Releasing a bound molecular spring with light: a visible light-triggered photosalient effect tied to polymorphism.

Here we present a study on the solid state properties of trans tetra-ortho-bromo azobenzene (4Br-Azo). Two distinct crystal polymorphs were identified: the α-phase and ß-phase. Notably, only the ß-phase exhibited an extraordinary photosalient effect (jumping/breaking) upon exposure to a wide range of visible light. Powder X-ray diffraction and Raman spectroscopy revealed that the ß-phase is metastable and can transition to the α-phase when subjected to specific stimuli like heat and light. Furthermore, single crystal X-ray diffraction and density functional theory calculations highlighted the significance of a highly strained conformer in the ß-phase, showing that the metastability of the phase potentially arises from relieving this strain. This metastability leads to a light induced phase transition, which appears to be the cause of the photosalient effect in these crystals. Interestingly the polymorphism at the core of 4Br-Azo's dynamic behavior is based on different arrangements of halogen based intermolecular interactions. It is possible that continued study on combining visible light capturing chromophores with halogen interaction-based polymorphism will lead to the discovery of even more visible light controlled dynamic crystal materials.

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.

Size-controlled synthesis of cyclodextrin-capped gold nanoparticles for molecular recognition using surface-enhanced Raman scattering.

Cyclodextrin (CD)-capped gold nanoparticles (AuNPs) can be applied in sensing, catalysis, and self-assembly processes due to their molecular recognition ability. As the plasmon resonance of AuNPs depends on their size, the size-controlled synthesis of CD-capped AuNPs is essential for the development of these applications. Herein, we successfully synthesized ß-CD-capped AuNPs with diameters of 24-85 nm using a seed-mediated growth method. The AuNPs were prepared using a ß-CD as both the reducing agent and the capping agent. Harsh reagents such as NaBH4 and NaOH were not used. The size-controlled synthesis of ß-CD-capped AuNPs was achieved by changing the amount of seed solution. We fabricated monolayers of ß-CD-capped AuNPs by liquid-liquid interfacial self-assembly for application in surface-enhanced Raman scattering (SERS). The SERS intensity is significantly improved by using larger ß-CD-capped AuNPs. In addition, we found that ß-CDs can detect pyrene with higher sensitivity than α-CDs on the basis of the difference in molecular recognition ability between α-CDs and ß-CDs.

Facile fabrication of self-assembled nanostructures of vertically aligned gold nanorods by using inkjet printing.

We demonstrated that the vertically aligned gold nanorods (AuNRs) were quickly and easily formed by using inkjet printing when aqueous dispersion of AuNRs containing a small amount of ethylene glycol (EG) was employed as an ink. It was observed that the content of EG in water suppressed rapid drying and convection in the droplets, which is favorable for the formation of the nanostructures.