Carlos Salas

Cellulose Nanofibrils: From Strong Materials to Bioactive Surfaces

Cellulose nanofi brils (CNF), also known as nanofi brillar cellulose (NFC), are an advanced biomaterial made mainly from renewable forest and agricultural resources that have demonstrated exceptional performance in composites. In addition, they have been utilized in barrier coatings, food, transparent fl exible fi lms and other applications. Research on CNF has advanced rapidly over the last decade and several of the fundamental questions about production and characterization of CNF have been addressed. An interesting shift in focus in the recent reported literature indicates increased efforts aimed at taking advantage of the unique properties of CNF. This includes its nanoscale dimensions, high surface area, unique morphology, low density and mechanical strength. In addition, CNF can be easily (chemically) modified and is readily available, renewable, and biodegradable. These facts are expected to materialize in a more widespread use of CNF. However, there is no clear indication of the most promising avenues for CNF deployment in commercial products. This review attempts to illustrate some exciting opportunities for CNF, specifi cally, in the development of aerogels, composites, bioactive materials and inorganic/organic hybrid materials.

On the Surface Interactions of Proteins with Lignin

Lignins are used often in formulations involving proteins but little is known about the surface interactions between these important biomacromolecules. In this work, we investigate the interactions at the solid-liquid interface of lignin with the two main proteins in soy, glycinin (11S) and β-conglycinin (7S). The extent of adsorption of 11S and 7S onto lignin films and the degree of hydration of the interfacial layers is quantified via Quartz crystal microgravimetry (QCM) and surface plasmon resonance (SPR). Solution ionic strength and protein denaturation (2-mercaptoethanol and urea) critically affect the adsorption process as protein molecules undergo conformational changes and their hydrophobic or hydrophilic amino acid residues interact with the surrounding medium. In general, the adsorption of the undenatured proteins onto lignin is more extensive compared to that of the denatured biomolecules and a large amount of water is coupled to the adsorbed molecules. The reduction in water contact angle after protein adsorption (by ~40° and 35° for undenatured 11S and 7S, respectively) is explained by strong nonspecific interactions between soy proteins and lignin.

Water-Wettable Polypropylene Fibers by Facile Surface Treatment Based on Soy Proteins

Modification of the wetting behavior of hydrophobic surfaces is essential in a variety of materials, including textiles and membranes that require control of fluid interactions, adhesion, transport processes, sensing, etc. This investigation examines the enhancement of wettability of an important class of textile materials, viz., polypropylene (PP) fibers, by surface adsorption of different proteins from soybeans, including soy flour, isolate,glycinin, and β-conglycinin. Detailed investigations of soy adsorption from aqueous solution (pH 7.4, 25 °C) on polypropylene thin films is carried out using quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). A significant amount of protein adsorbs onto the PP surfaces primarily due to hydrophobic interactions. We establish that adsorption of a cationic surfactant, dioctadecyldimethylammonium bromide (DODA) onto PP surfaces prior to the protein deposition dramatically enhances its adsorption. The adsorption of proteins from native (PBS buffer, pH 7.4, 25 °C) and denatured conditions (PBS buffer, pH 7.4, 95 °C) onto DODA-treated PP leads to a high coverage of the proteins on the PP surface as confirmed by a significant improvement in water wettability. A shift in the contact angle from 128° to completely wettable surfaces (≈0°) is observed and confirmed by imaging experiments conducted with fluorescence tags. Furthermore, the results from wicking tests indicate that hydrophobic PP nonwovens absorb a significant amount of water after protein treatment, i.e., the PP-modified surfaces become completely hydrophilic.

Curdlan in fibers as carriers of tetracycline hydrochloride: Controlled release and antibacterial activity

Curdlan (CURD) and polyethylene oxide were used to synthesize nanofibers as carriers of hydro soluble tetracycline hydrochloride (TCH). The viscosity, surface tension and conductivity of the precursor multicomponent aqueous solutions were determined and adjusted to produce defect-free fiber webs. Except for a slight increase in diameter, the addition of TCH did not affect the original morphology of the CURD/PEO nanofibers, as determined by FE-SEM imaging. However, the thermal stability of the system was enhanced (TGA and DSC). Moreover, water resistance, as measured with 24-h immersion tests, was observed upon crosslinking with glutaraldehyde. In-vitro activity measurements indicated a sustained and controlled TCH time-release pattern and excellent antibacterial activity against E. coli, as assessed by UV-vis spectroscopy and viable cell counting, respectively. Overall, we propose nanofibers based on CURD as promising platforms for scaffolds for wound dressing and drug delivery.

Interactions between Cellulolytic Enzymes with Native, Autohydrolysis, and Technical Lignins and the Effect of a Polysorbate Amphiphile in Reducing Nonproductive Binding

