Watanabe Satoshi, Inouchi Shun, Kunitake Masashi
Division of Applied Chemistry and Biochemistry, National Institute of Technology, Tomakomai College Nishikioka 443 Tomakomai Hokkaido 059-1275 Japan
Graduate School of Science and Technology, Kumamoto University 2-39-1 Kurokami, Chuo-ku Kumamoto City Kumamoto 860-8555 Japan.
RSC Adv. 2025 Mar 18;15(11):8404-8410. doi: 10.1039/d5ra00170f. eCollection 2025 Mar 17.
Crystal engineering methodologies based on reproducible and high-throughput fabrication of high-quality single crystals have attracted much attention. Crystal formation and growth are governed by crystal growth theory. The driving force of crystallization is systematically represented with phase diagrams. However, constructing phase diagrams usually requires relatively large quantities of samples (milligrams to grams) and substantial time (weeks to months) to evaluate many conditions. Therefore, an easy and quick methodology to obtain phase diagrams, revealing critical conditions for valuable samples, is required. Here, we proposed a new method to obtain phase diagrams based on nanoliter droplet arrays of nonvolatile ionic liquids prepared by inkjet printing. Anthracene derivatives and 1-octyl-4-methylpyridinium derivatives were used as the solute and solvent, respectively. Optimization of ejection conditions, such as applied voltage, frequency, pulse width, and head temperature, enabled the formation of a 0.5 nL droplet per ejection. Inkjet printing under these conditions formed nanodroplet arrays on substrates at a droplet-patterned density of 50 dots per cm. The volume of each patterned droplet was varied from 10 to 100 nL by changing the number of ejections. The dissolution temperature of anthracene at each concentration was obtained at a heating rate of 0.2 °C min. This heating rate was found to be 10 times faster than the conventional technique. The same phase diagram as that prepared by the conventional technique was obtained in the range of 75-300 mM. The standard deviation of the dissolution temperatures was 0.8 °C (2.5%). This technique will facilitate the crystallization of multiple and valuable samples.
基于高质量单晶的可重复和高通量制备的晶体工程方法已引起广泛关注。晶体的形成和生长受晶体生长理论支配。结晶的驱动力通过相图系统地表示。然而，构建相图通常需要相对大量的样品（毫克到克）和大量时间（数周数月）来评估多种条件。因此，需要一种简便快速的方法来获得相图，揭示有价值样品的关键条件。在此，我们提出了一种基于喷墨打印制备的非挥发性离子液体纳升级液滴阵列来获得相图的新方法。分别使用蒽衍生物和1-辛基-4-甲基吡啶鎓衍生物作为溶质和溶剂。对诸如施加电压、频率、脉冲宽度和喷头温度等喷射条件进行优化，使得每次喷射能够形成0.5 nL的液滴。在这些条件下进行喷墨打印，以每厘米50个点的液滴图案密度在基板上形成纳米液滴阵列。通过改变喷射次数，每个图案化液滴的体积在10至100 nL之间变化。以0.2℃/分钟的加热速率获得各浓度下蒽的溶解温度。发现该加热速率比传统技术快10倍。在75 - 300 mM范围内获得了与传统技术制备的相同相图。溶解温度的标准偏差为0.8℃（2.5%）。该技术将促进多种有价值样品的结晶。
