Award Abstract # 1904091
Quantifying and manipulating chirality and amplification of nanomaterials in liquid crystals

NSF Org: DMR
Division Of Materials Research
Recipient: KENT STATE UNIVERSITY
Initial Amendment Date: August 6, 2019
Latest Amendment Date: August 6, 2019
Award Number: 1904091
Award Instrument: Standard Grant
Program Manager: Birgit Schwenzer
bschwenz@nsf.gov
 (703)292-4771
DMR
 Division Of Materials Research
MPS
 Directorate for Mathematical and Physical Sciences
Start Date: September 1, 2019
End Date: August 31, 2022 (Estimated)
Total Intended Award Amount: $319,840.00
Total Awarded Amount to Date: $319,840.00
Funds Obligated to Date: FY 2019 = $319,840.00
History of Investigator:
  • Torsten Hegmann (Principal Investigator)
    thegmann@kent.edu
Recipient Sponsored Research Office: Kent State University
1500 HORNING RD
KENT
OH  US  44242-0001
(330)672-2070
Sponsor Congressional District: 14
Primary Place of Performance: Kent State University
Kent
OH  US  44242-0001
Primary Place of Performance
Congressional District:
14
Unique Entity Identifier (UEI): KXNVA7JCC5K6
Parent UEI:
NSF Program(s): CONDENSED MATTER PHYSICS,
SOLID STATE & MATERIALS CHEMIS
Primary Program Source: 01001920DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 7237, 8614
Program Element Code(s): 171000, 176200
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.049

ABSTRACT

NON-TECHNICAL SUMMARY
Chirality, most simply described by the absence of mirror symmetry, can be found everywhere in nature and probably in the universe. Established as a term by Lord Kelvin in 1894, and significantly advanced by Pasteur and others, chirality has significant implications in Chemistry, Biology, Physics, Cosmology, and Materials Science alike. Described as "universal asymmetry" by Wagniere, the origin of homochirality of life is one of the most central scientific questions. Amplification of chirality underpins most theories proposed to describe nature's homochirality, i.e. the use of exclusively one enantiomer (one handedness) of sugars and amino acids to build all life forms, from simple to complex. This project, supported by the Solid State and Materials Chemistry program as well as the Condensed Matter Physics program at NSF, advances recent findings that chirality emanating from nanoscale particles capped with a monolayer of chiral molecules is uniquely able to generate more intense responses in liquid crystals than their organic molecular chiral counterparts. The liquid crystalline state, pervasive in nature just like chirality, here serves as a powerful test platform to establish size-property and shape-property relationships governing the amplification of chirality through space. This research at Kent State University generates data that advance the understanding of nanoscale chirality and paves the way for new applications of nanoscale materials as chirality sensors, tunable chiral metamaterials, and chiral catalysts. Students experience a multidisciplinary training environment, utilize state-of-the-art equipment, and become proficient in presenting their research to peers. The project serves as a platform for several outreach activities including training of high school students, hands-on lectures and lab research for community college students, and a scientific symposium.

