Nanocellulose-Based Hybrid Scaffolds for Skin and Bone Tissue Engineering: A 10-Year Overview.

Cellulose, the most abundant polymer on Earth, has been widely utilized in its nanoform due to its excellent properties, finding applications across various scientific fields. As the demand for nanocellulose continues to rise and its ease of use becomes apparent, there has been a significant increase in research publications centered on this biomaterial. Nanocellulose, in its different forms, has shown tremendous promise as a tissue engineered scaffold for regeneration and repair. Particularly, nanocellulose-based composites and scaffolds have emerged as highly demanding materials for both soft and hard tissue engineering. Medical practitioners have traditionally relied on collagen and its analogue, gelatin, for treating tissue damage. However, the limited mechanical strength of these biopolymers restricts their direct use in various applications. This issue can be overcome by making hybrids of these biopolymers with nanocellulose. This review presents a comprehensive analysis of the recent and most relevant publications focusing on hybrid composites of collagen and gelatin with a specific emphasis on their combination with nanocellulose. While bone and skin tissue engineering represents two areas where a majority of researchers are concentrating their efforts, this review highlights the use of nanocellulose-based hybrids in these contexts.

Facile fabrication of arecanut palm sheath based robust hydrophobic cellulose nanopapers via self-assembly of ZnO nanoflakes and its shelf-life prediction for sustainable packaging applications.

Cellulose nanofibers have been extracted from arecanut palm sheath fibers via mild oxalic acid hydrolysis coupled with steam explosion technique. Cellulose nanofibers with diameter of 20.23 nm were obtained from arecanut palm sheath fibers. A series of robust hydrophobic cellulose nanopapers were fabricated by combining the synergistic effect of surface roughness induced by the successful deposition of zinc oxide (ZnO) nanoflakes and stearic acid modification via a simple and cost-effective method. In this work, agro-waste arecanut palm sheath was employed as a novel source for the extraction of cellulose nanofibers. 2 wt% of ZnO nanoflakes and 1 M concentration of stearic acid were used to fabricate mechanically robust hydrophobic cellulose nanopapers with a water contact angle (WCA) of 134°. During the deposition of zinc oxide nanoflakes on the CNP for inducing surface roughness, a hydrogen bonding interaction is formed between the hydroxyl groups of cellulose nanofibers and the zinc oxide nanoflakes. When this surface roughened CNP was dipped in stearic acid solution. The hydroxyl groups in zinc oxide nanoflakes undergoes esterification reaction with carboxyl groups in stearic acid solution forming an insoluble stearate layer and thus inducing hydrophobicity on CNP. The fabricated hydrophobic cellulose nanopaper displayed a tensile strength of 22.4 MPa and better UV blocking ability which is highly desirable for the sustainable packaging material in the current scenario. Furthermore, the service life of the pristine and modified cellulose nanopapers was predicted using the Arrhenius equation based on the tensile properties obtained during the accelerated ageing studies. The outcome of this study would be broadening the potential applications of hydrophobic and mechanically robust cellulose nanopapers in sustainable packaging applications.

Surfactant Assisted In Situ Synthesis of Nanofibrillated Cellulose/Polymethylsilsesquioxane Aerogel for Tuning Its Thermal Performance.

Nanofibrillated cellulose (NFC) and polymethylsilsesquioxane (PMSQ) based aerogel are prepared by the sol-gel method. The objective of this work is to study the impact of surfactant and base catalyst on the thermal and mechanical performance of the corresponding aerogel. The rheological premonitory assists in predicting the bulk properties of the aerogel. The chemical structure of the aerogel is studied by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and solid-state nuclear magnetic resonance (NMR). X-ray microtomographic (XMT) analysis confirms the homogeneous and monolithic structure of the aerogel. The lowest thermal conductivity is achieved as 23.21 mW m-1 K-1 with V-0 and HBF rating through UL-94 test. Thermal performance of aerogels is cross-verified through modeling and simulation in COMSOL multiphysics platform. The mechanical properties of aerogel are evaluated by monolithic compression test in axial and radial compression test up to 90% strain, cyclic compression loading-unloading, and reloading test, flexural test, and dynamic mechanical analysis. The time-temperature analysis has shown around 5 °C temperature difference in the middle of the room after using the aerogel panel at the exposed surface, which assists in the practical application of the synthesized aerogel panel.

