Ion-Induced Formation of Nanocrystalline Cellulose Colloidal Glasses Containing Nematic DomainsClick to copy article linkArticle link copied!
- Pascal Bertsch*Pascal Bertsch*E-mail: [email protected]. Phone: +41 44 632 67 62 (P.B.).Institute of Food Nutrition and Health, ETH Zurich, 8092 Zurich, SwitzerlandMore by Pascal Bertsch
- Antoni Sánchez-FerrerAntoni Sánchez-FerrerInstitute of Food Nutrition and Health, ETH Zurich, 8092 Zurich, SwitzerlandMore by Antoni Sánchez-Ferrer
- Massimo BagnaniMassimo BagnaniInstitute of Food Nutrition and Health, ETH Zurich, 8092 Zurich, SwitzerlandMore by Massimo Bagnani
- Stéphane IsabettiniStéphane IsabettiniInstitute of Food Nutrition and Health, ETH Zurich, 8092 Zurich, SwitzerlandMore by Stéphane Isabettini
- Joachim KohlbrecherJoachim KohlbrecherLaboratory for Neutron Scattering and Imaging, Paul Scherrer Institute, PSI, 5232 Villigen PSI, SwitzerlandMore by Joachim Kohlbrecher
- Raffaele MezzengaRaffaele MezzengaInstitute of Food Nutrition and Health, ETH Zurich, 8092 Zurich, SwitzerlandMore by Raffaele Mezzenga
- Peter Fischer*Peter Fischer*E-mail: [email protected] (P.F.).Institute of Food Nutrition and Health, ETH Zurich, 8092 Zurich, SwitzerlandMore by Peter Fischer
Abstract

Controlling the assembly of colloids in dispersion is a fundamental approach toward the production of functional materials. Nanocrystalline cellulose (NCC) is a charged nanoparticle whose colloidal interactions can be modulated from repulsive to attractive by increasing ionic strength. Here, we combine polarized optical microscopy, rheology, and small-angle scattering techniques to investigate (i) the concentration-driven transition from isotropic dispersion to cholesteric liquid crystals and (ii) salt-induced NCC phase transitions. In particular, we report on the formation of NCC attractive glasses containing nematic domains. At increasing NCC concentration, a structure peak was observed in small-angle X-ray scattering (SAXS) patterns. The evolution of the structure peak demonstrates the decrease in NCC interparticle distance, favoring orientational order during the isotropic–cholesteric phase transition. Small amounts of salt reduce the cholesteric volume fraction and pitch by a decrease in excluded volume. Beyond a critical salt concentration, NCC forms attractive glasses due to particle caging and reduced motility. This results in a sharp increase in viscosity and formation of viscoelastic glasses. The presence of nematic domains is suggested by the appearance of interference colors and the Cox–Merz rule failure and was confirmed by an anisotropic SAXS scattering pattern at q ranges associated with the presence of nematic domains. Thus, salt addition allows the formation of NCC attractive glasses with mechanical properties similar to those of gels while remaining optically active owed to entrapped nematic domains.
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- Hui Jie, Kai Feng, Mengfan Lu, Zhaoxia Jin. Modulation of Tannic Acid on the Cholesteric Structure of Cellulose Nanocrystals. Langmuir 2024, 40
(27)
, 13834-13843. https://doi.org/10.1021/acs.langmuir.4c00767
- Julia M. Antoniw, Madeleine T. Hallman, Michael V. Kiriakou, Timothy Morse, Emily D. Cranston. Colloidal Stability Window for Carboxylated Cellulose Nanocrystals: Considerations for Handling, Characterization, and Formulation. Langmuir 2023, 39
(30)
, 10321-10334. https://doi.org/10.1021/acs.langmuir.3c00319
- Marvin Detert, Tatiana Porto Santos, Amy Q. Shen, Vincenzo Calabrese. Alignment–Rheology Relationship of Biosourced Rod-Like Colloids and Polymers under Flow. Biomacromolecules 2023, 24
(7)
, 3304-3312. https://doi.org/10.1021/acs.biomac.3c00347