TECHNICAL SUMMARY
Significant advances in the understanding and application of the unique features of nanomaterial chirality are only possible if one can detect, measure, visualize, tune, and transfer nanomaterial chirality through space and across length scales. To study this, the ubiquitous liquid crystalline state offers unrivaled opportunities for both fundamental theoretical and applied experimental research on nanomaterial chirality, by permitting the visualization as well as quantification of chirality amplification at different length scales. A range of imaging techniques such as polarized optical microscopy, fluorescence confocal microscopy, and transmission electron microcopy are used to study these systems. Guided by first principle theoretical calculations of a pseudoscalar chirality index, this experimental work also establishes how chirality amplification at the nanoscale depends on the nanomaterial type, size, shape, and aspect ratio. The team synthesizes, characterizes, and studies chiral ligand-capped metal nanorods, nanodiscs, nanostars, nanotriangles, and nanocages decorated with chiral ligand shells in nematic liquid crystals, and compares experimental data of the helical twisting power to theoretical values of the calculated chirality index. To test how chirality amplification can be applied, chiral nematic microlens arrays similar to arthropod or compound eyes are created, and the use of magnetic fields in combination with anisometric chiral molecule-capped magnetic nanoparticles dispersed in nematic liquid crystal phases examined. The latter seeks to understand how competing elastic and magnetic forces of liquid crystal host and dispersed magnetic nanoparticles, respectively, can be translated into motion.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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(Showing: 1 - 10 of 12)
Gonçalves, Diana P. and Prévôt, Marianne E. and Üstünel, enay and Ogolla, Timothy and Nemati, Ahlam and Shadpour, Sasan and Hegmann, Torsten "Recent progress at the interface between nanomaterial chirality and liquid crystals" Liquid Crystals Reviews , v.9 , 2021 https://doi.org/10.1080/21680396.2021.1930596 Citation Details
Gonçalves, Diana P. N. and Hegmann, Torsten "Chirality Transfer from an Innately Chiral Nanocrystal Core to a Nematic Liquid Crystal: SurfaceModified Cellulose Nanocrystals" Angewandte Chemie International Edition , v.60 , 2021 https://doi.org/10.1002/anie.202105357 Citation Details
Gonçalves, Diana P. N. and Ogolla, Timothy and Hegmann, Torsten "Chirality Transfer from an Innately Chiral Nanocrystal Core to a Nematic Liquid Crystal 2: Lyotropic Chromonic Liquid Crystals" ChemPhysChem , v.24 , 2022 https://doi.org/10.1002/cphc.202200685 Citation Details
Liu, Jiao and Molard, Yann and Prévôt, Marianne E. and Hegmann, Torsten "Highly Tunable Circularly Polarized Emission of an Aggregation-Induced Emission Dye Using Helical Nano- and Microfilaments as Supramolecular Chiral Templates" ACS Applied Materials & Interfaces , v.14 , 2022 https://doi.org/10.1021/acsami.2c05012 Citation Details
Liu, Jiao and Shadpour, Sasan and Nemati, Ahlam and Prévôt, Marianne E. and Hegmann, Elda and Zhu, Chenhui and Hegmann, Torsten "Binary mixtures of bent-core molecules forming distinct types of B4 phase nano- and microfilament morphologies" Liquid Crystals , 2021 https://doi.org/10.1080/02678292.2020.1847333 Citation Details
Liu, Jiao and Shadpour, Sasan and Prévôt, Marianne E. and Chirgwin, Michael and Nemati, Ahlam and Hegmann, Elda and Lemieux, Robert P. and Hegmann, Torsten "Molecular Conformation of Bent-Core Molecules Affected by Chiral Side Chains Dictates Polymorphism and Chirality in Organic Nano- and Microfilaments" ACS Nano , v.15 , 2021 https://doi.org/10.1021/acsnano.1c00527 Citation Details
Nemati, Ahlam and Shadpour, Sasan and Querciagrossa, Lara and Mori, Taizo and Zannoni, Claudio and Hegmann, Torsten "Highly Sensitive, Tunable Chirality Amplification through Space Visualized for Gold Nanorods Capped with Axially Chiral Binaphthyl Derivatives" ACS Nano , v.13 , 2019 10.1021/acsnano.9b03787 Citation Details
Perera, Kelum and Nemati, Ahlam and Mann, Elizabeth K. and Hegmann, Torsten and Jákli, Antal "Converging Microlens Array Using Nematic Liquid Crystals Doped with Chiral Nanoparticles" ACS Applied Materials & Interfaces , v.13 , 2021 https://doi.org/10.1021/acsami.0c21044 Citation Details
Perera, Kelum and Nemati, Alham and Mann, Elizabeth and Hegmann, Torsten and Jákli, Antal I. "Optical properties of nematic microlenses doped with chiral nanoparticles" SPIE Organic Photonics + Electronics, 2020 , 2020 https://doi.org/10.1117/12.2568570 Citation Details
Perera, Kelum and Padmini, Haputhanhtrige Nilanthi and Mann, Elizabeth and Jákli, Antal "Polymer Stabilized Paraboloid Liquid Crystal Microlenses with Integrated PancharatnamBerry Phase" Advanced Optical Materials , v.10 , 2021 https://doi.org/10.1002/adom.202101510 Citation Details
Poryvai, Anna and mahel, Michal and vecová, Marie and Nemati, Ahlam and Shadpour, Sasan and Ulbrich, Pavel and Ogolla, Timothy and Liu, Jiao and Novotná, Vladimíra and Veverka, Miroslav and Vejpravová, Jana and Hegmann, Torsten and Kohout, Michal "Chiral, Magnetic, and Photosensitive Liquid Crystalline Nanocomposites Based on Multifunctional Nanoparticles and Achiral Liquid Crystals" ACS Nano , v.16 , 2022 https://doi.org/10.1021/acsnano.1c10594 Citation Details
(Showing: 1 - 10 of 12)