Biodegradable Poly(Butylene Succinate) Nanocomposites Based on Dimeric Surfactant Organomodified Clays with Enhanced Water Vapor Barrier and Mechanical Properties.

Biocomposites based on biodegradable polybutylene succinate (PBS) and organomodified clays (OMt) were prepared by melt blending process. The OMt nanofillers were obtained by ion exchange reaction between sodium montmorillonite (Mt) and gemini surfactants bearing 4-decyloxyphenylacetamide hydrophobic chains and ethylene or hexylene spacer. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and rheological measurement results showed that the investigated hybrids present a uniform dispersion with an exfoliation of clay into the PBS matrix, particularly for short spacer surfactant based composites. The effect of organoclay loading and composition on the thermal, mechanical, and barrier properties was also investigated. High clay loading and long gemini surfactant spacer lead to substantial improvement of Young modulus values by 21%, while low clay content induces a reduction of the hybrid's crystallinity due to strong OMt-PBS interactions. Compared to that of the neat PBS film, a significant reduction of the water vapor permeability (WVP) by 28% was obtained by adding only 3 wt % of PBS/OMt (2) which opens up prospects for this material in the field of food packaging. This study shows that gemini surfactant-modified organoclays can be used as effective nanofillers in a PBS matrix to access to value-added nanocomposites.

Mechanical and Hygroscopic Properties of Molded Pulp Products Using Different Wood-Based Cellulose Fibers.

With an increasing interest for molded pulp product (MPP) in the industry, it is important to fully understand how the manufacturing process is different from papermaking. One specific way to differentiate the processes is to compare their resulting products. As the paper industry uses several wood fibers with various pulping processes, it is interesting to compare some of these fibers, to further progress our understanding of the MPP process. In this study, six different wood fibers were used (as received) and analyzed to obtain the sample with the lowest moisture uptake and highest tensile properties. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and fiber analysis module (MorFi) observations were performed, as well as moisture uptake measurements after sorption and tensile tests. We observed significant differences between the fibers tested. Kraft fibers (bleached softwood kraft pulp (BSKP), bleached hardwood kraft pulp (BHKP), and unbleached softwood kraft pulp (USKP)) showed smoother surfaces and less non-cellulosic molecules, such as hemicellulose, lignin, and pectin, in the SEM images. Bleached chemi-thermomechanial pulp (BCTMP) and recycled pulps (R-NPM and R-CBB) both showed non-cellulosic molecules and rougher surfaces. These results were confirmed with the FTIR analysis. With kraft fibers, MPP mechanical properties were lower than non-kraft fibers. Resulting moisture uptake is in between the recycled fibers (lowest moisture uptake) and BCTMP (highest moisture uptake). The removal of non-cellulosic molecules reduces the mechanical properties of the resulting MPP. The incorporation of non-wood molecules, as found in recycled fibers, also reduces the mechanical properties, as well as moisture uptake, when compared with BCTMP.

Polylactic acid/Gemini surfactant modified clay bio-nanocomposites: Morphological, thermal, mechanical and barrier properties.

To improve PLA's properties and overcome its drawbacks such us poor thermal stability, resistance and gas barrier properties, several studies have been performed using different nanofillers. In this work, PLA nanocomposites reinforced by three organoclays, OMt(8-4-8), OMt(10-4-10) and OMt(12-4-12) at various weight percentages (1 and 3 wt%) were prepared by melt mixing using a twin-screw extruder. The organoclays were obtained from sodium montmorillionite and gemini surfactants bearing different hydrophobic chain lengths. The resulting nanocomposites have been characterized in terms of composition and morphology by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The thermal stability and cold crystallization behavior were accessed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect of clay composition and concentration on the mechanical and rheological properties of the nanocomposites as well as their water vapor permeability has been also investigated. The resulting nanocomposites exhibit a significantly reduced permeability as compared to unfilled PLA and an improved young modulus and toughness at the detriment of ductility.

Cellulose Nanofiber-Based Polyaniline Flexible Papers as Sustainable Microwave Absorbers in the X-Band.

