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Innovative bionanocomposite foams based on precipitated Kraft lignin (Lig) and Kraft black liquor (BL) loaded with sepiolite (Sep) were prepared. BL/Sep bionanocomposites were synthesized by emulsion templating and Lig/Sep bionanocomposites were prepared by freeze-drying, resulting in stable and rigid foams. BL/Sep bionanocomposites displayed a closed cell structure, a specific area between 19 and 35 m2/g and macropores of varying sizes. The porosity in this technique is achieved by the mechanical agitation of the emulsion. On the other hand, freeze-dried Lig/Sep bionanocomposites showed open cell morphology with surface areas ranging from 1 to 4 m2/g and uniform macropores due to the ice-templating process. The presence of sepiolite in both types of bionanocomposite foams improved their stiffness, with Young's moduli ranging from 0.21 to 9.6 MPa. The capacity of the foams to adsorb metals, drugs and dyes was evaluated and it was found that the synthesized bionanocomposite foams exhibiting similar adsorption capacities as that reported for lignin. Sepiolite significantly improved the adsorption of Cu(II), Cd(II), acetaminophen (ACT), and methylene blue (MB) in BL/Sep bionanocomposites. Meanwhile, the Lig/Sep bionanocomposites demonstrated superior adsorption capacities for the Cr(VI) anion and aromatic ring compounds, including ACT and MB. In this respect, these lignin-sepiolite foams can be considered as promising materials for the removal of pollutants in aqueous solution.

Cellulosic materials loaded with a novel zinc layered simple hydroxide (LSH) with allantoin in its structure (allant-ZnLSH) have been developed for potential application as wound dressings. The allant-ZnLSH biohybrid was synthesized by slow addition of a zinc chloride solution to an aqueous solution of allantoin, while adding a NaOH solution dropwise to maintain a controlled pH. The recovered precipitate was characterized by XRD, FTIR, chemical analysis, and FE-SEM. The allant-ZnLSH material was further incorporated into biopolymeric matrices such as hydroxypropylmethylcellulose (HPMC), carboxymethylcellulose (CMC) and cellulose nanofibers (CNF), because of their biocompatibility and biodegradability. The resulting films presented suitable mechanical properties, with Young's modulus values ranging between 1.3 and 3.9 GPa, as well as appropriate water vapor transmission rates (WVTR) for application in would healing, around 250–630 g/m2 per day. The bionanocomposite films also showed interesting barrier properties against the passage of UV light, while keeping a certain transparency in the visible range that would allow the healing process to be monitored without removing the dressing. Their antibacterial action was evaluated against E. coli and S. aureus in agar plates, showing only antimicrobial activity against the latter. The goal is to develop materials that can exhibit antimicrobial, and skin regenerative properties provided by the presence of zinc ions and allantoin, respectively.

Although hydroxypropyl methylcellulose (HPMC) has been proposed as renewable substitute for traditional plastic, its barrier and active properties need to be improved. Thus, the combination of an organic residue such as kraft lignin (0-10% w/w) and a natural clay such as montmorillonite (3% w/w) by application of ultrasound can significantly improve HPMC properties. This is most likely due to the close interaction between lignin and montmorillonite, which leads to delamination of the clay and improves its dispersion within the HPMC matrix. Specifically, the addition of kraft lignin to the bionanocomposite films provided them with UV-shielding, antioxidant capacity and antibacterial activity. The incorporation of 3% montmorillonite resulted in reductions of 65.8% and 11.4% in oxygen (OP) and water vapor permeabilities (WVP), respectively. Moreover, a reduction of 43.8% in WVP was achieved when both lignin (1%) and montmorillonite (3%) were incorporated, observing a synergistic effect. Thus, the HPMC bionanocomposite with 1% lignin and 3% montmorillonite, presented good thermal stability and mechanical strength with significantly improved gas barrier permeability, as well as UV-shielding (maintaining a good transparency), antioxidant and antibacterial activities.

The development of nanocellulose-clay materials resulted of great relevance, as it opened up the applications of nanocellulose, but it still requires new approaches that could contribute to improve the preparation procedures and the features of this type of biohybrid materials. In this context, nanocellulose-sepiolite (NC-S) biocomposite foams and films have already been successfully tested for some applications. However, the influence of the nanocellulose properties on sepiolite-cellulose interactions, and consequently on the final properties and potential applications of NC-S biohybrid materials, has not been previously studied. To address this knowledge gap, four kinds of nanocelluloses produced from elm biomass (non-chemically pretreated lignocellulose and bleached cellulose nanofibers (LCNFs and CNFs, respectively), TEMPO-oxidized cellulose nanofibers (TOCNFs) and cellulose nanocrystals (CNCs)) were characterized and used to develop NC-S nanopapers. A stronger interaction was found between sepiolite and negatively charged nanocelluloses (TOCNFs and CNCs), improving their thermal stability and mechanical properties by increasing the sepiolite content. Furthermore, the type of nanocellulose and the sepiolite content could be adjusted to tune the flammability, water permeability and mechanical and optical properties of the NC-S nanopapers. Graphical abstract: [Figure not available: see fulltext.]

TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl)-oxidized cellulose nanofibers (CNF) were assembled to fibrous clay sepiolite (SEP) by means of a high shear homogenizer and an ultrasound treatment followed by lyophilization using three different methods: normal freezing, directional freezing, and a sequential combination of both methods. Methyltrimethoxysilane (MTMS) was grafted to the foam surface by the vapor deposition method to introduce hydrophobicity to the resulting materials. Both the SEP addition (for the normal and directional freezing methods) and the refreezing preparation procedure enhanced the compressive strength of the foams, showing compressive moduli in the range from 28 to 103 kPa for foams loaded with 20% w/w sepiolite. Mercury intrusion porosimetry shows that the average pore diameters were in the range of 30-45 µm depending on the freezing method. This large porosity leads to materials with very low apparent density, around 6 mg/cm3, and very high porosity >99.5%. In addition, water contact angle measurement and Fourier-transform infrared spectroscopy (FTIR) were applied to confirm the foam hydrophobicity, which is suitable for use as an oil sorbent. The sorption ability of these composite foams has been tested using olive and motor oils as models of organophilic liquid adsorbates, observing a maximum sorption capacity of 138 and 90 g/g, respectively.

