In this study, we conducted successful experiments on ethylenediamine sulfate (EDS), an organic compound, to investigate its enantioselectivity in chiral crystallization. We employed optical trapping with circularly polarized laser beams, using a continuous wave laser at 1064 nm. By focusing the laser at the air–solution interface of a heavy water-saturated EDS solution, the formation of sub-micrometer-sized chiral EDS crystals was verified. Two generated enantiomorphs (d-crystal and l-crystal) were identified by the rotating analyzer method. The enantioselectivity in the chiral crystallization of EDS was assessed through 30 to 60 times experiments conducted under various conditions of laser powers and polarization modes, utilizing the count of generated crystals for each enantiomorph in the evaluation. Circularly polarized lasers at a specific power created an imbalance in the generation probability of the enantiomorphs, resulting in crystal enantiomeric excess values of 23% and −30%. The enantioselectivity mechanism was explored from two perspectives: refractive index differences of two enantiomorphs and 3D helical optical forces. Study of the thermodynamic mechanism was insufficient to explain the outcomes. Conversely, the 3D helical optical force mechanism revealed that the forces acting on EDS clusters in solution induced helical fluid motion, driving EDS nucleation, with the helicity of fluid motion determining the crystal’s chirality. This approach will present new insights into chirality in industrial and research fields, with potential applications in regard to improving optical resolution and addressing the origin of homochirality.
REFERENCES
1.
A.
Favre-Bulle
, A. B.
Stilgoe
, E. K.
Scott
, and H.
Rubinsztein-Dunlop
, “Optical trapping in vivo: Theory, practice, and applications
,” Nanophotonics
8
, 1023
–1040
(2019
).2.
C. J.
Bustamante
, Y. R.
Chemla
, S.
Liu
, and M. D.
Wang
, “Optical tweezers in single-molecule biophysics
,” Nat. Rev. Methods Primers
1
, 25
(2021
).3.
H.
Masuhara
and K.
Yuyama
, “Optical force-induced chemistry at solution surfaces
,” Annu. Rev. Phys. Chem.
72
, 565
–589
(2021
).4.
A.
Kritzinger
, A.
Forbes
, and P. B. C.
Forbes
, “Optical trapping and fluorescence control with vectorial structured light
,” Sci. Rep.
12
, 17690
(2022
).5.
H. M.
Rivy
, S. A.
Aljunid
, E.
Lassalle
, N. I.
Zheludev
, and D.
Wilkowski
, “Single atom in a superoscillatory optical trap
,” Commun. Phys.
6
, 155
(2023
).6.
A.
Ashkin
, “Acceleration and trapping of particles by radiation pressure
,” Phys. Rev. Lett.
24
, 156
–159
(1970
).7.
A.
Ashkin
, J. M.
Dziedzic
, J. E.
Bjorkholm
, and S.
Chu
, “Observation of a single-beam gradient force optical trap for dielectric particles
,” Opt. Lett.
11
, 288
–290
(1986
).8.
T.
Sugiyama
, T.
Adachi
, and H.
Masuhara
, “Crystallization of glycine by photon pressure of a focused CW laser beam
,” Chem. Lett.
36
, 1480
–1481
(2007
).9.
T.
Sugiyama
, K. I.
Yuyama
, and H.
Masuhara
, “Laser trapping chemistry: From polymer assembly to amino acid crystallization
,” Acc. Chem. Res.
45
, 1946
–1954
(2012
).10.
J.-R.
Tu
, A.
Miura
, K. I.
Yuyama
, H.
Masuhara
, and T.
Sugiyama
, “Crystal growth of lysozyme controlled by laser trapping
,” Cryst. Growth Des.
14
, 15
–22
(2014
).11.
Y.
Tsuboi
, T.
Shoji
, and N.
Kitamura
, “Optical trapping of amino acids in aqueous solutions
,” J. Phys. Chem. C
114
, 5589
–5593
(2010
).12.
A.-C.
Cheng
, H.
Masuhara
, and T.
Sugiyama
, “Evolving crystal morphology of potassium chloride controlled by optical trapping
,” J. Phys. Chem. C
124
, 6913
–6921
(2020
).13.
