Bio-inspired magnetically responsive silicone cilia: fabrication strategy and interaction with biological mucus

Cilia are biological structures essential to drive the mobility of secretions and maintain the proper function of the respiratory airways. However, this motile self-cleaning process is significantly compromised in the presence of silicone tracheal prosthesis, leading to biofilm growth and impeding effective treatment. To address this challenge and enhance the performance of these devices, we propose the fabrication of magnetic silicone cilia, with the prospect of their integration onto silicone prostheses. The present study presents a fabrication method based on magnetic self-assembly and assesses the interaction behavior of the cilia array with biological mucus. This protocol allows for the customization of cilia dimensions across a wide range of aspect ratios (from 6 to 85) and array densities (from 10 to 80 cilia/mm2) by adjusting the fabrication parameters, offering flexibility for adjustments according to their required characteristics. Furthermore, we evaluated the suitability of different cilia arrays for biomedical applications by analyzing their interaction with bullfrog mucus, simulating the airways environment. Our findings demonstrate that the fabricated cilia are mechanically resistant to the viscous fluid and still exhibit controlled movement under the influence of an external moving magnet. A correlation between cilia dimensions and mucus wettability profile suggests a potential role in facilitating mucus depuration, paving the way for further advancements aimed at enhancing the performance of silicone prostheses in clinical settings.

Bio-Inspired Magnetically Responsive Silicone Cilia: Fabrication Strategy and Interaction with Biological Mucus.

Cilia are biological structures essential to drive the mobility of secretions and maintain the proper function of the respiratory airways. However, this motile self-cleaning process is significantly compromised in the presence of silicone tracheal prosthesis, leading to biofilm growth and impeding effective treatment. To address this challenge and enhance the performance of these devices, we propose the fabrication of magnetic silicone cilia, with the prospect of their integration onto silicone prostheses. The present study presents a fabrication method based on magnetic self-assembly and assesses the interaction behavior of the cilia array with biological mucus. This protocol allows for the customization of cilia dimensions across a wide range of aspect ratios (from 6 to 85) and array densities (from 10 to 80 cilia/mm2) by adjusting the fabrication parameters, offering flexibility for adjustments according to their required characteristics. Furthermore, we evaluated the suitability of different cilia arrays for biomedical applications by analyzing their interaction with bullfrog mucus, simulating the airways environment. Our findings demonstrate that the fabricated cilia are mechanically resistant to the viscous fluid and still exhibit controlled movement under the influence of an external moving magnet. A correlation between cilia dimensions and mucus wettability profile suggests a potential role in facilitating mucus depuration, paving the way for further advancements aimed at enhancing the performance of silicone prostheses in clinical settings.

Cubosome-carrying bacterial cellulose membrane as a versatile drug delivery platform.

Using advanced nanotechnology membranes has opened up new possibilities in the field of biomedicine, particularly for controlled drug delivery and especially for topical use. Bacterial cellulose membranes (BCM), particularly, have gained prominence owing to their distinctive attributes, including remarkable water retention, safety, biodegradability, and tunable gas exchange. However, they are aqueous matrices and, for this reason, of limited capacity for incorporation of apolar compounds. Cubosomes are lipid nanoparticles composed of a surfactant bicontinuous reverse cubic phase, which, owing to their bicontinuous structure, can incorporate both polar and apolar compounds. Therefore, these particles present a promising avenue for encapsulating and releasing drugs and biomolecules due to their superior entrapment efficiency. In this study, we aim to extend earlier investigations using polymeric hydrogels for cubosome immobilization, now using BCMs, a more resilient biocompatible matrix. Phytantriol cubosome-loaded BCMs were prepared by three distinct protocols: ex situ incorporation into wet BCMs, ex situ incorporation by swelling of dry BCMs, and an in situ process with the growth of BCMs in a sterile medium already containing cubosomes. Our investigation revealed that these methodologies ensured that cubosomes remained integral, uniformly distributed, and thoroughly dispersed within the membrane, as confirmed using Small-Angle X-ray Scattering (SAXS) and high-resolution confocal microscopy. The effective incorporation and sustained release of diclofenac were validated across the different BCMs and compared with hyaluronic acid (HA) hydrogel in our previous studies. Furthermore, the resistance against cubosome leaching from the three BCM and HA hydrogel samples was quantitatively evaluated and contrasted. We hope that the outcomes from this research will pave the way for innovative use of this platform in the incorporation and controlled release of varied active agents, amplifying the already multifaceted applicability of BCMs.