A series of flexible, lightweight, and highly conductive cellulose nanopapers were fabricated through in situ polymerization of aniline monomer on to cellulose nanofibers with a rationale for attenuating electromagnetic radiations within 8.2-12.4 GHz (X band). The demonstrated paper exhibits good conductivity due to the formation of a continuous coating of polyaniline (PANI) over the cellulose nanofibers (CNF) during in situ polymerization, which is evident from scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction analysis. The free hydroxyl groups on the surface of nanocellulose fibers promptly form intermolecular hydrogen bonding with PANI, which plays a vital role in shielding electromagnetic radiations and makes the cellulose nanopapers even more robust. These composite nanopapers exhibited an average shielding effectiveness of ca. -23 dB (>99% attenuation) at 8.2 GHz with 1 mm paper thickness. The fabricated papers exhibited an effective attenuation of electromagnetic waves by a predominant absorption mechanism (ca. 87%) rather than reflection (ca. 13%), which is highly desirable for the present-day telecommunication sector. Unlike metal-based shields, these demonstrated PANI/CNF papers have given a new platform for designing green microwave attenuators via an absorption mechanism. The prime novelty of the present study is that these robust PANI/CNF nanopapers have the ability to attenuate incoming microwave radiations to an extent that is 360% higher than the shielding effectiveness value reported in the previous literature. This makes them suitable for use in commercial electronic gadgets. This demonstrated work also opens up new avenues for using cellulose nanofibers as an effective substrate for fabricating conductive flexible papers using polyaniline. The direct current conductivity value of PANI/CNF nanopaper was 0.314 S/cm, which is one of the key requisites for the fabrication of efficient electromagnetic shields. Nevertheless, such nanopapers also open up an arena of applications such as electrodes for supercapacitors, separators for Li-S, Li-polymer batteries, and other freestanding flexible paper-based devices.

Thermal Superinsulating Materials Made from Nanofibrillated Cellulose-Stabilized Pickering Emulsions.

Thermal superinsulating properties of biobased materials are investigated via the structuration of aerogels through a biphasic system. Highly stable Pickering emulsions are produced using TEMPO-oxidized cellulose nanofibrils (NFC) adsorbed at an oil/water interface. NFCs form an entangled system of clusters of droplets that lead to excellent mechanical properties. The emulsions produced are strong gels that are further used as template to form aerogels. The freeze-dried emulsions result in porous bioaerogels with extremely low densities (0.012-0.030 g/cm3). We describe a hierarchical morphology with three levels of porosity: an alveolar organization of larger macropores due to ice crystals, spherical smaller macropores induced by the emulsion template, and mesoporous domains localized at the pore walls level. The low-density bioaerogels have compression moduli as high as 1.5 MPa and can be deformed up to 60% strain before the structure collapse. NFC aerogels have thermal superinsulating properties; the lowest thermal conductivity obtained is 0.018 W/(m·K). In the context of the development of sustainable materials, we demonstrate that NFC-stabilized Pickering emulsions are excellent templates to produce fully biobased, mechanically strong thermal superinsulating materials.

Spray freeze-dried nanofibrillated cellulose aerogels with thermal superinsulating properties.

Nanofibrillated cellulose (NFC) aerogels were prepared by spray freeze-drying (SFD). Their structural, mechanical and thermal insulation properties were compared to those of NFC aerogels prepared by conventional freeze-drying (CFD). The purpose of this investigation is to develop superinsulating bioaerogels by reducing their pore size. Severe reduction of the aerogel pore size and skeleton architecture were observed by SEM, aerogels prepared by SFD method show a fibril skeleton morphology, which defines a mesoporous structure. BET analyses confirm the appearance of a new organization structure with pores of nanometric sizes. As a consequence, the thermal insulation properties were significantly improved for SFD materials compared to CFD aerogel, reaching values of thermal conductivity as low as 0.018W/(mK). Moreover, NFC aerogels have a thermal conductivity below that of air in ambient conditions, making them one of the best cellulose based thermal superinsulating material.

Swelling of Poly(n-butyl methacrylate) Films Exposed to Supercritical Carbon Dioxide: A Comparative Study with Polystyrene.

We report here the swelling and relaxation properties of confined poly(n-butyl methacrylate) (PBMA) films having thicknesses of less than 70 nm under supercritical carbon dioxide (scCO2) using the X-ray reflectivity technique. Swellability is found to be dominant in thinner films compared to thicker ones as a consequence of the confinement-induced densification of the former. Swellability is proportionately increased with the density of the film. PBMA films exhibit a more significant swelling than do PS films, and their differences become more prominent with the increase in film thickness. A comparison between the results obtained for polystyrene (PS) and PBMA ultrathin films reveals that the swellability is dependent upon the specific intermolecular interaction between CO2 and the chemical groups available in the polymers. Owing to strong Lewis acid-base interactions with scCO2 and the lower glass-transition temperature (bulk Tg ≈ 29 °C), PBMA films exhibit a greater amount of swelling than do PS films (bulk Tg ≈ 100 °C). Though they reach to the different swollen state upon exposition, identical relaxation behavior as a function of aging time is evidenced. This unprecedented behavior can be ascribed to the strong bonding between trapped CO2 and PBMA that probably impedes the release of CO2 molecules from the swollen PBMA films manifested in suppressed relaxation.