Understanding enzyme-substrate interactions is critical in designing strategies for bioconversion of lignocellulosic biomass. In this study we monitored molecular events, in situ and in real time, including the adsorption and desorption of cellulolytic enzymes on lignins and cellulose, by using quartz crystal microgravimetry and surface plasmon resonance. The effect of a nonionic surface active molecule was also elucidated. Three lignin substrates relevant to the sugar platform in biorefinery efforts were considered, namely, hardwood autohydrolysis cellulolytic (HWAH), hardwood native cellulolytic (MPCEL), and nonwood native cellulolytic (WSCEL) lignin. In addition, Kraft lignins derived from softwoods (SWK) and hardwoods (HWK) were used as references. The results indicated a high affinity between the lignins with both, monocomponent and multicomponent enzymes. More importantly, the addition of nonionic surfactants at concentrations above their critical micelle concentration reduced remarkably (by over 90%) the nonproductive interactions between the cellulolytic enzymes and the lignins. This effect was hypothesized to be a consequence of the balance of hydrophobic and hydrogen bonding interactions. Moreover, the reduction of surface roughness and increased wettability of lignin surfaces upon surfactant treatment contributed to a lower affinity with the enzymes. Conformational changes of cellulases were observed upon their adsorption on lignin carrying preadsorbed surfactant. Weak electrostatic interactions were determined in aqueous media at pH between 4.8 and 5.5 for the native cellulolytic lignins (MPCEL and WSCEL), whereby a ∼20% reduction in the enzyme affinity was observed. This was mainly explained by electrostatic interactions (osmotic pressure effects) between charged lignins and cellulases. Noteworthy, adsorption of nonionic surfactants onto cellulose, in the form cellulose nanofibrils, did not affect its hydrolytic conversion. Overall, our results highlight the benefit of nonionic surfactant pretreatment to reduce nonproductive enzyme binding while maintaining the reactivity of the cellulosic substrate.

Adsorption of Glycinin and β-Conglycinin on Silica and Cellulose: Surface Interactions as a Function of Denaturation, pH, and Electrolytes

Soybean proteins have found uses in different nonfood applications due to their interesting properties. We report on the kinetics and extent of adsorption on silica and cellulose surfaces of glycinin and β-conglycinin, the main proteins present in soy. Quartz crystal microgravimetry (QCM) experiments indicate that soy protein adsorption is strongly affected by changes in the physicochemical environment. The affinity of glycinin and the mass adsorbed on silica and cellulose increases (by ca. 13 and 89%, respectively) with solution ionic strength (as it increases from 0 to 100 mM NaCl) due to screening of electrostatic interactions. In contrast, β-conglycinin adsorbs on the same substrates to a lower extent and the addition of electrolyte reduces adsorption (by 25 and 57%, respectively). The addition of 10 mM 2-mercaptoethanol, a denaturing agent, reduces the adsorption of both proteins with a significant effect for glycinin. This observation is explained by the cleavage of disulfide bonds which allows unfolding of the molecules and promotes dissociation into subunits that favors more compact adsorbed layer structures. In addition, adsorption of glycinin onto cellulose decreases with lowering the pH from neutral to pH 3 due to dissociation of the macromolecules, resulting in flatter adsorbed layers. The respective adsorption isotherms fit a Langmuir model and QCM shifts in energy dissipation and frequency reveal multiple-step kinetic processes indicative of changes in adlayer structure.

Experimental and computational study of the effect of alcohols on the solution and adsorption properties of a nonionic symmetric triblock copolymer.

This study investigates the effect of alcohols on the solution and adsorption properties of symmetric triblock nonionic copolymers comprising blocks of ethylene oxide (EO) and propylene oxide (PO) (EO(37)PO(56)EO(37)). The cloud point, surface tension, critical micelle concentration (CMC), and maximum packing at the air-water interface are determined, and the latter is compared to the amount of polymer that adsorbs from solution onto polypropylene (PP) and cellulose surfaces. The interaction energy and radius of micelles are calculated by using molecular dynamics (MD) simulations. Equivalent MD bead parameters were used in dynamic density functional theory (DDFT) simulations to study the influence of alcohols on the phase behavior of EO(37)PO(56)EO(37) and its adsorption on PP from aqueous solutions. The simulation results agree qualitatively with the experimental observations. Ethanol acts as a good cosolvent for EO(37)PO(56)EO(37) and reduces the amount of EO(37)PO(56)EO(37) that adsorbs on PP surfaces; however, little or no influence is observed on the adsorption on cellulose. Interestingly, longer chain alcohols, such as 1-pentanol, produce the opposite effect. Overall, the solution and adsorption properties of nonionic symmetric triblock copolymers in the presence of alcohols are rationalized by changes in solvency and the hydrophobic effect.

Nanocellulose and Proteins: Exploiting Their Interactions for Production, Immobilization, and Synthesis of Biocompatible Materials

Nanocellulose has been used with promising results as reinforcement material in composites, many of which include hydrophobic polymers. However, the hydrophilic nature of nanocellulose can be better exploited in composites that incorporate high surface energy systems as well as in applications that can benefit from such properties. In fact, proteins can be ideal components in these cases. This paper reviews such aspects, which are based on the remarkable mechanical properties of nanocellulose. This material also exhibits low density, high aspect ratio, high surface area, and can be modified by substitution of its abundant hydroxyl groups. It also shows biocompatibility, low toxicity, and biodegradability. Convenient biotechnological methods for its production are of interest not only because of the possible reduction in processing energy but also because of positive environmental aspects. Thus, enzymatic treatments are favorable for effecting fiber deconstruction into nanocellulose. In addition to reviewing nanocellulose production by enzymatic routes, we discuss incorporation of enzyme activity to produce biodegradable systems for biomedical applications and food packaging. Related applications have distinctive features that take advantage of protein–cellulose interactions and the possibility of changing nanocellulose properties via enzymatic or protein treatments.

Role of textile substrate hydrophobicity on the adsorption of hydrosoluble nonionic block copolymers

The adsorption of polyalkylene glycols and co-polymers of ethylene oxide and propylene oxide on substrates relevant to textiles with varying surface energies (cellulose, polypropylene, nylon and polyester) was studied by using quartz crystal microgravimetry. Langmuirian-type isotherms were observed for the adsorption profiles of nonionic block polymers of different architectures. The affinity with the surfaces is discussed based on experimental observations, which highlights the role of hydrophobic effects. For a given type of block polymer, micellar and monomeric adsorption is governed by the balance of polymer structure (mainly, chain length of hydrophobic segments) and substrates surface energy.