Biohybrid materials were prepared by co-assembling the three following components: nanotubular halloysite, microfibrous sepiolite, and cellulose nanofibers dispersed in water, in order to exploit the most salient features of each individual component and to render homogeneous, flexible, yet strong films. Indeed, the incorporation of halloysite improves the mechanical performance of the resulting hybrid nanopapers and the assembly of the three components modifies the surface features concerning wetting properties compared to pristine materials, so that the main characteristics of the resulting materials become tunable with regard to certain properties. Owing to their hierarchical porosity together with their diverse surface characteristics, these hybrids can be used in diverse biomedical/pharmaceutical applications. Herein, for instance, loading with two model drugs, salicylic acid and ibuprofen, allows controlled and sustained release as deduced from antimicrobial assays, opening a versatile path for developing other related organic-inorganic materials of potential interest in diverse application fields.

Nanotechnology can alleviate the current challenges posed by the COVID-19 pandemic. Viral particles of coronaviruses including SARS-CoV-2 as well as other enveloped viruses like the Influenza virus could be considered as an approximation to functional core-shell nanoparticles and therefore, their study enters the realm of nanotechnology. Current research investigation and recent patents dealing with aspects of immunogenic and non-immunogenic prophylaxis, detection and diagnosis as well as therapeutics and treatments are introduced and discussed in the present review.

[EN] Based on the unique ability of defibrillated sepiolite (SEP) to form stable and homogeneous colloidal dispersions of diverse types of nanoparticles in aqueous media under ultrasonication, multicomponent conductive nanoarchitectured materials integrating halloysite nanotubes (HNTs), graphene nanoplatelets (GNPs) and chitosan (CHI) have been developed. The resulting nanohybrid suspensions could be easily formed into films or foams, where each individual component plays a critical role in the biocomposite: HNTs act as nanocontainers for bioactive species, GNPs provide electrical conductivity (enhanced by doping with MWCNTs) and, the CHI polymer matrix introduces mechanical and membrane properties that are of key significance for the development of electrochemical devices. The resulting characteristics allow for a possible application of these active elements as integrated multicomponent materials for advanced electrochemical devices such as biosensors and enzymatic biofuel cells. This strategy can be regarded as an >a la carte> menu, where the selection of the nanocomponents exhibiting different properties will determine a functional set of predetermined utility with SEP maintaining stable colloidal dispersions of different nanoparticles and polymers in water.

[EN] In this work, organic–inorganic hybrid nanoarchitectures were prepared in a single coprecipitation step by assembling magnesium–aluminum layered double hydroxides (MgAl-LDH) and a sepiolite fibrous clay, with the simultaneous encapsulation of the herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA) as the MgAl-LDH retains its ion exchange properties. The synthetic procedure was advantageous in comparison to the incorporation of MCPA by ion exchange after the formation of the LDH/sepiolite nanoarchitecture in a previous step, as it was less time consuming and gave rise to a higher loading of MCPA. The resulting MCPA-LDH/sepiolite nanoarchitectures were characterized by various physicochemical techniques (XRD, FTIR and 29Si NMR spectroscopies, CHN analysis and SEM) that revealed interactions of LDH with the sepiolite fibers through the silanol groups present on the outer surface of sepiolite, together with the intercalation of MCPA in the LDH confirmed by the increase in the basal spacing from 0.77 nm for the pristine LDH to 2.32 nm for the prepared materials. The amount of herbicide incorporated in the hybrid nanoarchitectures prepared by the single-step coprecipitation method surpassed the CEC of LDH (ca. 330 mEq/100 g), with values reaching 445 mEq/100 g LDH for certain compositions. This suggests a synergy between the inorganic solids that allows the nanoarchitecture to exhibit better adsorption properties than the separate components. Additionally, in the release assays, the herbicide incorporated in the hybrid nanoarchitectures could be completely released, which confirms its suitability for agricultural applications. In order to achieve a more controlled release of the herbicide and to act for several days on the surface of the soil, the hybrid nanoarchitectures were encapsulated in a biopolymer matrix of alginate/zein and shaped into spheres. In in vitro tests carried out in bidistilled water, a continuous release of MCPA from the bionanocomposite beads w

Lipid-based bio-nanohybrids were evaluated as carriers of viral particles in the development of thermally stable and efficacious vaccines against influenza A. Herein, the surfaces of the microfibrous clay sepiolite and the Mg/Al-type layered double hydroxide were modified with a bilayer lipid membrane on which influenza A virions were immobilised. These vaccines were highly immunogenic in mice and stability studies revealed that thermal and lyophilisation resistance were significantly enhanced when compared with a standard aluminium adjuvant. These findings might be attributable to the colloidal behaviour in combination with the biomimetic interface which improves the carrier-virus interactions and preserves the molecular architecture of the viral particles. All these characteristics make the here presented clay-lipid biohybrid materials promising candidates for vaccine formulations. Clay-lipid bio-nanohybrids were evaluated as carriers of viral antigens in the development of thermally stable and efficacious vaccines against influenza A. The biomimetic lipid interfaces on sepiolite and an Mg/Al-type layered double hydroxide afford improved immunogenicity compared with standard aluminium adjuvants and modulate support-antigen interactions to ensure thermal stability of the immobilised virions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.