Assessing the Structure and Equilibrium Conditions of Complex Coacervate Core Micelles by Varying Their Shell Composition and Medium Ionic Strength.

Complex coacervates result from an associative phase separation commonly involving oppositely charged polyelectrolytes. When this associative interaction occurs between charged-neutral diblock copolymers and oppositely charged homopolymers, a nanometric aggregate called a complex coacervate core micelle, C3M, is formed. Recent studies have addressed the issue of their thermodynamic or kinetic stability but without a clear consensus. To further investigate this issue, we have studied C3Ms formed by the combination of poly(diallyldimethylammonium) and copolymer poly(acrylamide)-b-poly(acrylate) using different preparation protocols. Dynamic light scattering and small-angle X-ray scattering measurements suggest that these structures are in an equilibrium condition because the aggregates do not vary with different preparation protocols or upon aging. In addition, their stability and structures are critically dependent on several parameters such as the density of neutral blocks in their shell and the ionic strength of the medium. Decreasing the amount of copolymer in the system and, hence, the density of neutral blocks in the shell results in an increase in the aggregate size because of the core growth, although their globular shape is retained. On the other hand, larger clusters of micelles were formed at higher ionic strengths. Partially replacing 77% of the copolymer with a homopolymer of the same charge or increasing the ionic strength of the system (above 100 mmol L-1 NaCl) leads to a metastable state, after which phase separation is eventually observed. SAXS analyses reveal that this phase separation above a certain salt concentration occurs due to the coagulation of individual micelles that seem to retain their individual globular structures. Overall, these results confirm earlier claims that equilibrium C3Ms are achieved close to 1:1 charge stoichiometry but also reveal that these conditions may vary at different shell densities or higher ionic strengths, which constitute vital information for envisioning future applications of C3Ms.

Chitosan/Virgin-Coconut-Oil-Based System Enriched with Cubosomes: A 3D Drug-Delivery Approach.

Emulsion-based systems that combine natural polymers with vegetable oils have been identified as a promising research avenue for developing structures with potential for biomedical applications. Herein, chitosan (CHT), a natural polymer, and virgin coconut oil (VCO), a resource obtained from coconut kernels, were combined to create an emulsion system. Phytantriol-based cubosomes encapsulating sodium diclofenac, an anti-inflammatory drug, were further dispersed into CHT/VCO- based emulsion. Then, the emulsions were frozen and freeze-dried to produce scaffolds. The scaffolds had a porous structure ranging from 20.4 to 73.4 µm, a high swelling ability (up to 900%) in PBS, and adequate stiffness, notably in the presence of cubosomes. Moreover, a well-sustained release of the entrapped diclofenac in the cubosomes into the CHT/VCO-based system, with an accumulated release of 45 ± 2%, was confirmed in PBS, compared to free diclofenac dispersed (80 ± 4%) into CHT/VCO-based structures. Overall, the present approach opens up new avenues for designing porous biomaterials for drug delivery through a sustainable pathway.

Complexes of Charged-Neutral Block Copolymers and Surfactants: Process-Dependent Features and Long-Term Stability of Their Aqueous Dispersions.

