Motion is an essential process for many living organisms and for artificial robots and machines. To date, creating self-propelled motion in nano-to-macroscopic-sized objects has been a challenging issue for scientists. Herein, we report the directional and continuous motion of crystals on a glass surface when irradiated simultaneously with two different wavelengths, using simple azobenzenes as a photoresponsive organic compound. The direction of the motion can be controlled by the position of the light sources, and the crystals can even climb vertical surfaces. The motion is driven by crystallization and melting at the front and rear edges of the crystal, respectively, via photochemical conversion between the crystal and liquid phases induced by the trans–cis isomerization of azobenzenes. This finding could lead to remote-controlled micrometre-sized vehicles and valves on solid substrates.
The direct and reversible transformation of matter between the solid and liquid phases by light at constant temperature is of great interest because of its potential applications in various manufacturing settings. We report a simple molecular design strategy for the phase transitions: azobenzenes having para-dialkoxy groups with a methyl group at the meta-position. The photolithography processes were demonstrated using the azobenzene as a photoresist in a single process combining development and etching of a copper substrate.
Trans-cis photoisomerization in an azo compound containing azobenzene chromophores and long alkyl chains leads to a photoinduced crystal-melt transition (PCMT). X-ray structure analysis of this crystal clarifies the characteristic coexistence of the structurally ordered chromophores through their π···π interactions and disordered alkyl chains around room temperature. These structural features reveal that the PCMT starts near the surface of the crystal and propagates into the depth, sacrificing the π···π interactions. A temporal change of the powder X-ray diffraction pattern under light irradiation and a two-component phase diagram allow qualitative analysis of the PCMT and the following reconstructive crystallization of the cis isomer as a function of product accumulation. This is the first structural characterization of a compound showing the PCMT, overcoming the low periodicity that makes X-ray crystal structure analysis difficult.
Chemical analysis of biotite in representative granitic rocks in Japan shows that the total Al (TAl) content changes with the metal type of the accompanying hydrothermal ore deposits and increases in the following order: Pb‐Zn and Mo deposits < Cu‐Fe and Sn deposits < W deposits < non‐mineralized granitic rocks. The TAl content of biotite in granitic rocks may be a useful indicator for distinguishing between mineralized and non‐mineralized granitic rocks. A good positive correlation is seen between the TAl content of biotite and the solidification pressure of the granitic rocks estimated by sphalerite and hornblende geobarometers and the mineral assemblages of the surrounding rocks. These facts suggest that the TAl content of biotite can be used to estimate the solidification pressure (P) of the granitic rocks. The following empirical equation was obtained:
where TAl designates the total Al content in biotite on the basis O = 22. According to the obtained biotite geobarometer, it is estimated that Pb‐Zn and Mo deposits were formed at pressures below 1 kb, Cu‐Fe and Sn deposits at 1–2 kb, W deposits at 2–3 kb and non‐mineralized granitic rocks were solidified at pressures above 3 kb.
The photocontrol of the macroscopic alignment of nanostructured 2D ion-transporting pathways is described. The uniplanar homogeneous alignment of the thermotropic smectic (Sm) liquid-crystalline (LC) phase has been successfully achieved via photoinduced reorientation of the azobenzene groups of the imidazolium-based LC material. The ionic layers of the Sm LC phase are macroscopically oriented perpendicular to the surface of the glass substrate. The oriented films show anisotropic ion conduction in the Sm phase. This is the first example of the macroscopic photoalignment of ion-conductive LC arrays. Reversible switching of homeotropic and homogeneous alignments has also been achieved for the LC material. These materials and the alignment methodology may be useful in the development of ion-based circuits and memory devices.
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