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Almeida, APC, Oliveira J, Fernandes SN, Godinho MH, Canejo JP.  2020.  All-cellulose composite membranes for oil microdroplet collection, 2020. 27(8):4665-4677. AbstractWebsite

Oil spills on ocean waters represent a major threat to marine ecosystems. A significant part of the spilled oil is dispersed in microdroplets that are not recovered by traditional oil-removing methods. In this work, we report on the manufacture of cellulose acetate (CA) electrospun non-woven membranes, stamped with different cellulose nanocrystal (CNC) patterns. We demonstrate the use of the membranes produced as selective oil microdroplets removal from water emulsions with an efficiency up to 80%. Screenprinting was used to imprint different CNC designs on the CA surface membranes. To promote the adhesion between the CNCs and the CNCs with the CA fibers the membrane was subjected to a thermal and chemical treatments. Oil droplets were collected under water in the oleophilic CNC pattern while the water could flow through the hydrophilic CA electrospun non-woven membrane.

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Almeida, APC, Canejo JP, Almeida PL, Godinho MH.  2019.  Cholesteric-type cellulosic structures: from plants to applications. Liquid Crystals. :accepted.Website
Silva, PES, da Rosa RR, Chagas R, Fernandes SN, Godinho MH.  2021.  Colourful Patterns in Cellulose-Based Liquid Crystals. Liquid Crystals and their Application. 21(4):53-60.412702article_2021_21_4_53-60.pdf
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Saraiva, DV, Chagas R, de Abreu BM, Gouveia CN, Silva PES, Godinho MH, Fernandes SN.  2020.  Flexible and Structural Coloured Composite Films from Cellulose Nanocrystals/Hydroxypropyl Cellulose Lyotropic Suspensions. Crystals. 10, Number 2 AbstractWebsite

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.

Germano, GCM, Machado YDR, Martinho L, Fernandes SN, Costa AMLM, Pecoraro E, Gomes ASL, Carvalho ICS.  2020.  Flexible random lasers in dye-doped bio-degradable cellulose nanocrystalline needles, 2020. Journal of the Optical Society of America BJournal of the Optical Society of America B. 37(1):24-29.: OSA AbstractWebsite

In 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 ${\rm CNCs}+{\rm Rh6G}+{\rm hydroxypropyl}$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.

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Ventura, C, Marques C, Cadete J, Vilar M, Pedrosa JFS, Pinto F, Fernandes SN, da Rosa RR, Godinho MH, Ferreira PJT, Louro H, Silva MJ.  2022.  Genotoxicity of Three Micro/Nanocelluloses with Different Physicochemical Characteristics in MG-63 and V79 Cells. Journal of Xenobiotics. 12:91–108., Number 2 AbstractWebsite

(1) Background: Nanocellulose is an innovative engineered nanomaterial with an enormous potential for use in a wide array of industrial and biomedical applications and with fast growing economic value. The expanding production of nanocellulose is leading to an increased human exposure, raising concerns about their potential health effects. This study was aimed at assessing the potential toxic and genotoxic effects of different nanocelluloses in two mammalian cell lines; (2) Methods: Two micro/nanocelluloses, produced with a TEMPO oxidation pre-treatment (CNFs) and an enzymatic pre-treatment (CMFs), and cellulose nanocrystals (CNCs) were tested in osteoblastic-like human cells (MG-63) and Chinese hamster lung fibroblasts (V79) using the MTT and clonogenic assays to analyse cytotoxicity, and the micronucleus assay to test genotoxicity; (3) Results: cytotoxicity was observed by the clonogenic assay in V79 cells, particularly for CNCs, but not by the MTT assay; CNF induced micronuclei in both cell lines and nucleoplasmic bridges in MG-63 cells; CMF and CNC induced micronuclei and nucleoplasmic bridges in MG-63 cells, but not in V79 cells; (4) Conclusions: All nanocelluloses revealed cytotoxicity and genotoxicity, although at different concentrations, that may be related to their physicochemical differences and availability for cell uptake, and to differences in the DNA damage response of the cell model.

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Trindade, AC, Carreto M, Helgesen G, Knudsen KD, Puchtler F, Breu J, Fernandes S, Godinho MH, Fossum JO.  2020.  Photonic composite materials from cellulose nanorods and clay nanolayers, 2020. 229(17):2741-2755. AbstractWebsite

Cellulose nano crystals (CNCs) are promising materials for energy efficient buildings related to the control of reflectivity and heat absorption/reflection of light. In this sense it is important to improve CNCs films fire retardant properties, which can be achieved by adding clays. Cellulose nanocrystals (CNCs) and nanolayers obtained from Sodium Fluorohectorite (NaFh) synthetic clay are both known to form liquid crystalline phases in aqueous suspensions. CNCs form cholesteric phases, which structure is preserved after water evaporation, while dry NaFh nanolayers aligned films collapse. In this initial work, it is shown that CNCs are compatible with NaFh clay. We demonstrate that the liquid crystalline phase of CNCs in water is not destroyed by the presence of NaFh nanolayers. The NaFh nanolayers act as planar anchoring surfaces to the cellulose nanorods and, after evaporation of the water coloured films are obtained. The precursor solutions and the photonic films were investigated by Describe several techniques.

Chagas, R, Silva PES, Fernandes SN, Žumer S, Godinho MH.  2020.  Playing the blues, the greens and the reds with cellulose-based structural colours, 2020. Faraday Discussions. 223:247-260.: The Royal Society of Chemistry AbstractWebsite

Structural 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.

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Santos, AFM, Cruz C, Godinho MH, Dionísio M, Figueirinhas JL, Branco LC.  2022.  Synthesis and characterisation of ionic liquid crystals based on substituted pyridinium cations, 2022. Liquid CrystalsLiquid Crystals. :1-13.: Taylor & Francis AbstractWebsite
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Silva, PES, Chagas R, Fernandes SN, Pieranski P, Selinger RLB, Godinho MH.  2021.  Travelling colourful patterns in self-organized cellulose-based liquid crystalline structures, 2021. 2(1):79. AbstractWebsite

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.

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Kumar, A, Cruz C, Figueirinhas JL, Sebastião PJ, Trindade AC, Fernandes SN, Godinho MH, Fossum JO.  2021.  Water Dynamics in Composite Aqueous Suspensions of Cellulose Nanocrystals and a Clay Mineral Studied through Magnetic Resonance Relaxometry, 2021. The Journal of Physical Chemistry BThe Journal of Physical Chemistry B. 125(46):12787-12796.: American Chemical Society AbstractWebsite
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