K. I.
Yuyama
, D.-S.
Chiu
, Y.-E.
Liu
, T.
Sugiyama
, and H.
Masuhara
, “Crystal growth and dissolution dynamics of L-phenylalanine controlled by solution surface laser trapping
,” Cryst. Growth Des.
18
, 7079
–7087
(2018
).14.
T.
Rungsimanon
, K. I.
Yuyama
, T.
Sugiyama
, H.
Masuhara
, N.
Tohnai
, and M.
Miyata
, “Control of crystal polymorph of glycine by photon pressure of a focused continuous wave near-infrared laser beam
,” J. Phys. Chem. Lett.
1
, 599
–603
(2010
).15.
J.
Cruz-Cabeza
, N.
Feeder
, and R. J.
Davey
, “Open questions in organic crystal polymorphism
,” Commun. Chem.
3
, 142
(2020
).16.
Q.
Shi
, H.
Chen
, Y.
Wang
, J.
Xu
, Z.
Liu
, and C.
Zhang
, “Recent advances in drug polymorphs: Aspects of pharmaceutical properties and selective crystallization
,” Int. J. Pharm.
611
, 121320
(2022
).17.
R.
Censi
and P.
DiMartino
, “Polymorph impact on the bioavailability and stability of poorly soluble drugs
,” Molecules
20
, 18759
–18776
(2015
).18.
J. T.
Sertório
, R.
Lacchini
, L. M.
Amaral
, A. C. T.
Palei
, R. C.
Cavalli
, V. C.
Sandrim
, G.
Duarte
, and J. E.
Tanus-Santos
, “Haptoglobin polymorphism affects nitric oxide bioavailability in preeclampsia
,” J. Hum. Hypertens.
27
, 349
–354
(2013
).19.
J.
Ceramella
, D.
Iacopetta
, A.
Franchini
, M.
De Luca
, C.
Saturnino
, I.
Andreu
, M. S.
Sinicropi
, and A.
Catalano
, “A look at the importance of chirality in drug activity: Some significative examples
,” Appl. Sci.
12
, 10909
(2022
).20.
P.
Silvestri
and P. J. J.
Colbon
, “The growing importance of chirality in 3D chemical space exploration and modern drug discovery approaches for hit-ID
,” ACS Med. Chem. Lett.
12
, 1220
–1229
(2021
).21.
W. H.
Brooks
, W. C.
Guida
, and K. G.
Daniel
, “The significance of chirality in drug design and development
,” Curr. Top. Med. Chem.
11
, 760
–770
(2011
).22.
D. M.
Whitacre
, Reviews of Environmental Contamination and Toxicology
(Springer
, 2012
), Vol. 217
.23.
Y.
Liu
, J.
Xiao
, J.
Koo
, and B.
Yan
, “Chirality-driven topological electronic structure of DNA-like materials
,” Nat. Mater.
20
, 638
–644
(2021
).24.
H.
Kuang
, C.
Xu
, and Z.
Tang
, “Emerging chiral materials
,” Adv. Mater.
32
, 2005110
(2020
).25.
P. H.
Chuong
, L. A.
Nguyen
, and H.
He
, “Chiral drugs: An overview
,” Int. J. Biomed. Sci.
2
, 85
–100
(2006
).26.
I.
Putman
and D. W.
Armstrong
, “Recent advances in the field of chiral crystallization
,” Chirality
34
, 1338
–1354
(2022
).27.
T.
Matsuura
and H.
Koshima
, “Introduction to chiral crystallization of achiral organic compounds: Spontaneous generation of chirality
,” J. Photochem. Photobiol., C
6
, 7
–24
(2005
).28.
A. K.
Scott
, “Stereoisomers and drug toxicity
,” Drug Saf.
8
, 149
–159
(1993
).29.
E.
Dorey
, “Chiral drugs viable, despite failure
,” Nat. Biotechnol.
18
, 1239
–1240
(2000
).30.
W.
Jung
, J.
Kwon
, W.
Cho
, and J.
Yeom
, “Chiral biomaterials for nanomedicines: From molecules to supraparticles
,” Pharmaceutics
14
, 1951
(2022
).31.
