Living cells interfaced with a range of polyelectrolyte coatings, magnetic and noble metal nanoparticles, hard mineral shells and other complex nanomaterials can perform functions often completely different from their original specialisation. Such "cyborg cells" are already finding a range of novel applications in areas like whole cell biosensors, bioelectronics, toxicity microscreening, tissue engineering, cell implant protection and bioanalytical chemistry. In this tutorial review, we describe the development of novel methods for functionalisation of cells with polymers and nanoparticles and comment on future advances in this technology in the light of other literature approaches. We review recent studies on the cell viability and function upon direct deposition of nanoparticles, coating with polyelectrolytes, polymer assisted assembly of nanomaterials and hard shells on the cell surface. The cell toxicity issues are considered for many practical applications in terms of possible adverse effects of the deposited polymers, polyelectrolytes and nanoparticles on the cell surface.
Biomimetic architectural assembly of clay nanotube shells on yeast cells was demonstrated producing viable artificial hybrid inorganic-cellular structures (armoured cells). These modified cells were preserved for one generation resulting in the intact second generation of cells with delayed germination.
We propose a novel keratin treatment of human hair by its aqueous mixtures with natural halloysite clay nanotubes. The loaded clay nanotubes together with free keratin produce micrometer-thick protective coating on hair. First, colloidal and structural properties of halloysite/keratin dispersions and the nanotube loaded with this protein were investigated. Above the keratin isoelectric point (pH = 4), the protein adsorption into the positive halloysite lumen is favored because of the electrostatic attractions. The ζ-potential magnitude of these core–shell particles increased from −35 (in pristine form) to −43 mV allowing for an enhanced colloidal stability (15 h at pH = 6). This keratin-clay tubule nanocomposite was used for the immersion treatment of hair. Three-dimensional-measuring laser scanning microscopy demonstrated that 50–60% of the hair surface coverage can be achieved with 1 wt % suspension application. Hair samples have been exposed to UV irradiation for times up to 72 h to explore the protection capacity of this coating by monitoring the cysteine oxidation products. The nanocomposites of halloysite and keratin prevent the deterioration of human hair as evident by significant inhibition of cysteic acid. The successful hair structure protection was also visually confirmed by atomic force microscopy and dark-field hyperspectral microscopy. The proposed formulation represents a promising strategy for a sustainable medical coating on the hair, which remediates UV irradiation stress.
Halloysites as tubular alumosilicates are introduced as inexpensive natural nanoparticles to form and stabilize oil–water emulsions. This stabilized emulsion is shown to enable efficient interfacial catalytic reactions. Yield, selectivity, and product separation can be tremendously enhanced, e.g., for the hydroformylation reaction of dodecene to tridecanal. In perspective, this type of formulation may be used for oil spill dispersions. The key elements of the described formulations are clay nanotubes (halloysites) which are highly anisometric, can be filled by helper molecules, and are abundantly available in thousands of tons, making this technology scalable for industrial applications
Composite films based on cellulose, chitosan and halloysite clay nanotubes were prepared using a solution casting method, which allowed for a uniform distribution of nanotubes within the material and provided control over the morphology of the composite. The mechanical performance of these bio nanocomposites is influenced by humidity and the nanotubes showed a plasticisation effect on the polymeric matrix. The composites of chitosan and halloysite nanotubes (HNTs), with modified hydrophobic inner lumens, resulted in a technique for controlled and sustainable surface cleaning. Lignocellulose wood microfibres modified with HNTs were also produced by a layer-by-layer assembly. The obtained material represents a composite well suited for making paper sheets for biomedical applications, where enhanced porosity can be crucial. Toxicity tests carried out on biopolymer–halloysite composites showed that these nanocomposites are safe for cell cultures up to 0·5 mg/mL of free clay nanotubes.
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