- Pascal Bertsch, Mani Diba, David J. Mooney, Sander C. G. Leeuwenburgh. Self-Healing Injectable Hydrogels for Tissue Regeneration. Chemical Reviews 2023, 123
(2)
, 834-873. https://doi.org/10.1021/acs.chemrev.2c00179
- Vincenzo Calabrese, Stylianos Varchanis, Simon J. Haward, Amy Q. Shen. Alignment of Colloidal Rods in Crowded Environments. Macromolecules 2022, 55
(13)
, 5610-5620. https://doi.org/10.1021/acs.macromol.2c00769
- Mohsen Esmaeili, Kyle George, Gelareh Rezvan, Nader Taheri-Qazvini, Rui Zhang, Monirosadat Sadati. Capillary Flow Characterizations of Chiral Nematic Cellulose Nanocrystal Suspensions. Langmuir 2022, 38
(7)
, 2192-2204. https://doi.org/10.1021/acs.langmuir.1c01881
- Blaise L. Tardy, Bruno D. Mattos, Caio G. Otoni, Marco Beaumont, Johanna Majoinen, Tero Kämäräinen, Orlando J. Rojas. Deconstruction and Reassembly of Renewable Polymers and Biocolloids into Next Generation Structured Materials. Chemical Reviews 2021, 121
(22)
, 14088-14188. https://doi.org/10.1021/acs.chemrev.0c01333
- Vincenzo Calabrese, Simon J. Haward, Amy Q. Shen. Effects of Shearing and Extensional Flows on the Alignment of Colloidal Rods. Macromolecules 2021, 54
(9)
, 4176-4185. https://doi.org/10.1021/acs.macromol.0c02155
- Pascal Bertsch, Michael Diener, Jozef Adamcik, Nathalie Scheuble, Thomas Geue, Raffaele Mezzenga, Peter Fischer. Correction to Adsorption and Interfacial Layer Structure of Unmodified Nanocrystalline Cellulose at Air/Water Interfaces. Langmuir 2020, 36
(7)
, 1848-1849. https://doi.org/10.1021/acs.langmuir.0c00263
- Guang Chu, Gleb Vasilyev, Dan Qu, Shengwei Deng, Long Bai, Orlando J. Rojas, Eyal Zussman. Structural Arrest and Phase Transition in Glassy Nanocellulose Colloids. Langmuir 2020, 36
(4)
, 979-985. https://doi.org/10.1021/acs.langmuir.9b03570
- Pascal Bertsch, Livia Schneider, Giovanni Bovone, Mark W. Tibbitt, Peter Fischer, Stefan Gstöhl. Injectable Biocompatible Hydrogels from Cellulose Nanocrystals for Locally Targeted Sustained Drug Release. ACS Applied Materials & Interfaces 2019, 11
(42)
, 38578-38585. https://doi.org/10.1021/acsami.9b15896
- Pascal Bertsch, Peter Fischer. Interfacial Rheology of Charged Anisotropic Cellulose Nanocrystals at the Air–Water Interface. Langmuir 2019, 35
(24)
, 7937-7943. https://doi.org/10.1021/acs.langmuir.9b00699
- Kento Nakamine, Yuto Yokoyama, William Kai Alexander Worby, Masakazu Muto, Yoshiyuki Tagawa. Flow birefringence of cellulose nanocrystal suspensions in three-dimensional flow fields: revisiting the stress-optic law. Cellulose 2024, 31
(12)
, 7405-7420. https://doi.org/10.1007/s10570-024-06045-x
- Miao Cheng, Wentao Xia, Ruirui Wang, Shaoqing Pan, Tongyu Shen, Qianqian Liu, Jing Hu, Tao Wei, Yun Ling, Wanfei Li, Bo Liu. Highly dispersed cobalt clusters/nanoparticles embedded in cellulose nanocrystal derived carbon aerogel as efficient sulfur host for high performance lithium sulfur batteries. Journal of Power Sources 2024, 608 , 234645. https://doi.org/10.1016/j.jpowsour.2024.234645
- Shuyu Lu, Xinna Hu, Bo Xu, Chenyu Bai, Tianhui Wang, Tao Ma, Yi Song. Effects of different salt ions on the structure and rheological behavior of sulfated cellulose nanocrystal hydrogel. Food Hydrocolloids 2024, 151 , 109799. https://doi.org/10.1016/j.foodhyd.2024.109799
- Yuan Xu, Elliot P. Gilbert, Anna Sokolova, Jason R. Stokes. Phase transition and gelation in cellulose nanocrystal-based aqueous suspensions studied by SANS. Journal of Colloid and Interface Science 2024, 658 , 660-670. https://doi.org/10.1016/j.jcis.2023.12.041
- Vincenzo Calabrese, Tatiana Porto Santos, Carlos G. Lopez, Minne Paul Lettinga, Simon J. Haward, Amy Q. Shen. Extensibility governs the flow-induced alignment of polymers and rod-like colloids. Physical Review Research 2024, 6
(1)
