Playing the blues, the greens and the reds with cellulose-based structural colours

POCI- 01-0145-FEDER-007688 (Reference UIDB/50025/2020-2023) PTDC/CTM-BIO/6178/2014 M-ERA-NET2/0007/2016 PTDC/CTM-REF/30529/2017 EUTOPIA CA17139 Slovenian Research Agency Grant Z1-5441 P1-0099Structural vivid colours can arise from the interference of light reflected from structures exhibiting periodicity on scales in the range of visible wavelengths. This effect is observed with light reflected from cell-walls of some plants and exoskeletons of certain insects. Sometimes the colour sequence observed for these structures consists of nearly circular concentric rings that vary in colour from Red, Orange, Yellow, Green, Cyan to Blue, from the periphery to the centre, similarly to the colour scheme sequence observed for the rainbow (ROYGB). The sequence of colours has been found for solid films obtained from droplets of aqueous cellulose nanocrystals (CNCs) suspensions and attributed to a "coffee ring"effect. In this work, coloured lyotropic solutions and solid films obtained from a cellulose derivative in the presence of trifluoroacetic acid (TFA), which acts as a "reactive solvent", are revisited. The systems were investigated with spectroscopy, using circularly and linearly polarised light, coupled with a polarised optical microscope (POM) and scanning electron microscopy (SEM). The lyotropic cholesteric liquid crystalline solutions were confined in capillaries to simplify 1D molecular diffusion along the capillary where an unexpected sequence of the structural colours was observed. The development and reappearance of the sequence of vivid colours seem consistent with the reaction-diffusion of the "reactive solvent"in the presence of the cellulosic chains. The strong TFA acts as an auto-catalyst for the chemical reaction between TFA and the hydroxyl groups, existing along the cellulosic chain, and diffuses to the top and bottom along the capillaries, carrying dissolved cellulosic chains. Uncovering the precise mechanism of colour sequence and evolution over time in cellulosic lyotropic solutions has important implications for future optical/sensors applications and for the understanding of the development of cellulose-based structures in nature. This journal isauthorsversionpublishe

Colourful patterns in cellulose-based liquid crystals

POCI-01-0145-FEDER-007688 UIDB/50025/2020-2023 EUTOPIA CA17139Cellulose-based thermotropic and lyotropic liquid crystals can be obtained from macromolecules or colloidal particles, such as cellulose nanocrystals. Thermotropic liquid crystals are produced by the effect of temperature, while lyotropic liquid crystals occur in solution for a given range of concentration, pressure, and temperature. Cellulose liquid crystals can form chiral nematic phases characterized by Bragg-type reflections of circularly polarized light. This characteristic is related to a helical structure formed by pseudo nematic layers twisted around an optical axis. The helical structure is characterized by the values of pitch and helicity. The later can be right- (R) or left- (L) handed. Cellulose liquid crystals are well described in literature. They are a source of materials for many applications, including the production of photonic chiral materials. Although many questions remain unanswered such as the origin of helicity of cellulosic chiral structures and those related to out-ofequilibrium systems. In this paper, we are focused at the out-of-equilibrium systems obtained from lyotropic cellulose-based liquid crystals. The development of colorful patterns involving the pitch variation in space and time of self-organized cellulose cholesteric structures is revised.publishersversionpublishe

Travelling colourful patterns in self-organized cellulose-based liquid crystalline structures

Publisher Copyright: © 2021, The Author(s)Cellulose-based systems are useful for many applications. However, the issue of self-organization under non-equilibrium conditions, which is ubiquitous in living matter, has scarcely been addressed in cellulose-based materials. Here, we show that quasi-2D preparations of a lyotropic cellulose-based cholesteric mesophase display travelling colourful patterns, which are generated by a chemical reaction-diffusion mechanism being simultaneous with the evaporation of solvents at the boundaries. These patterns involve spatial and temporal variation in the amplitude and sign of the helix´s pitch. We propose a simple model, based on a reaction-diffusion mechanism, which simulates the observed spatiotemporal colour behaviour.publishersversionpublishe

Ionically Modified Cellulose Nanocrystal Self-Assembled Films with a Mesoporous Twisted Superstructure: Polarizability and Application in Ion-Gated Transistors

