied the physical states of the bromonaphthalimides, the phosphorescence remained unaltered for the solvent‐free liquid in air. As the first report, a solvent‐free liquid of a long swallow‐tailed bromonaphthalimide exhibits room‐temperature phosphorescence in air. Doping of the phosphor with carbonyl guests resulted in enhanced phosphorescence, and hence a large‐area paintable phosphorescent liquid composite with improved lifetime and quantum yield was developed.
The room‐temperature phosphorescence features of a solvent‐free organic liquid phosphor in air were explored. Doping of the phosphor with carbonyl guests resulted in enhanced phosphorescence, and hence a large‐area paintable phosphorescent liquid composite with improved lifetime and quantum yield was developed.
The distribution of the anthropogenic radionuclide 241Am, a decay product of 241Pu discharged from atmospheric tests of nuclear weapons, was investigated to resolve its horizontal and vertical ...migration in the Tropical East Pacific. We analyzed 241Am concentrations in seawater samples collected in 2003. On comparing the 241Am concentrations with the previously determined concentrations of 239+240Pu in the same samples, the vertical profiles of 241Am were found to be similar to those of 239+240Pu. At some stations, the maximum concentration of 241Am occurred 100–200 m deeper than that of 239+240Pu. The 241Am/239+240Pu ratios in the North Pacific and South Pacific were comparable to one another, and were the typical ratio for the Pacific. The 241Am distribution was influenced by the water mass at depths below 400 m. The 241Am data support the view there is a current flowing at depths of 400–3000 m from the North Pacific through the Equator to the South Pacific. In addition, the 241Am vertical profile was explained by using a 1-D scavenging model that considers the decay of 241Pu and adsorption and scavenging by suspended particles. The different depths for the maximum concentrations of 241Am and 239+240Pu observed at some stations were well explained by the model and by the distribution of CaCO3 particles. The residence time of 241Am in the Pacific was also estimated by using the model.
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•241Am is a decay product of 241Pu discharged from atmospheric nuclear weapons tests.•Its utility as a tracer was investigated.•241Am concentrations were explained by a 1-D scavenging model.•Data demonstrated a current flows at depths of 400–3000 m from the North to South Pacific.•Residence times are 550 yr where particle settling is important and 1940 yr in others.
The clustered regularly interspaced short palindromic repeats (CRISPR)/CRISPR-associated system (Cas) is widely used for mediating the knock-in of foreign DNA into the genomes of various organisms. ...Here, we report a process of CRISPR/Cas-mediated knock-in via non-homologous end joining by the direct injection of Cas9/gRNA ribonucleoproteins (RNPs) in the crustacean Daphnia magna, which is a model organism for studies on toxicology, ecology, and evolution. First, we confirmed the cleavage activity of Cas9 RNPs comprising purified Cas9 proteins and gRNAs in D. magna. We used a gRNA that targets exon 10 of the eyeless gene. Cas9 proteins were incubated with the gRNAs and the resulting Cas9 RNPs were injected into D. magna eggs, which led to a typical phenotype of the eyeless mutant, i.e., eye deformity. The somatic and heritable mutagenesis efficiencies were up to 96% and 40%, respectively. Second, we tested the CRISPR/Cas-mediated knock-in of a plasmid by the injection of Cas9 RNPs. The donor DNA plasmid harboring the fluorescent reporter gene was designed to contain the gRNA recognition site. The co-injection of Cas9 RNPs together with the donor DNAs resulted in generation of one founder animal that produced fluorescent progenies. This transgenic Daphnia had donor DNA at the targeted genomic site, which suggested the concurrent cleavage of the injected plasmid DNA and genomic DNA. Owing to its simplicity and ease of experimental design, we suggest that the CRISPR/Cas-mediated knock-in method represents a promising tool for studying functional genomics in D. magna.
Transcription activator-like effector nucleases (TALENs) are versatile tools that enable the insertion of DNA into different organisms. Here, we confirmed TALEN-mediated knock-in via non-homologous ...end joining in the crustacean Daphnia magna, a model organism for ecological and toxicological genomics. We tested two different TALENs, ey1 TALEN and ey2 TALEN, both of which target the eyeless locus. The donor DNA plasmid, harbouring the H2B-GFP reporter gene, was designed to contain both TALEN target sites and was co-injected with each TALEN mRNA into eggs. The ey1 TALEN and ey2 TALEN constructs both resulted in H2B-GFP expression in Daphnia with a germline transmission efficiency of 3%. Of the three transgenic animals generated, two had donor DNA at the targeted genomic site, which suggested concurrent cleavage of the injected plasmid DNA and genome DNA. The availability of such tools that are capable of targeted knock-in of foreign genes will be extremely useful for advancing the knowledge of gene function and contribute to an increased understanding of functional genomics in Daphnia.
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