Aqueous dispersions of charged-neutral block copolymers (poly(acrylamide)-b-poly(acrylate)) complexed with an oppositely charged surfactant (dodecyltrimethylammonium) have been prepared by different approaches: the simple mixing of two solutions (MS approach) containing the block copolymer and surfactant, with their respective simple counterions, and dispersion of a freeze-dried complex salt prepared in the absence of simple counterions (CS approach). The CS particles were investigated under different conditions: dispersion of a CS in salt-free water and dispersion of a CS in a dilute salt solution, the latter condition yielding dispersions with the same composition as the MS process. Additionally, aged dispersions (up to 6 months) and dispersed complexes of the polyacrylate homopolymer and dodecyltrimethylammonium surfactant were evaluated. By employing different characterization techniques, it was seen that dispersions prepared by the MS approach display nanometric spherical particles with disordered cores, and poor colloidal stability, partially caused by the absence of surface charge (ζ-potential close to zero). Oppositely, anisometric particles were formed in CS dispersions and were large enough to sustain micellar cubic cores. The CS particles presented long-time colloidal stability, partially due to a net negative surface charge, but the stability varied with the length of the neutral block composing the corona. Our results demonstrate that all dispersed particles are metastable structures, with physicochemical properties strongly dependent on the preparation procedure, thus making these particles suitable for fundamental studies and potential applications where accurate control of their properties, including size, shape, internal structure, and stability, is desired.

Interaction of polyelectrolyte-shell cubosomes with serum albumin for triggering drug release in gastrointestinal cancer.

Nano-structured and functionalized materials for encapsulation, transport, targeting and controlled release of drugs are of high interest to overcome low bioavailability in oral administration. We develop lipid-based cubosomes, which are surface-functionalized with biocompatible chitosan-N-arginine and alginate, displaying internal liquid crystalline structures. Polyelectrolyte-shell (PS) cubosomes have pH-responsive characteristics profitable for oral delivery. The obtained PScubosomes can strongly interact with serum albumin, a protein which is released in the stomach under gastric cancer conditions. An effective thermodynamic PScubosome-protein interaction was characterized at pH 2.0 and 7.4 by isothermal titration calorimetry at 37 °C. A high increment of the albumin conformation transition temperature was evidenced by differential scanning calorimetry upon incubation with PScubosomes. The performed structural studies by synchrotron small-angle X-ray scattering (SAXS) revealed essential alterations in the internal liquid crystalline topology of the nanocarriers including an Im3m to Pn3m transition and a reduction of the cubic lattice parameters. The PScubosome nanoparticle interaction with serum albumin, leading to inner structural changes in a range of temperatures, promoted the release of water from the cubosomal nanochannels. Altogether, the results revealed effective interactions of the PScubosomes with albumin under simulated gastrointestinal pH conditions and suggested promising nanocarrier characteristics for triggered oral drug release.

Assessing the Contribution of the Neutral Blocks in DNA/Block-Copolymer Polyplexes: Poly(acrylamide) vs. Poly(ethylene Oxide).

The interaction of DNA with different block copolymers, namely poly (trimethylammonium chloride methacryloyoxy)ethyl)-block-poly(acrylamide), i.e., (PTEA)-b-(PAm), and poly (trimethylammonium chloride methacryloyoxy)ethyl)-block-poly(ethylene oxide), i.e., (PTEA)-b-(PEO), was studied. The nature of the cationic block was maintained fixed (PTEA), whereas the neutral blocks contained varying amounts of acrylamide or (ethylene oxide) units. According to results from isothermal titration microcalorimetry measurements, the copolymers interaction with DNA is endothermic with an enthalpy around 4.0 kJ mol−1 of charges for (PTEA)-b-(PAm) and 5.5 kJ mol−1 of charges for (PTEA)-b-(PEO). The hydrodynamic diameters of (PTEA)-b-(PEO)/DNA and (PTEA)-b-(PAm)/DNA polyplexes prepared by titration were around 200 nm at charge ratio (Z+/−) < 1. At Z+/− close and above 1, the (PTEA)50-b-(PAm)50/DNA and (PTEA)50-b-(PAm)200/DNA polyplexes precipitated. Interestingly, (PTEA)50-b-(PAm)1000/DNA polyplexes remained with a size of around 300 nm even after charge neutralization, probably due to the size of the neutral block. Conversely, for (PTEA)96-b-(PEO)100/DNA polyplexes, the size distribution was broad, indicating a more heterogeneous system. Polyplexes were also prepared by direct mixture at Z+/− of 2.0, and they displayed diameters around 120−150 nm, remaining stable for more than 10 days. Direct and reverse titration experiments showed that the order of addition affects both the size and charge of the resulting polyplexes.