K.
Toyoda
, H.-T.
Su
, K.
Miyamoto
, T.
Sugiyama
, and T.
Omatsu
, “Chiral crystallization manipulated by orbital angular momentum of light
,” Optica
10
, 332
(2023
).32.
A.-C.
Cheng
, H.
Niinomi
, T.
Omatsu
, S.
Ishida
, K.
Sasaki
, and T.
Sugiyama
, “Plasmonic manipulation-controlled chiral crystallization of sodium chlorate
,” J. Phys. Chem. Lett.
11
, 4422
–4426
(2020
).33.
H.
Niinomi
, T.
Sugiyama
, M.
Tagawa
, K.
Murayama
, S.
Harada
, and T.
Ujihara
, “Enantioselective amplification on circularly polarized laser-induced chiral nucleation from a NaClO3 solution containing Ag nanoparticles
,” CrystEngComm
18
, 7441
–7448
(2016
).34.
R.
Ward
, G. W.
Copeland
, and A. J.
Alexander
, “Chiral hide-and-seek: Retention of enantiomorphism in laser-induced nucleation of molten sodium chlorate
,” J. Chem. Phys.
135
, 114508
(2011
).35.
E. R.
Barber
, N. L. H.
Kinney
, and A. J.
Alexander
, “Pulsed laser-induced nucleation of sodium chlorate at high energy densities
,” Cryst. Growth Des.
19
, 7106
–7111
(2019
).36.
G. H.
Wagnière
, On Chirality and the Universal Asymmetry: Reflections on Image and Mirror
(Wiley VCH
, Weinheim
, 2007
).37.
A.
Guijarro
and M.
Yus
, The Origin of Chirality in the Molecules of Life
(RSC Publishing
, Cambridge
, 2009
).38.
M.
Briard
, C.
Brandel
, and V.
Dupray
, “Strong enhancement of nucleation efficiency of aqueous ethylenediamine sulfate solutions by nonphotochemical laser-induced nucleation: Investigations on the role of solid impurities in the mechanism
,” Cryst. Growth Des.
23
, 7169
–7178
(2023
).39.
L. A.
Cuccia
, L.
Koby
, J. B.
Ningappa
, and M.
Dakessian
, “Chiral crystallization of ethylenediamine sulfate
,” J. Chem. Educ.
82
, 1043
(2005
).40.
A.
Matsumoto
, T.
Ide
, Y.
Kaimori
, S.
Fujiwara
, and K.
Soai
, “Asymmetric autocatalysis triggered by chiral crystal of achiral ethylenediamine sulfate
,” Chem. Lett.
44
, 688
–690
(2015
).41.
T. P. T.
Nguyen
, P. S. M.
Cheung
, L.
Werber
, J.
Gagnon
, R.
Sivakumar
, C.
Lennox
, A.
Sossin
, Y.
Mastai
, and L. A.
Cuccia
, “Directing the Viedma ripening of ethylenediammonium sulfate using "Tailor-made" chiral additives
,” Chem. Commun.
52
, 12626
–12629
(2016
).42.
K.
Jayaraman
, A.
Choudhury
, and C. N. R.
Rao
, “Sulfates of organic diamines: Hydrogen-bonded structures and properties
,” Solid State Sci.
4
, 413
–422
(2002
).43.
K.
Sakurai
, “A direct determination of the crystal structure of ethylenediammonium sulphate
,” J. Phys. Soc. Jpn.
16
, 1205
–1213
(1961
).44.
K.
Setoura
, K.
Fujita
, S.
Ito
, and H.
Miyasaka
, “Temperature elevation and fluid convection under optical trapping condition as revealed by fluorescence correlation spectroscopy
,” J. Nanophotonics
13
, 012504
(2018
).45.
S.
Ito
, T.
Sugiyama
, N.
Toitani
, G.
Katayama
, and H.
Miyasaka
, “Application of fluorescence correlation spectroscopy to the measurement of local temperature in solutions under optical trapping condition
,” J. Phys. Chem. B
111
, 2365
–2371
(2007
).46.
S.
Albaladejo
, M. I.
Marqués
, M.