https://doi.org/10.1103/PhysRevResearch.6.L012042
- Peter N. A. Speets, Jeroen Kalkman. Experiment and theory of the complex refractive index of dense colloidal media. Journal of the Optical Society of America A 2024, 41
(2)
, 214. https://doi.org/10.1364/JOSAA.510603
- Max Engelhardt, Hans Albert Gilg, Klaus Richter, Antoni Sanchez-Ferrer. Adhesion-related properties of silver birch (Betula Pendula Roth) wood as affected by hydrophilic extraction. Wood Science and Technology 2024, 58
(1)
, 379-402. https://doi.org/10.1007/s00226-023-01526-x
- Hannah Tideland, Jelka Feldhusen, Amit Kumar Sonker, Gunnar Westman. Bendable transparent films from cellulose nanocrystals–Study of surface and microstructure-property relationship. Carbohydrate Polymer Technologies and Applications 2023, 6 , 100367. https://doi.org/10.1016/j.carpta.2023.100367
- Mahesh Parit, Zhihua Jiang. Cellulose nanocrystal films: effect of electrolyte and lignin addition on self-assembly, optical, and mechanical properties. Cellulose 2023, 30
(15)
, 9405-9423. https://doi.org/10.1007/s10570-023-05464-6
- Hao Hu, Xiao Zhang, Wei Liu, Qingxi Hou, Yixiang Wang. Advances in bioinspired and multifunctional biomaterials made from chiral cellulose nanocrystals. Chemical Engineering Journal 2023, 474 , 145980. https://doi.org/10.1016/j.cej.2023.145980
- Sungyun Kim, ChaeRim Hwang, Da In Jeong, JiHye Park, Han‐Jun Kim, KangJu Lee, Junmin Lee, Seung‐Hwan Lee, Hyun‐Jong Cho. Nanorod/nanodisk‐integrated liquid crystalline systems for starvation, chemodynamic, and photothermal therapy of cancer. Bioengineering & Translational Medicine 2023, 8
(5)
https://doi.org/10.1002/btm2.10470
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- Aref Abbasi Moud, Aliyeh Abbasi Moud. Flow and assembly of cellulose nanocrystals (CNC): A bottom-up perspective - A review. International Journal of Biological Macromolecules 2023, 232 , 123391. https://doi.org/10.1016/j.ijbiomac.2023.123391
- Kiyoon Min, Giyoong Tae. Cellular infiltration in an injectable sulfated cellulose nanocrystal hydrogel and efficient angiogenesis by VEGF loading. Biomaterials Research 2023, 27
(1)
https://doi.org/10.1186/s40824-023-00373-y
- Minhyung Kim, Suhnue Kim, Nuri Han, Sanghyun Lee, Hyungsup Kim. Understanding viscoelastic behavior of hybrid nanocellulose film based on rheological and electrostatic observation in blended suspension. Carbohydrate Polymers 2023, 300 , 120218. https://doi.org/10.1016/j.carbpol.2022.120218
- Miao Cheng, Junjie Liu, Xiaomian Wang, Yabing Li, Wentao Xia, Qianqian Liu, Jing Hu, Tao Wei, Yun Ling, Bo Liu, Wanfei Li. In-situ synthesis of Bi nanospheres anchored in 3D interconnected cellulose nanocrystal derived carbon aerogel as anode for high-performance Mg-ion batteries. Chemical Engineering Journal 2023, 451 , 138824. https://doi.org/10.1016/j.cej.2022.138824
- Qiyao Sun, Viviane Lutz-Bueno, Jiangtao Zhou, Ye Yuan, Peter Fischer. Polymer induced liquid crystal phase behavior of cellulose nanocrystal dispersions. Nanoscale Advances 2022, 4
(22)
, 4863-4870. https://doi.org/10.1039/D2NA00303A
- Da In Jeong, Sungyun Kim, Min-Hwan Kim, In-Soo Yoon, Seung-Hwan Lee, Dae-Duk Kim, Hyun-Jong Cho. Donepezil hydrochloride-reinforced cellulose nanocrystal-aggregated gel structure for long-acting drug delivery. Carbohydrate Polymers 2022, 296 , 119887. https://doi.org/10.1016/j.carbpol.2022.119887
- Wei Fan, Jiaqi Li, Lihong Wei, Yan Xu. Carboxylated cellulose nanocrystal films with tunable chiroptical properties. Carbohydrate Polymers 2022, 289 , 119442. https://doi.org/10.1016/j.carbpol.2022.119442
- Connor Lane, David Rode, Thomas Rösgen. Birefringent properties of aqueous cellulose nanocrystal suspensions. Cellulose 2022, 29
(11)