Stabilizing both oil droplets and titanium dioxide nanoparticles in aqueous dispersion with nanofibrillated cellulose.

Nanocellulose is a well-known stabilizer for several colloidal dispersions, including emulsions and solid nanoparticles, replacing surfactants, polymers, and other additives, and therefore providing more minimalistic and eco-friendly formulations. However, could this ability be extended to stabilize oil droplets and inorganic nanoparticles simultaneously in the same colloidal system? This work aimed to answer this question. We evaluated both cationic and anionic nanofibrillated celluloses to stabilize both titanium dioxide nanoparticles and oil droplets. The resulting suspensions held their macroscopic stability for up to 2 months, regardless of pH or surface charge. Cryo-TEM images revealed a complex network formation involving nanofibers and TiO2 nanoparticles, which agrees with the high viscosity values and gel-like behavior found in rheology measurements. We propose that the formation of this network is responsible for the simultaneous stabilization of oil droplets and TiO2 nanoparticles, and that this may be used as a formulation tool for other complex systems.

How to Predict the Order of Phase Separation of Polyelectrolyte Complexes and Their Miscibility.

The mixture of two oppositely charged polyelectrolyte solutions results in complexation that may lead to an associative phase separation, forming a highly concentrated phase in both polyelectrolytes in equilibrium with a dilute phase. In this work, we aim to investigate what controls the order of complexation when more polyelectrolytes of the same charge are present. For this, the effect of the addition of a third oppositely charged polyelectrolyte in a mixture of two polyelectrolytes with the same charge was studied. Our results show that, under certain conditions, the electrostatic complexation takes place selectively, where one polyanion (or polycation) phase separates first, followed by the other phase separation, with both complexes at their 1:1 charge stoichiometry. Infrared analyses of the phase-separated complexes confirmed that, in a mixture of polyanions, poly(styrenesulfonate) is complexed first, followed by poly(acrylate). For polycations, these analyses showed that poly(diallyldimethylammonium) is preferentially complexed over poly(allylamine). These results suggest that electrostatic complexation occurs following the sequence predicted as in an acid/base titration, where the acidic/basic strength of the involved polyions dictates which one is complexed first. In this respect, the order of complexation can be associated with the equivalence pH for each pair, which we propose can be used as a parameter to predict phase separation in polyelectrolyte mixtures. In addition, we have investigated the miscibility of these complex mixtures, confirming that multiphasic complexes are formed whenever the polyions display ionizable groups with different acid/basic strengths and that this can also be related to their equivalence pH.

Versatile Diblock Polyampholytes Can Form Two Types of Charged and Internally Structured Core-Shell Particles by Complexation with Cationic or Anionic Surfactants.

We used diblock poly(acrylic acid)-b-poly(2-dimethylamino ethyl methacrylate) (PAA-b-PDMAEMA) polyampholytes to prepare core-shell complexes with ionic surfactants. The dispersions have been characterized by means of small-angle X-ray scattering (SAXS), cryogenic transmission electron microscopy (Cryo-TEM), dynamic light-scattering, and zeta potential methods. Using cationic or anionic surfactants it is possible to produce particles with either positively or negatively charged shells, both having an internal liquid-crystalline core structure. For the different systems, different preparation protocols were found to be successful to produce stable and reproducible particles. The particle morphologies depend on the surfactant used. Complexes with the cationic surfactant hexadecyltrimethylammonium (CTA+) form oblate particles, while complexes with dodecyl sulfate (DS-) form cylindrical rods. In both complexes, the smallest dimension of the core does not exceed twice the block length of the core-forming polymer block. For the particles with CTA+, nonelectrostatic attractive interactions among the PDMAEMA chains in the shells seem to be present, affecting the particle shape. In both types of particles, the surfactant in the core forms rod-like aggregates, arranged in a two-dimensional hexagonal structure with the surfactant rods aligned with the axis of rotational symmetry in the particle. With charged polymer chains in the shell, the aggregates present a striking stability over time, displaying no change in particle size over the time scale investigated (10 months). Nevertheless, the aggregates are highly dynamic in nature, and their shapes and structures can be changed dramatically in dispersion, without intermediate precipitation, by changes in the composition of the medium. Specifically, a transition from aggregates with cationic surfactant to aggregates with anionic surfactant can be achieved.