FCT – Portuguese Foundation for Science and Technology through the Ph.D. scholarship SFRH/BD/125191/2016. project PapEl, reference PTDC/CTM-NAN/5172/2014. project CHIHC, reference PTDC/NAN-MAT/32558/2017. project PTDC/CTM-BIO/6178/2014, M-ERA-NET2/0007/2016 (CellColor). POR Lisboa2020 through project PTDC/CTM-REF/30529/2017. D.G. acknowledges the support from FCT – Portuguese Foundation for Science and Technology through the AdvaMTech PhD program scholarship PD/BD/52627/2014.Mesoporous structures made of cellulose nanocrystals (CNCs) and their self-assembly into films are of great interest not only due to their abundancy and sustainability but also due to their ease of chemical modification and nanoscale biomimicry capabilities. However, their implementation in (opto)electronic devices requires further understanding on how these self-assembled twisted mesoporous superstructures respond to electrical stimulus. In this regard, this work focuses on the infiltration of solid CNC droplets with three distinct alkali ions (Li+, Na+, and K+) to yield films with improved electrochemical response when compared to pristine ones, while preserving their photonic character. Electrochemical characterization shows capacitances of up to 2.5 μF cm–2 allowing for their integration as solid-state gate electrolytes in amorphous indium–gallium–zinc–oxide transistors, resulting in low operating voltages (10 cm2 V–1 s–1. Devices fabricated on Na+ and K+ infiltrated CNC films present the best characteristics, indicating pure capacitive charging of the semiconductor. The insights presented here contribute to applications in solid-state ionics in mesoporous structures or the combination of optically active electrolytes capable of providing unique functionalities in ion-gated transistors and circuitry.publishersversionpublishe

Observing short-range orientational order in small-molecule liquids

AG and TA acknowledge the funding from Slovenian Research Agency, Basic core funding grant P1-0125. SNF, MGH acknowledge the FCT—Portuguese Foundation for Science and Technology projects PIDDAC (POCI-01-0145-FEDER-007688, Reference UIDB/50025/2020-2023). Publisher Copyright: © 2022, The Author(s).Local molecular ordering in liquids has attracted a lot of interest from researchers investigating crystallization, but is still poorly understood on the molecular scale. Classical nucleation theory (CNT), a macroscopic thermodynamic description of condensation, has shortcomings when dealing with clusters consisting of tens of molecules. Cluster formation and local order fluctuations in liquid media are difficult to study due to the limited spatial resolution of electron- and photon-imaging methods. We used NMR relaxometry to demonstrate the existence of dynamic clusters with short-range orientational order in nominally isotropic liquids consisting of elongated molecules. We observed clusters in liquids where the local ordering is driven by polar, steric, and hydrogen-bond interactions between the molecules. In the case of a liquid crystal, measuring the local orientational order fluctuations allowed us to observe the size of these clusters diverging when approaching the phase transition from the isotropic to the nematic phase. These fluctuations are described in terms of rotational elasticity as a consequence of the correlated reorientations of the neighbouring molecules. Our quantitative observations of the dynamic clusters in liquids, numbering about ten or fewer molecules, indicate that this is a general phenomenon in various types of liquids.publishersversionpublishe

Flexible and structural coloured composite films from cellulose nanocrystals/hydroxypropyl cellulose lyotropic suspensions

FEDER funds through the COMPETE 2020 Program, National Funds through FCT -Portuguese Foundation for Science and Technology and POR Lisboa2020, PTDC/CTM-BIO/6178/2014, M-ERA-NET2/0007/2016 (CellColor) and PTDC/CTM-REF/30529/2017 (NanoCell2SEC).Lyotropic colloidal aqueous suspensions of cellulose nanocrystals (CNCs) can, after solvent evaporation, retain their chiral nematic arrangement. As water is removed the pitch value of the suspension decreases and structural colour-generating films, which are mechanically brittle in nature, can be obtained. Increasing their flexibility while keeping the chiral nematic structure and biocompatible nature is a challenging task. However, if achievable, this will promote their use in new and interesting applications. In this study, we report on the addition of different amounts of hydroxypropyl cellulose (HPC) to CNCs suspension within the coexistence of the isotropic-anisotropic phases and infer the influence of this cellulosic derivative on the properties of the obtained solid films. It was possible to add 50 wt.% of HPC to a CNCs aqueous suspension (to obtain a 50/50 solids ratio) without disrupting the LC phase of CNCs and maintaining a left-handed helical structure in the obtained films. When 30 wt.% of HPC was added to the suspension of CNCs, a strong colouration in the film was still observed. This colour shifts to the near-infrared region as the HPC content in the colloidal suspension increases to 40 wt.% or 50 wt.% The all-cellulosic composite films present an increase in the maximum strain as the concentration of HPC increases, as shown by the bending experiments and an improvement in their thermal properties.publishersversionpublishe

Rheo-optical characterization of liquid crystalline acetoxypropylcellulose melt undergoing large shear flow and relaxation after flow cessation

