Browsing by Author "Wu, Chi-Shiun"

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Bidirectional polymorphic conversion by focused femtosecond laser irradiation
(2020-06-01)
Wu, Chi-Shiun
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Yoshikawa, Hiroshi Y.
;
Sugiyama, Teruki
;
交大名義發表
;
應用化學系
We present bidirectional polymorphic conversion of L-phenylalanine by focused femtosecond laser irradiation. When the femtosecond laser beam is focused at an air/solution interface of its unsaturated solution, the plate-like anhydrous crystals are generated from the laser focus. This crystal nucleation is realized by local concentration increase achieved by femtosecond laser trapping, which is the first demonstration of femtosecond laser trapping-induced crystallization. Furthermore, the whisker-like monohydrate crystals are produced by continuing the femtosecond laser irradiation on the surface of the plate-like crystals. On the contrary, when a focused femtosecond laser irradiation is applied to the whisker-like monohydrate crystals, the plate-like crystals are formed, meaning that an unstable phase is successfully produced from a stable phase. The dynamics and mechanism of the bidirectional polymorphic conversion are explained from the viewpoint of the nucleation rate theory considering solution concentration around the surface of laser-induced cavitation bubbles. (c) 2020 The Japan Society of Applied Physics
Growth Promotion of Targeted Crystal Face by Nanoprocessing via Laser Ablation
(2019-10-10)
Wu, Chi-Shiun
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Ikeyama, Jun
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Nakabayashi, Seiichiro
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Sugiyama, Teruki
;
Yoshikawa, Hiroshi Y.
Control of crystal shape is an indispensable step for various applications of crystalline products. However, obtaining the desired crystal shape by conventionally tuning environmental conditions (temperature, additives, etc.) cannot always be reached. Recently, we have developed an innovative approach for spatiotemporal control of crystal growth of proteins and amino acids by locally modifying crystal structure (e.g., formation of screw dislocations) via femtosecond (fs) laser ablation. In this work, to clarify the appropriate laser condition for controlling the shape of single crystals with minimized damage, we first systematically investigated the dependence of pulse duration on laser ablation and crystal growth of L-phenylalanine (L-Phe). By using a laser system with tunable pulse durations from fs to nanoseconds (ns), we found fs laser ablation can offer nanometer-sized, sharp etching of which diameter was smaller than the diffraction limit. By utilizing such nanoprocessing via fs laser ablation for promoting the growth of a targeted crystal face, we successfully demonstrated the preparation of a bulky crystal of L-Phe, which is difficult to be obtained by conventional crystallization methods.
Laser trapping-induced crystallization of L-phenylalanine through its high-concentration domain formation
(2014)
Yuyama, Ken-ichi
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Wu, Chi-Shiun
;
Sugiyama, Teruki
;
Masuhara, Hiroshi
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應用化學系
We present the laser trapping-induced crystallization of L-phenylalanine through high-concentration domain formation in H2O and D2O solutions which is achieved by focusing a continuous-wave (CW) near-infrared laser beam at the solution surface. Upon laser irradiation into the H2O solution, laser trapping of the liquid-like clusters increases the local concentration, accompanying laser heating, and a single plate-like crystal is eventually prepared at the focal spot. On the other hand, in the D2O solution, a lot of the monohydrate needle-like crystals are observed, not at the focal spot where the concentration is high enough to trigger crystal nucleation, but in the 0.5-1.5 mm range from the focal spot. The dynamics and mechanism of the amazing crystallization behaviour induced by laser trapping are discussed from the viewpoints of the concentration increase due to laser heating depending on solvent, the large high-concentration domain formation by laser trapping of liquid-like clusters, and the orientational disorder of molecules/clusters at the domain edge.
Pseudopolymorph Control of L-Phenylalanine Achieved by Laser Trapping
(2018-09-01)
Wu, Chi-Shiun
;
Hsieh, Pei-Yun
;
Yuyama, Ken-ichi
;
Masuhara, Hiroshi
;
Sugiyama, Teruki
We demonstrate pseudopolymorph control of L-phenylalanine (L-Phe) with laser trapping method by tuning laser power, polarization, and initial solution concentration. When a continuous-wave near-infrared laser beam of 1064 nm was focused at an air/solution interface of L-Phe D2O solutions with different saturation, L-Phe crystallization was always observed within 30 min-irradiation, even from unsaturated solution. Either whisker- or plate-like crystals were generated depending on given conditions, and identified by Raman spectroscopy to be two L-Phe pseudopolymorphs of monohydrate and anhydrous forms, respectively. The absolute control of L-Phe pseudopolymorphism was achieved by changing the initial solution concentration. In unsaturated solution, laser trapping always produced only one anhydrous crystal at the focus, which can never be produced on spontaneous nucleation at ordinary temperatures and pressures, while in supersaturated solution, a number of monohydrate crystals were densely distributed in an area ranging from 500 mu m to 1 mm away from the focus. Moreover, in saturated solution, laser power and polarization contributed to the pseudopolymorphism. As laser power was increased, linearly and circularly polarized laser irradiation increased the formation probability of the anhydrous and monohydrate crystals, respectively. The dynamics and mechanism of laser trapping-induced pseudopolymorphism of L-Phe are discussed in view of the formation of a highly concentrated domain consisting of the liquid-like clusters and the stability of the clusters in the domain under electromagnetic field of trapping laser.