Characterization of cubosomes immobilized in hydrogels of hyaluronic acid and their use for diclofenac controlled delivery.

Cubosomes are dispersions of bicontinuous surfactant phases that constitute an assertive option to carry and release drugs and biomolecules, offering high efficiency of entrapment and specificity towards biological targets. This paper reports, for the first time to the best of our knowledge, the immobilization and characterization of cubosomes in chemically cross-linked oxi-hyaluronic acid and the evaluation of their use for controlled delivery of diclofenac, which is chosen as a model drug. Immobilized cubosomes prepared with phytantriol and bearing either negative or positive charges (in this case due to the addition of a cationic surfactant) were characterized by small angle X-ray scattering (SAXS) analysis and high-resolution confocal microscopy, confirming that their internal structure remains unaltered and that they appear uniformly distributed within the hydrogel matrix. Their release properties were assessed, and a limited leaching of the cubosomes from the hydrogel matrix with sustained release of the entrapped diclofenac was confirmed. These results enable the use of immobilized cubosomes as an attractive platform for biomedical applications, significantly extending the already promising features of cubosomes.

Molecular Assembly in Block Copolymer-Surfactant Nanoparticle Dispersions: Information on Molecular Exchange and Apparent Solubility from High-Resolution and PFG NMR.

Internally structured block copolymer-surfactant particles are formed when the complex salts of ionic-neutral block copolymers neutralized by surfactant counterions are dispersed in aqueous media. Here, we report the 1H NMR signal intensities and self-diffusion coefficients (D, from pulsed field gradient nuclear magnetic resonance, PFG NMR) of trimethyl alkylammonium surfactant ions and the poly(acrylamide)-block-poly(acrylate) (PAAm-b-PA) polyions forming such particles. The results reveal the presence of an "NMR-invisible" (slowly exchanging) fraction of aggregated surfactant ions in the particle core and an "NMR-visible" fraction consisting of surface surfactant ions in rapid exchange with the surfactant ions dissociated into the aqueous domain. They also confirm that the neutral PAAm blocks are exposed to water at the particle surface, while the PA blocks are buried in the particle core. The self-diffusion of the polyions closely agree with the self-diffusion of a hydrophobic probe molecule solubilized in the particles, showing that essentially all copolymer chains are incorporated in the aggregates. Through centrifugation, we prepared macroscopically phase-separated systems with a phase concentrated in particles separated from a clear dilute phase. D values for the surfactant and block copolymer indicated that the dilute phase contained small aggregates (ca. 5 nm) of surfactant ions and a few anionic-neutral block copolymer chains. Regardless of the overall concentration of the sample, the fraction of block copolymer found in the dilute phase was nearly constant. This indicates that the dilute fraction represented a tail of small particles created by the dispersion process rather than a true thermodynamic solubility of the complex salts.

Preparation of Poly(acrylate)/Poly(diallyldimethylammonium) Coacervates without Small Counterions and Their Phase Behavior upon Salt Addition towards Poly-Ions Segregation.

In this work, we report the phase behavior of polyelectrolyte complex coacervates (PECs) of poly(acrylate) (PA-) and poly(diallyldimethylammonium) (PDADMA+) in the presence of inorganic salts. Titrations of the polyelectrolytes in their acidic and alkaline forms were performed to obtain the coacervates in the absence of their small counterions. This approach was previously applied to the preparation of polymer-surfactant complexes, and we demonstrate that it also succeeded in producing complexes free of small counterions with a low extent of Hofmann elimination. For phase behavior studies, two different molar masses of poly(acrylate) and two different salts were employed over a wide concentration range. It was possible to define the regions at which associative and segregative phase separation take place. The latter one was exploited in more details because the segregation phenomenon in mixtures of oppositely charged polyelectrolytes is scarcely reported. Phase composition analyses showed that there is a strong segregation for both PA- and PDADMA+, who are accompanied by their small counterions. These results demonstrate that the occurrence of poly-ion segregation in these mixtures depends on the anion involved: in this case, it was observed with NaCl, but not with Na2SO4.