The rheological and structural characteristics of acetoxypropylcellulose (APC) nematic melt are studied at shear rates ranging from 10 s 1 to 1000 s 1 which are relevant to extrusion based processes. APC shows a monotonic shear thinning behavior over the range of shear rates tested. The negative extrudate-swell shows a minimum when a critical shear rate g_ c is reached. For shear rates smaller than g_ c, the flowinduced texture consists of two set of bands aligned parallel and normal to the flow direction. At shear rates larger than g_ c, the flow induced texture is reminiscent of a 2 fluids structure. Close to the shearing walls, domains elongated along the flow direction and stacked along the vorticity are imaged with POM, whereas SALS patterns indicate that the bulk of the sheared APC is made of elliptical domains oriented along the vorticity. No full nematic alignment is achieved at the largest shear rate tested. Below g_ c, the stress relaxation is described by a stretched exponential. Above g_ c, the stress relaxation is described by a fast and a slow process. The latter coincides with the growth of normal bands thicknesses, as the APC texture after flow cessation consists of two types of bands with parallel and normal orientations relative to the flow direction. Both bands thicknesses do not depend on the applied shear rate, in contrast to their orientation.This work was partially supported by the Portuguese Science and Technology Foundation through projects, PTDC/CTM/099595/2008, PTDC/CTM/101776/2008, PTDC/CTM-POL/1484/2012 and UID/CTM/500025/2013. S.N. Fernandes and J.P. Canejo acknowledge FCT for grants SFRH/BPD/78430/2011 and SFRH/BPD/101041/2014, respectively. Funding for project "Matepro e Optimizing Materials and Processes", with reference NORTE-07-0124-FEDER-000037 FEDER COMPETE, is also acknowledged

Structural Color and Iridescence in Transparent Sheared Cellulosic Films

Shear transparent cellulose free-standing thin films can develop iridescence similar to that found in petals of the tulip Queen of the Night. The iridescence of the film arises from the modulation of the surface into bands periodically spread perpendicular to the shear direction. Small amounts of nanocrystalline cellulose (NCC) rods in the precursor liquid-crystalline solutions do not disturb the optical properties of the solutions but enhance the mechanical characteristics of the films and affects their iridescence. Smaller bands periodicity, not affected by the NCC rods, slightly deviated from the shear direction is also observed. NCCs are crucial to tune and understand the film's surface features formation. Our findings could lead to new materials for application in soft reflective screens and devices

Flexible random lasers in dye-doped bio-degradable cellulose nanocrystalline needles

M-ERA-NET2/0007/2016 POCI-01-0145-FEDER-007688 PTDC/CTM-BIO/6178/2014 PTDC/CTM-REF/30529/2017 UID/CTM/50025In this work, we developed and investigated a random laser based on rhodamine6G (Rh6G) in ethylene glycol (EG) solution with varying cellulose nanocrystalline (CNC) needles as scatterers in the lasing media. Besides the suspension-in-cuvette scheme, an alternative configuration was also employed: a dye-CNC flexible self-supported thick-film (70 µm) random laser made by drop casting of the CNCs + Rh6G + hydroxypropyl cellulose suspension. In relation to conventional scatterers, the biodegradable cellulose nanocompounds showed a comparable reduction in both the spectral full width at half-maximum and the energy threshold values, with an optimal concentration of 5 mg [CNC]/ml[EG] in suspension. Its performance was also compared with other cellulose-based random lasers, presenting advantages for some parameters. The flexible film configuration showed similar results, but contained 10% less Rh6G than the suspension.authorsversionpublishe

Investigation of potential respiratory adverse effects of micro/nanofibrillated cellulose and cellulose nanocrystals using human lung cell lines.

Abstract publicado em: Environ Mol Mutagen. 2022 Aug;63(Suppl 1):72-73. (Abstracts from the 13th International Conference on Environmental Mutagens and 53rd Annual Meeting of the Environmental Mutagenesis and Genomics Society). https://onlinelibrary.wiley.com/toc/10982280/2022/63/S1Micro/nanofibrillated (CMF/CNF) and nanocrystalline (CNC) celluloses are innovative materials with enormous potential for industrial and biomedical applications. Their expanding production/application urges the investigation of their safety for human health. This study aimed at investigating the potential respiratory outcomes of two CMF/CNF and one CNC produced from bleached Eucalyptus globulus kraft pulp using human alveolar epithelial (A549) cells grown in monoculture or co-cultured with THP-1 monocyte-derived macrophages, by assessing their cellular uptake, cytotoxic, immunotoxic, genotoxic, and epigenetic effects. The nanocelluloses were characterized for their physicochemical properties: CMF displays a low percentage of nanofibrils while CNF comprises 100% fibrils with a diameter (D) circa 11 nm; CNC consists of nanorods with D of 4-5 nm and aspect ratio around 42. TEM analysis evidenced that CMF and CNF were internalised into A549 cells whereas CNC were not. Neither cytotoxicity (colorimetric and clonogenic assays) nor ROS induction was observed for any of the nanocelluloses. CMF caused chromosomal alterations (in vitro micronucleus assay) in A549 cells while negative results were obtained in co-culture and for the other micro/nanocelluloses in mono- or co-culture. Results in progress of DNA damage and gene mutation analyses will complement mutagenesis assessment. Additionally, potential inflammatory and epigenetic effects are being evaluated. These results contribute to the weight of evidence of nanocelluloses biological effects and knowledge of the underlying molecular mechanisms. Such information will drive the synthesis of the safest nanocelluloses,thus minimising potential negative impacts of their use on human and environmental health.FCT/MCTES through nacional funds (PTDC/SAU-PUB/32587/2017; UIDP/00009/2020; UIDB/00009/2020; 020.07168.BD)info:eu-repo/semantics/publishedVersio