Laroche
, and J. J.
Sáenz
, “Scattering forces from the curl of the spin angular momentum of a light field
,” Phys. Rev. Lett.
102
, 113602
(2009
).47.
A. J.
Alexander
and P. J.
Camp
, “Non-photochemical laser-induced nucleation
,” J. Chem. Phys.
150
, 040901
(2019
).48.
T.
Sugiyama
and S.-F.
Wang
, “Manipulation of nucleation and polymorphism by laser irradiation
,” J. Photochem. Photobiol., C
52
, 100530
(2022
).49.
R.
Ward
and A. J.
Alexander
, “Nonphotochemical laser-induced nucleation of potassium halides: Effects of wavelength and temperature
,” Cryst. Growth Des.
12
, 4554
–4561
(2012
).50.
L. F.
Alexander
and N.
Radacsi
, “Application of electric fields for controlling crystallization
,” CrystEngComm
21
, 5014
–5031
(2019
).51.
H.
Niinomi
, T.
Sugiyama
, A.-C.
Cheng
, M.
Tagawa
, T.
Ujihara
, H. Y.
Yoshikawa
, R.
Kawamura
, J.
Nozawa
, J. T.
Okada
, and S.
Uda
, “Chiral optical force generated by a superchiral near-field of a plasmonic triangle trimer as origin of giant bias in chiral nucleation: A simulation study
,” J. Phys. Chem. C
125
, 6209
–6221
(2021
).52.
H.
Eyring
, H.-C.
Liu
, and D.
Caldwell
, “Optical rotatory dispersion and circular dichroism
,” Chem. Rev.
68
, 525
–540
(1968
).53.
S.-F.
Wang
and T.
Sugiyama
, “Femtosecond laser-driven enantioselectivity on achiral–chiral polymorphic transition
,” Cell Rep. Phys. Sci.
4
, 101323
(2023
).54.
M.
Sakamoto
, N.
Uemura
, R.
Saito
, H.
Shimobayashi
, Y.
Yoshida
, T.
Mino
, and T.
Omatsu
, “Chirogenesis and amplification of molecular chirality using optical vortices
,” Angew. Chem., Int. Ed.
60
, 12819
–12823
(2021
).55.
L.
Allen
, M. W.
Beijersbergen
, R. J. C.
Spreeuw
, and J. P.
Woerdman
, “Orbital angular momentum of light and the transformation of Laguerre–Gaussian laser modes
,” Phys. Rev. A
45
, 8185
–8189
(1992
).56.
K. Y.
Bliokh
, E. A.
Ostrovskaya
, M. A.
Alonso
, O. G.
Rodríguez-Herrera
, D.
Lara
, and C.
Dainty
, “Spin-to-orbital angular momentum conversion in focusing, scattering, and imaging systems
,” Opt. Express
19
, 26132
–26149
(2011
).57.
K. Y.
Bliokh
, F. J.
Rodríguez-Fortuño
, F.
Nori
, and A. V.
Zayats
, “Spin–orbit interactions of light
,” Nat. Photonics
9
, 796
–808
(2015
).58.
M.
Kuroha
, S.
Nambu
, S.
Hattori
, Y.
Kitagawa
, K.
Niimura
, Y.
Mizuno
, F.
Hamba
, and K.
Ishii
, “Chiral supramolecular nanoarchitectures from macroscopic mechanical rotations: Effects on enantioselective aggregation behavior of phthalocyanines
,” Angew. Chem., Int. Ed.
58
, 18454
–18459
(2019
).59.
J. M.
Ribó
, J.
Crusats
, F.
Sagués
, J.
Claret
, and R.
Rubires
, “Chiral sign induction by vortices during the formation of mesophases in stirred solutions
,” Science
292
, 2063
–2066
(2001
).60.
O.
Ohno
, Y.
Kaizu
, and H.
Kobayashi
, “J‐aggregate formation of a water‐soluble porphyrin in acidic aqueous media
,” J. Chem. Phys.
99
, 4128
–4139
(1993
).© 2024 Author(s). Published under an exclusive license by AIP Publishing.
2024
Author(s)
You do not currently have access to this content.
