Kai Hua

Surface Modified Nanocellulose Fibers Yield Conducting Polymer-Based Flexible Supercapacitors with Enhanced Capacitances

We demonstrate that surface modified nanocellulose fibers (NCFs) can be used as substrates to synthesize supercapacitor electrodes with the highest full electrode-normalized gravimetric (127 F g(-1)) and volumetric (122 F cm(-3)) capacitances at high current densities (300 mA cm(-2) ≈ 33 A g(-1)) until date reported for conducting polymer-based electrodes with active mass loadings as high as 9 mg cm(-2). By introducing quaternary amine groups on the surface of NCFs prior to polypyrrole (PPy) polymerization, the macropore volume of the formed PPy-NCF composites can be minimized while maintaining the volume of the micro- and mesopores at the same level as when unmodified or carboxylate groups functionalized NCFs are employed as polymerization substrates. Symmetric, aqueous electrolyte-based, devices comprising these porosity-optimized electrodes exhibit device-specific volumetric energy and power densities of 3.1 mWh cm(-3) and 3 W cm(-3) respectively; which are among the highest values reported for conducting polymer electrodes in aqueous electrolytes. The functionality of the devices is verified by powering a red light-emitting diode with the device in different mechanically challenging states.

Translational study between structure and biological response of nanocellulose from wood and green algae

The influence of nanostructure on the cytocompatibility of cellulose films is analyzed providing insight into how physicochemical properties of surface modified microfibrillated cellulose (MFC) and Cladophora nanocellulose (CC) affect the materials cytocompatibility. CC is modified through TEMPO-mediated oxidation and glycidyltrimethylammonium chloride (EPTMAC) condensation to obtain anionic and cationic nanocellulose samples respectively, while anionic and cationic MFC samples are obtained by carboxymethylation and EPTMAC condensation respectively. Films of unmodified, anionic and cationic MFC and CC are prepared by vacuum filtration and characterized in terms of specific surface area, pore size distribution, degree of crystallinity, surface charge and water content. Human dermal fibroblasts are exposed to culture medium extracts of the films in an indirect contact cytotoxicity test. Moreover, cell adhesion and viability are evaluated in a direct contact assay and the effects of the physicochemical properties on cell behavior are discussed. In the indirect cytotoxicity test no toxic leachables are detected, evidencing that the CC and MFC materials are non-cytotoxic, independently of the chemical treatment that they have been subjected to. The direct contact tests show that carboxymethylated-MFC presents a more cytocompatible profile than unmodified and trimethylammonium-MFC. TEMPO–CC promotes fibroblast adhesion and presents cell viability comparable to the results obtained with the tissue culture material Thermanox. We hypothesize that the distinct aligned nanofiber structure present in the TEMPO–CC films is responsible for the improved cell adhesion. Thus, by controlling the surface properties of cellulose nanofibers, such as chemistry, charge, and orientation, cell adhesion properties can be promoted.

Surface Chemistry of Nanocellulose Fibers Directs Monocyte/Macrophage Response

The effect of surface functionalization of nanofibrillated cellulose (NFC) on monocyte/macrophage (MM) behavior is investigated to understand how the physicochemical properties of nanocelluloses influence the interactions of such materials with biological systems. Films of anionic (a-), cationic (c-), and unmodified (u-) NFC were synthesized and characterized in terms of surface charge. THP-1 monocytes were cultured on the surface of the films for 24 h in the presence and absence of lipopolysaccharide, and the cell response was evaluated in terms of cell adhesion, morphology, and secretion of TNF-α, IL-10, and IL-1ra. The results show that MMs cultured on carboxymethylated-NFC films (a-NFC) are activated toward a proinflammatory phenotype, whereas u-NFC promotes a mild activation of the studied cells. The presence of hydroxypropyltrimethylammonium groups on c-NFC, however, does not promote the activation of MMs, indicating that c-NFC closely behaves as an inert material in terms of MM activation. None of the materials is able to directly activate the MMs toward an anti-inflammatory response. These results may provide a foundation for the design of future NFC-based materials with the ability to control MM activation and may expand the use of NFC in biomedical applications.

