Photo-controllable microcleaner: photo-induced crawling motion and particle transport of azobenzene crystals on a liquid-like surface.

Organic crystals of 3,3'-dimethylazobenzene (DMAB) exhibit photo-induced crawling motion on solid surfaces when they are simultaneously irradiated with ultraviolet and visible light from opposite directions. DMAB crystals are candidates for light-driven cargo transporters, having simple chemical compositions and material structures. However, fast crawling motion without significant shape deformation has not yet been achieved. In this study, compared with hydrophilic glass and conventional hydrophobic surfaces with alkyl chains, siloxane-based hybrid surfaces, which are "liquid-like surfaces," result in the fastest crawling motion (4.2 µm min-1) while the droplet-like shape of DMAB crystals is maintained. Additionally, we successfully demonstrate that the DMAB crystals are capable of capturing and carrying silica particles on the hybrid surface. The transport direction is changed on demand without releasing the particles by simply changing the irradiation direction. The particles can be left on the substrate by removing the DMAB crystals via sublimation at room temperature. This result showcases a new concept of "photo-controllable microcleaner" that can operate a series of cargo capture-carry-release tasks. We expect this transporter to contribute to the development of crystal actuators, microfluidics, and microscale molecular flasks/reactors.

Visualization of the Dynamics of Photoinduced Crawling Motion of 4-(Methylamino)Azobenzene Crystals via Diffracted X-ray Tracking.

The photoinduced crawling motion of crystals is a continuous motion that azobenzene molecular crystals exhibit under light irradiation. Such motion enables object manipulation at the microscale with a simple setup of fixed LED light sources. Transportation of nano-/micromaterials using photoinduced crawling motion has recently been reported. However, the details of the motion mechanism have not been revealed so far. Herein, we report visualization of the dynamics of fine particles in 4-(methylamino)azobenzene (4-MAAB) crystals under light irradiation via diffracted X-ray tracking (DXT). Continuously repeated melting and recrystallization of 4-MAAB crystals under light irradiation results in the flow of liquid 4-MAAB. Zinc oxide (ZnO) particles were introduced inside the 4-MAAB crystals to detect diffracted X-rays. The ZnO particles rotate with the flow of liquid 4-MAAB. By using white X-rays with a wide energy width, the rotation of each zinc oxide nanoparticle was detected as the movement of a bright spot in the X-ray diffraction pattern. It was clearly shown that the ZnO particles rotated increasingly as the irradiation light intensity increased. Furthermore, we also found anisotropy in the rotational direction of ZnO particles that occurred during the crawling motion of 4-MAAB crystals. It has become clear that the flow perpendicular to the supporting film of 4-MAAB crystals is enhanced inside the crystal during the crawling motion. DXT provides a unique means to elucidate the mechanism of photoinduced crawling motion of crystals.

Correction: Synthesis of figure-of-eight helical bisBODIPY macrocycles and their chiroptical properties.

Correction for 'Synthesis of figure-of-eight helical bisBODIPY macrocycles and their chiroptical properties' by Makoto Saikawa et al., Chem. Commun., 2016, 52, 10727-10730.

Synthesis and Unique Optical Properties of Selenophenyl BODIPYs and Their Linear Oligomers.

A series of selenophene-substituted boron-dipyrrin (BODIPY) monomers and selenophene-linked BODIPY oligomers was synthesized. The synthesized BODIPYs show good absorption/emission properties in the red to near-infrared region. Furthermore, some of the selenophenyl BODIPYs are not only useful fluorophores but also good photosensitizers to produce singlet oxygen.

Synthesis of figure-of-eight helical bisBODIPY macrocycles and their chiroptical properties.

A macrocyclic bisBODIPY (bis(boron-dipyrromethene)) complex [1B2] with a figure-of-eight helicity was synthesized and successfully resolved. [1B2] was proven to be one of the most efficient red-emitting CPL (circularly polarized luminescence) fluorophores reported to date (λ = 663 nm, |glum| = 9 × 10(-3), ΦF = 0.58).

Synthesis of a new family of ionophores based on aluminum-dipyrrin complexes (ALDIPYs) and their strong recognition of alkaline earth ions.

Mononuclear and dinuclear aluminum-dipyrrin complexes (ALDIPYs) were synthesized as a new family of ionophores. They exhibited colorimetric and fluorometric responses to alkaline earth ions in an aqueous mixed solvent. The strong recognition was achieved via multipoint interactions with the oxygen atoms appropriately incorporated into the ligand framework.