From Associative to Segregative Phase Separation: The Phase Behavior of Poly(acrylate)/Dodecyltrimethylammonium Complex Salts in the Presence of NaBr and NaCl.

We report here a systematic study on the phase behavior of dodecyltrimethylammonium-poly(acrylate) (C12TAPA) complex salts upon addition of simple salts (NaBr and NaCl). Complex salts of poly(acrylate) of two molar masses were employed (2000 and 450,000 g mol-1). Systems containing different surfactant mesophases were observed, whose structures were elucidated by small-angle X-ray scattering analyses. Overall, we observe a transition from associative to segregative phase separation intercalated with monophasic regions. In terms of surfactant association, a transition from micellar cubic phases to an isotropic micellar solution was observed, where these two phases occur in equilibrium with a dilute phase as a consequence of associative phase separation. However, as the salt concentration increases, segregative phase separation is observed, and scattering analyses of the surfactant-rich phase indicate the growth of micellar aggregates. These results are discussed in terms of the electrolyte effect screening the interactions between the oppositely charged surfactant and polymer and as a result of salting-out effects of the different electrolytes that prevail at higher concentrations.

Latanoprost-loaded phytantriol cubosomes for the treatment of glaucoma.

Glaucoma is a degenerative optic neuropathy characterized by increased intraocular pressure that if untreated can result in blindness. Ophthalmological drug therapy is a challenge of great clinical importance due to the diversity of ocular biological barriers which commonly causes limited or no effectiveness for drugs delivered through the eye. In this work, we proposed the development of nanosized cubic liquid crystals (cubosomes) as a new drug carrier system for latanoprost, an anti-glaucoma drug. Latanoprost-loaded phytantriol cubosomes (CubLnp) were prepared using a top-down method. Latanoprost concentration in the formulations ranged from 0.00125% to 0.02% w/v. All cubosomes displayed an average size around 200 nm, a low polydispersity index of 0.1 and zeta potential values around -25 mV, with an encapsulation efficiency of about 90%. Structural studies revealed that cubosomes displayed a double-diamond surface, Pn3m cubic-phase structure, and was not affected by drug loading. Calorimetric studies revealed a fast and exothermic interaction between latanoprost and cubosomes. According to in vitro essays, latanoprost release from cubosomes was slow in time, evidencing a sustained release profile. Based on this behavior, the in vivo hypotensive intraocular effect was evaluated by means of the subconjunctival administration of CubLnp in normotensive rabbits. We obtained promising results in comparison with a marketed latanoprost formulation (0.005% w/v).

Effect of Molecular Architecture and Composition on the Aggregation Pathways of POEGMA Random Copolymers in Water.

Understanding of the temperature-induced phase transition of poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) random copolymers with varied composition remains largely incomplete. Upon heating they can form either macroscopically phase-separated aggregates or micelles. We examined the effect of polymer architecture by rationally designing and synthesizing various POEGMA copolymer structures via atom transfer radical polymerization using OEGMA monomers of different EO lengths. Micelle formation occurred for copolymers with a small fraction of long side chains counterbalanced by an appropriate number of short side chains, while macroscopic phase separation occurred for other copolymer compositions. In some copolymer compositions and architectures, micelle formation followed by macroscopic phase separation occurred, and the temperature of these phase transitions could be tailored accordingly. This new strategy allows the control over the microstructure and specific transition temperatures enabling, for instance, the preparation of nanocarriers for encapsulating hydrophobic compounds.

Adhesive Sponge Based on Supramolecular Dimer Interactions as Scaffolds for Neural Stem Cells.