Aspirin degradation in surface-charged TEMPO-oxidized mesoporous crystalline nanocellulose

TEMPO-mediated surface oxidation of mesoporous highly crystalline Cladophora cellulose was used to introduce negative surface charges onto cellulose nanofibrils without significantly altering other structural characteristics. This enabled the investigation of the influence of mesoporous nanocellulose surface charges on aspirin chemical stability to be conducted. The negative surface charges (carboxylate content 0.44±0.01 mmol/g) introduced on the mesoporous crystalline nanocellulose significantly accelerated aspirin degradation, compared to the starting material which had significantly less surface charge (0.06±0.01 mmol/g). This effect followed from an increased aspirin amorphisation ability in mesopores of the oxidized nanocellulose. These results highlight the importance of surface charges in formulating nanocellulose for drug delivery.

Transition from Bioinert to Bioactive Material by Tailoring the Biological Cell Response to Carboxylated Nanocellulose

This work presents an insight into the relationship between cell response and physicochemical properties of Cladophora cellulose (CC) by investigating the effect of CC functional group density on the response of model cell lines. CC was carboxylated by electrochemical TEMPO-mediated oxidation. By varying the amount of charge passed through the electrolysis setup, CC materials with different degrees of oxidation were obtained. The effect of carboxyl group density on the materials physicochemical properties was investigated together with the response of human dermal fibroblasts (hDF) and human osteoblastic cells (Saos-2) to the carboxylated CC films. The introduction of carboxyl groups resulted in CC films with decreased specific surface area and smaller total pore volume compared with the unmodified CC (u-CC). While u-CC films presented a porous network of randomly oriented fibers, a compact and aligned fiber pattern was depicted for the carboxylated-CC films. The decrease in surface area and total pore volume, and the orientation and aggregation of the fibers tended to augment parallel to the increase in the carboxyl group density. hDF and Saos-2 cells presented poor cell adhesion and spreading on u-CC, which gradually increased for the carboxylated CC as the degree of oxidation increased. It was found that a threshold value in carboxyl group density needs be reached to obtain a carboxylated-CC film with cytocompatibility comparable to commercial tissue culture material. Hence, this study demonstrates that a normally bioinert nanomaterial can be rendered bioactive by carefully tuning the density of charged groups on the material surface, a finding that not only may contribute to the fundamental understanding of biointerface phenomena, but also to the development of bioinert/bioactive materials.

Nanocellulose from green algae modulates the in vitro inflammatory response of monocytes/macrophages

The response of monocytes and macrophages to functionalized Cladophora nanocellulose (CC) films was evaluated. Carboxyl-CC and hydroxypropyltrimethylammonium-CC [referred to as anionic-CC (a-CC) and cationic-CC (c-CC), respectively] were synthesized by TEMPO-mediated oxidation and epoxypropyltrimethylammonium chloride condensation of unmodified CC (u-CC). The cell response to u-CC, a-CC and c-CC of untreated and phorbol 12-myristate-13 acetate treated THP-1 cells, i.e. monocytes and macrophages, in the presence and absence of lipopolysaccharide (LPS) was studied. u-CC impairs the viability of THP-1 monocytes and macrophages most probably due to the presence of impurities. In the absence of LPS, the functionalized materials behave as inert materials in terms of the inflammatory response of both monocytes and differentiated macrophages. Under pro-inflammatory stimuli the functionalized CC films suppressed the inflammatory response induced by LPS. The a-CC material with its aggregated, aligned fibre structure caused a more pronounced reduction of TNF-α levels compared to the c-CC film that exhibited non-aggregated, randomly oriented fibres. These results push forward the option of using functionalized CC materials in the biomedical field.