TY - JOUR
T1 - Microfluidic Laser-Induced Nucleation of Supersaturated Aqueous Glycine Solutions
AU - Hua, Tianyi
AU - Valentín-Valentín, Celymar
AU - Gowayed, Omar
AU - Lee, Seongha
AU - Garetz, Bruce A.
AU - Hartman, Ryan L.
N1 - Funding Information:
This work was supported in part by the MRSEC Program of the National Science Foundation under Award Number DMR-1420073.
Funding Information:
This material is based upon work supported by the Materials Research Science and Engineering Center (MRSEC) program of the National Science Foundation under Award Number DMR-1420073.
Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/10/7
Y1 - 2020/10/7
N2 - Nonphotochemical laser-induced nucleation (NPLIN) of supersaturated aqueous glycine solutions was studied at a wavelength of 1064 nm using a microfluidic device. Crystal shape, size, and number were characterized in situ in real time on the chip. The influence of the laser pulse intensity on the nucleation kinetics was reported. Aging of the supersaturated solutions was necessary to observe NPLIN; fresh solutions did not nucleate. Crystal structure was found to switch from the α- to the γ-polymorph as the supersaturation increased. The observed number of crystals formed exhibited a threshold intensity but was otherwise proportional to the laser intensity, consistent with the dielectric polarization model, although the "lability"calculated from classical nucleation theory was too large by many orders of magnitude. Dynamic light scattering data revealed nanodroplets, hundreds of nanometers in diameter, formed in aged supersaturated aqueous glycine solutions; these submicron sized nanodroplets were apparently necessary for NPLIN. A new model combining the dielectric polarization model and two-step nucleation theory via submicron nanodroplets was proposed to explain these observations, providing a reasonable match between experiment and theory.
AB - Nonphotochemical laser-induced nucleation (NPLIN) of supersaturated aqueous glycine solutions was studied at a wavelength of 1064 nm using a microfluidic device. Crystal shape, size, and number were characterized in situ in real time on the chip. The influence of the laser pulse intensity on the nucleation kinetics was reported. Aging of the supersaturated solutions was necessary to observe NPLIN; fresh solutions did not nucleate. Crystal structure was found to switch from the α- to the γ-polymorph as the supersaturation increased. The observed number of crystals formed exhibited a threshold intensity but was otherwise proportional to the laser intensity, consistent with the dielectric polarization model, although the "lability"calculated from classical nucleation theory was too large by many orders of magnitude. Dynamic light scattering data revealed nanodroplets, hundreds of nanometers in diameter, formed in aged supersaturated aqueous glycine solutions; these submicron sized nanodroplets were apparently necessary for NPLIN. A new model combining the dielectric polarization model and two-step nucleation theory via submicron nanodroplets was proposed to explain these observations, providing a reasonable match between experiment and theory.
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U2 - 10.1021/acs.cgd.0c00669
DO - 10.1021/acs.cgd.0c00669
M3 - Article
AN - SCOPUS:85095130418
SN - 1528-7483
VL - 20
SP - 6502
EP - 6509
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 10
ER -