Functional Supramolecular Architectures of Dipyrrin Complexes

Dynamic formation of self-assemblies from molecular components is a useful and efficient way to produce molecular and supramolecular architectures with sophisticated functions. The labile coordination bond and dynamic covalent bond as a reversible bond have often been used to create a well-organized supramolecular self-assembly. In order to realize sophisticated novel functions of the supramolecular self-assemblies, dipyrrin complexes have recently been employed as a functional unit and incorporated into the supramolecular architectures because of their outstanding properties and functions such as a high photostability and strong light absorption/emission. This review article summarizes recent development in functional supramolecular architectures of the dipyrrin complexes produced by coordination to a metal ion and dynamic covalent bond formation. We first describe the synthesis and unique functions of a series of discrete supramolecular architectures: helicates, macrocycles, and cages. The polymeric supramolecular self-assemblies with 1D, 2D, and 3D structures are then introduced as a functional infinite supramolecular architecture

Response speed control of helicity inversion based on a “regulatory enzyme”-like strategy

In biological systems, there are many signal transduction cascades in which a chemical signal is transferred as a series of chemical events. Such successive reaction systems are advantageous because the efficiency of the functions can be finely controlled by regulatory enzymes at an earlier stage. However, most of artificial responsive molecules developed so far rely on single-step conversion, whose response speeds have been difficult to be controlled by external stimuli. In this context, developing artificial conversion systems that have a regulation step similar to the regulatory enzymes has been anticipated. Here we report a novel artificial two-step structural conversion system in which the response speed can be controlled based on a regulatory enzyme-like strategy. In this system, addition of fluoride ion caused desilylation of the siloxycarboxylate ion attached to a helical complex, resulting in the subsequent helicity inversion. The response speeds of the helicity inversion depended on the reactivity of the siloxycarboxylate ions; when a less-reactive siloxycarboxylate ion was used, the helicity inversion rate was governed by the desilylation rate. This is the first artificial responsive molecule in which the overall response speed can be controlled at the regulation step separated from the function step

Functional Supramolecular Architectures of Dipyrrin Complexes

Dynamic formation of self-assemblies from molecular components is a useful and efficient way to produce molecular and supramolecular architectures with sophisticated functions. The labile coordination bond and dynamic covalent bond as a reversible bond have often been used to create a well-organized supramolecular self-assembly. In order to realize sophisticated novel functions of the supramolecular self-assemblies, dipyrrin complexes have recently been employed as a functional unit and incorporated into the supramolecular architectures because of their outstanding properties and functions such as a high photostability and strong light absorption/emission. This review article summarizes recent development in functional supramolecular architectures of the dipyrrin complexes produced by coordination to a metal ion and dynamic covalent bond formation. We first describe the synthesis and unique functions of a series of discrete supramolecular architectures: helicates, macrocycles, and cages. The polymeric supramolecular self-assemblies with 1D, 2D, and 3D structures are then introduced as a functional infinite supramolecular architecture

Uniquely folded shapes, photophysical properties, and recognition abilities of macrocyclic BODIPY oligomers

Macrocyclic BODIPY/dipyrrin tetramers and pentamers connected by m‐phenylene linkers were synthesized. Their uniquely folded shapes were revealed by a single‐crystal X‐ray diffraction analysis, and their dynamic structural behaviors in solution were investigated by variable‐temperature NMR measurements. The BODIPY oligomers exhibited strong emission properties without quenching. Furthermore, the BODIPY pentamer interacted with an ammonium cation utilizing the negatively charged binding pockets in which the polarized Bδ+–Fδ− bonds are present

Synthesis of per(5-N-carboxamide-5-dehydroxylmethyl)-β-cyclodextrins and their selective recognition ability utilizing multiple hydrogen bonds

Per(5-N-carboxamide-5-dehydroxylmethyl)-β-cyclodextrin derivatives with seven equivalent amide groups directly attached to each pyranose ring were synthesized. The amide cyclodextrins show unique recognition properties toward hydrogen phosphonate anions. An X-ray crystallographic analysis revealed its recognition mode in which unsymmetrically arranged amide groups play distinctive roles both as a hydrogen bond donor and acceptor

Activation of invariant natural killer T cells stimulated with microbial α-mannosyl glycolipids

Some synthetic and bacterial glycolipids presented by CD1d specifically activate invariant NKT (iNKT) cells bearing an invariant Vα14-Jα18 (mouse) or Vα24-Jα18 (human) TCR. The antigenic glycolipids identified to date consist of two hydrophobic chains and an α-glycoside in which the 2′-OH group is in the cis orientation toward the anomeric group, namely, either an α-galactoside or an α-glucoside. Several microbial α-mannosyl glycolipids, in which the 2′-OH group is in the trans orientation, were herein examined to establish whether they have potential to activate iNKT cells. We found that α-mannnosyl1-3 (6′-O-acyl α-mannosyl)-1-1 monoacylglycerol and cholesteryl 6′-O-acyl α-mannoside, found in Saccharopolyspora and Candida albicans, respectively, induced the activation of iNKT cells, dependent on CD1d. In contrast, α-mannosyldiacylglycerol found in Streptococcus suis or α-mannosylceramide demonstrated markedly less antigenicity for iNKT cells. The potentially antigenic α-mannosyl glycolipids contributed to the protection of mice against infection with S. pneumoniae in which iNKT cells have previously been found to participate. Furthermore, these glycolipids induced the production of proinflammatory cytokines by macrophages, thereby suggesting their recognition by specific pattern recognition receptors (PRRs). Collectively, these results suggest that these microbial α-mannosyl glycolipids are capable of being recognized by both the invariant TCR and PRRs and inducing immune responses

Synergy in supramolecular chemistry

Synergy and Cooperativity in Multi-metal Supramolecular Systems, T. NabeshimaHierarchically Assembled Titanium Helicates, Markus AlbrechtSupramolecular Hosts and Catalysts Formed by Self-assembly of Multinuclear Zinc Complexes in Aqueous Solution, Shin AokiSupramolecular Assemblies Based on Interionic Interactions, H. MaedaSupramolecular Synergy in the Formation and Function of Guanosine Quadruplexes, Jeffery T. DavisOn-Surface Chirality in Porous Self-Assembled Monolayers at Liquid-Solid Interface, Kazukuni Taha

極性応答的な着脱能をもつ分子コートを導入した発光性分子の創製

科学研究費助成事業 研究成果報告書：挑戦的萌芽研究2014-2015課題番号 : 2662012