Improving cell-material interactions of nonadhesive scaffolds is crucial for the success of biomaterials in tissue engineering. Due to their high surface area and open pore structure, sponges are widely reported as absorbent materials for biomedical engineering. The biocompatibility and biodegradability of polysaccharide sponges, coupled with the chemical functionalities of supramolecular dimers, make them promising combinations for the development of adhesive scaffolds. Here, a supramolecular tactic based on (UPy)-modified polysaccharide associated with three-dimensional structure of sponges was developed to reach enhanced cellular adhesion. For this purpose, three approaches were examined individually in order to accomplish this goal. In the first approach, the backbone polysaccharides with noncell adhesive properties were modified via a modular tactic using UPy-dimers. Hereupon, the physical-chemical characterizations of the supramolecular sponges were performed, showing that the presence of supramolecular dimers improved their mechanical properties and induced different architectures. In addition, small-angle neutron scattering (SANS) measurements and rheology experiments revealed that the UPy-dimers into agarose backbone are able to reorganize in thinning aggregates. It is also demonstrated that the resulted UPy-agarose (AGA-UPy) motifs in surfaces can promote cell adhesion. Finally, the last approach showed the great potential for use of this novel material in bioadhesive scaffolds indicating that neural stem cells show a spreading bias in soft materials and that cell adhesion was enhanced for all UPy-modified sponges compared to the reference, i.e. unmodified sponges. Therefore, by functionalizing sponge surfaces with UPy-dimers, an adhesive supramolecular scaffold is built which opens the opportunity its use neural tissues regeneration.

Inclusion Complexation between α-Cyclodextrin and Oligo(ethylene glycol) Methyl Ether Methacrylate.

The preparation of inclusion complexes based on α-cyclodextrin (α-CD) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA) was investigated aiming to reveal complexation particularities and thermodynamic and kinetic aspects as a function of the oligomer architecture. Small-angle X-ray scattering and isothermal titration calorimetry measurements revealed that oligomer molecular weight controls both the kinetics and thermodynamics of inclusion. Unlike linear ethylene glycol polymers, OEGMA groups possess a methacrylate group, which seems to act as a stopper, affecting their mode of complexation. Nuclear magnetic resonance spectra and relaxation measurements support the fact that methacrylate groups lie outside the α-CD ring and that a full sequential complexation of the oligomer ethylene oxide groups is not observed. These results allied to the temperature sensitivity of these oligomers and enable possible routes for chemical modifications and design of new stimuli-responsive materials.

Double stabilization mechanism of O/W Pickering emulsions using cationic nanofibrillated cellulose.

HYPOTHESIS: Hydrophobic oleic acid/water interfaces are negatively charged. Hence, the use of cationic nanocelluloses as stabilizers of Pickering emulsions could improve the colloidal stability due to the electrostatic complexation at the oil-water interface. EXPERIMENTS: Two cationic nanofibrillated cellulose (cNFCs) with two degrees of substitution were prepared and used as stabilizers of Pickering emulsions. The adsorption of cNFCs at the oil: water interface was evaluated by interfacial tension, atomic force microscopy, and centrifugation measurements. LUMiSizer and optical microscopy techniques were used to analyze the colloidal stability and oil droplets morphology, respectively. Besides, the rheological behavior of the continuous aqueous phase was determined through flow and stress sweep curves. Finally, the dispersion of cNFCs in a diluted emulsion was visualized by cryogenic transmission electron microscopy (cryo-TEM). FINDINGS: Cationic NFCs were more efficient in partitioning to the oil:water interface compared to their anionic analogous, oCNF. The electrostatic attraction between the positively charged trimethylammonium groups and the negatively charged deprotonated oleic acid reduced the interfacial tension and improved the colloidal stability of O/W Pickering emulsions. cNFCs dispersed in the aqueous phase were found to increase the viscosity, decelerating the oil drops coalescence. Therefore, the stabilization of cNFCs Pickering emulsions had a synergistic effect from the electrostatic complexation at the liquid-liquid interface and network formation in the aqueous phase, as visualized by cryo-TEM.