PROJECT OUTCOMES REPORT

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

Intellectual merit of this project is in the collective experimental data that support the notion that size, shape, and AR of chiral ligand-capped nanoshapes affect the efficacy of chirality transfer to a surrounding reporter medium, here a nematic liquid crystal phase, in very predictable ways via independent calculations of a two-dimensional (2-D) shape compatibility corrected chirality indicators. Almost each of the gold nanoshapes capped with a chiral ligand shell outperforms the neat organic chiral molecules with respect to their ability to transfer chirality to the N-LC host medium. We established a very systematic correlation between purely geometric concepts and experimental chirality transfer data. This methodology provides a broadly expandable tool to a priori predict experimental chirality transfer efficacy data, which was here realized by measuring the induced helical pitch and calculating the helical twisting power in an induced chiral nematic liquid crystal medium for essentially any possible nanoshape varying in size, shape, or aspect ration; all without much need to alter the chemical nature of the chiral molecules decorating the nanoshape surface.

To further elucidate the role of core chirality, we studied cellulose nanocrystals (CNCs), and experiments using both neat CNCs and CNCs-functionalized with chiral or achiral pro-mesogenic molecules revealed that the contribution to chirality transfer from a molecular and morphologically chiral core is likely considerable. Thus, a dense network of chiral molecules on the surface of the gold nanoshapes appears to be the key driving force for their unusually high ability to transfer chirality to a surrounding achiral nematic liquid crystal medium, fundamentally affected by shape congruency. Yet, any further enhancement of the chirality transfer efficacy can likely be accomplished by introducing nanoshapes featuring both a chiral core and shape matching to the nematic liquid crystal host molecules. We foresee that the utility of the mathematical and computational concepts may soon be significantly advanced by machine learning and artificial intelligence (AI) strategies, and as such support familiar ?you cannot put a square peg in a round hole? metaphors for molecular and nanoscale chirality transfer systems. Ultimately, a further expansion of these concepts to lyotropic LC systems that are biologically significantly more relevant as well as to applications seems was all but inevitable and now show that these chirality transfer efficacy mechanism are more universal.

In broader impact, we have also demonstrated that chiral nanomatereials as well as other chiral organic additives can be used to generate microlenses, that such microlenses can be used to measure the helical twisting power of nanograms of chiral solutes in a nematic liquid crystal, and that organic chiral templates based on the B4 phase can be used to generate circularly polarized emission with high efficiency. Finally, the combination of structural color exhibited by all the B4 templates with the aggregation-induced emission inherent to the dye used was demonstrated as a potential avenue for applications as temperature-rate detection sensors or anti-counterfeiting tags.

 


Last Modified: 11/09/2022
Modified by: Torsten Hegmann

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