, 6093-6107. https://doi.org/10.1007/s10570-022-04646-y
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- Vincenzo Calabrese, Stylianos Varchanis, Simon J. Haward, John Tsamopoulos, Amy Q. Shen. Structure-property relationship of a soft colloidal glass in simple and mixed flows. Journal of Colloid and Interface Science 2021, 601 , 454-466. https://doi.org/10.1016/j.jcis.2021.05.103
- Tomas Rosén, Ruifu Wang, HongRui He, Chengbo Zhan, Shirish Chodankar, Benjamin S. Hsiao. Understanding ion-induced assembly of cellulose nanofibrillar gels through shear-free mixing and
in situ
scanning-SAXS. Nanoscale Advances 2021, 3
(17)
, 4940-4951. https://doi.org/10.1039/D1NA00236H
- Pierre Munier, Andi Di, Seyed Ehsan Hadi, Martin Kapuscinski, Mo Segad, Lennart Bergström. Assembly of cellulose nanocrystals and clay nanoplatelets studied by time-resolved X-ray scattering. Soft Matter 2021, 17
(23)
, 5747-5755. https://doi.org/10.1039/D1SM00251A
- Ulises Casado, Verónica L. Mucci, Mirta I. Aranguren. Cellulose nanocrystals suspensions: Liquid crystal anisotropy, rheology and films iridescence. Carbohydrate Polymers 2021, 261 , 117848. https://doi.org/10.1016/j.carbpol.2021.117848
- Tomas Rosén, Ruifu Wang, HongRui He, Chengbo Zhan, Shirish Chodankar, Benjamin S. Hsiao. Shear-free mixing to achieve accurate temporospatial nanoscale kinetics through scanning-SAXS: ion-induced phase transition of dispersed cellulose nanocrystals. Lab on a Chip 2021, 21
(6)
, 1084-1095. https://doi.org/10.1039/D0LC01048K
- Kyongok Kang, Alexey Eremin. Solvent-dependent morphology and anisotropic microscopic dynamics of cellulose nanocrystals under electric fields. Physical Review E 2021, 103
(3)
https://doi.org/10.1103/PhysRevE.103.032606
- Sayyed Ahmad Khadem, Massimo Bagnani, Raffaele Mezzenga, Alejandro D. Rey. Relaxation dynamics in bio-colloidal cholesteric liquid crystals confined to cylindrical geometry. Nature Communications 2020, 11
(1)
https://doi.org/10.1038/s41467-020-18421-9
- Saffron J. Bryant, Marcelo A. da Silva, Kazi M. Zakir Hossain, Vincenzo Calabrese, Janet L. Scott, Karen J. Edler. Deep eutectic solvent in water pickering emulsions stabilised by cellulose nanofibrils. RSC Advances 2020, 10
(61)
, 37023-37027. https://doi.org/10.1039/D0RA07575B
- Aleksandar Y. Mehandzhiyski, Nicolas Rolland, Mohit Garg, Jakob Wohlert, Mathieu Linares, Igor Zozoulenko. A novel supra coarse-grained model for cellulose. Cellulose 2020, 27
(8)
, 4221-4234. https://doi.org/10.1007/s10570-020-03068-y
- Dinesh Sundaravadivelu Devarajan, Pouria Nourian, Gregory B. McKenna, Rajesh Khare. Molecular simulation of nanocolloid rheology: Viscosity, viscoelasticity, and time-concentration superposition. Journal of Rheology 2020, 64
(3)
, 529-543. https://doi.org/10.1122/1.5125142
- Pascal Bertsch, Peter Fischer. Adsorption and interfacial structure of nanocelluloses at fluid interfaces. Advances in Colloid and Interface Science 2020, 276 , 102089. https://doi.org/10.1016/j.cis.2019.102089
- Yuan Xu, Aleks Atrens, Jason R. Stokes. A review of nanocrystalline cellulose suspensions: Rheology, liquid crystal ordering and colloidal phase behaviour. Advances in Colloid and Interface Science 2020, 275 , 102076. https://doi.org/10.1016/j.cis.2019.102076
- Jotam Bergfreund, Qiyao Sun, Peter Fischer, Pascal Bertsch. Adsorption of charged anisotropic nanoparticles at oil–water interfaces. Nanoscale Advances 2019, 1
(11)
, 4308-4312. https://doi.org/10.1039/C9NA00506D
- Kyongok Kang, Pascal Bertsch, Peter Fischer. Coupling of long-wavelength density fluctuations to orientations in cellulose nanocrystal suspensions under external fields. Physical Review E 2019, 100
(5)
https://doi.org/10.1103/PhysRevE.100.052606
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