Multi-scale cellulose based new bio-aerogel composites with thermal super-insulating and tunable mechanical properties.

Bio-composite aerogels based on bleached cellulose fibers (BCF) and cellulose nanoparticles having various morphological and physico-chemical characteristics are prepared by a freeze-drying technique and characterized. The various composite aerogels obtained were compared to a BCF aerogel used as the reference. Severe changes in the material morphology were observed by SEM and AFM due to a variation of the cellulose nanoparticle properties such as the aspect ratio, the crystalline index and the surface charge density. BCF fibers form a 3D network and they are surrounded by the cellulose nanoparticle thin films inducing a significant reduction of the size of the pores in comparison with a neat BCF based aerogel. BET analyses confirm the appearance of a new organization structure with pores of nanometric sizes. As a consequence, a decrease of the thermal conductivities is observed from 28mWm(-1)K(-1) (BCF aerogel) to 23mWm(-1)K(-1) (bio-composite aerogel), which is below the air conductivity (25mWm(-1)K(-1)). This improvement of the insulation properties for composite materials is more pronounced for aerogels based on cellulose nanoparticles having a low crystalline index and high surface charge (NFC-2h). The significant improvement of their insulation properties allows the bio-composite aerogels to enter the super-insulating materials family. The characteristics of cellulose nanoparticles also influence the mechanical properties of the bio-composite aerogels. A significant improvement of the mechanical properties under compression is obtained by self-organization, yielding a multi-scale architecture of the cellulose nanoparticles in the bio-composite aerogels. In this case, the mechanical property is more dependent on the morphology of the composite aerogel rather than the intrinsic characteristics of the cellulose nanoparticles.

In Vitro and In Vivo Evaluation of Pectin/Copper Exchanged Faujasite Composite Membranes.

The biocompatibility and excellent ion exchange capacity make faujasites ideal candidates for tissue engineering applications. A novel pectin/copper exchanged faujasite hybrid membrane was synthesized by solvent casting technique, using calcium chloride as the crosslinking agent. AFM images revealed the egg-box model organization of calcium cross-linked pectin chains used as a matrix. The morphology of composite membranes was characterized by SEM and their elemental composition was determined using EDX. The higher contact angle of P (1%) when compared to that of native pectin figured out an enhanced hydrophobicity of hybrid material. The embedded faujasite particles maintained their crystalline structure as revealed by XRD and their interactions with the polymer matrix was evaluated by FTIR. The composite membrane with 1% (w/w) of copper exchanged faujasite, P(1%), exhibited better thermal stability, excellent antibacterial activity, controlled swelling and degradation. Finally, it displayed cell viability of 89% on NIH3T3 fibroblast cell lines and aided in improving wound healing and re-epithelialisation in Sprague Dawley rats. The obtained data suggested their potential as ideal matrices for efficient treatment of burn wounds.

Stability of Polymer Ultrathin Films (<7 nm) Made by a Top-Down Approach.

In polymer physics, the dewetting of spin-coated polystyrene ultrathin films on silicon remains mysterious. By adopting a simple top-down method based on good solvent rinsing, we are able to prepare flat polystyrene films with a controlled thickness ranging from 1.3 to 7.0 nm. Their stability was scrutinized after a classical annealing procedure above the glass transition temperature. Films were found to be stable on oxide-free silicon irrespective of film thickness, while they were unstable (<2.9 nm) and metastable (>2.9 nm) on 2 nm oxide-covered silicon substrates. The Lifshitz-van der Waals intermolecular theory that predicts the domains of stability as a function of the film thickness and of the substrate nature is now fully reconciled with our experimental observations. We surmise that this reconciliation is due to the good solvent rinsing procedure that removes the residual stress and/or the density variation of the polystyrene films inhibiting thermodynamically the dewetting on oxide-free silicon.

Experimental evidence of ultrathin polymer film stratification by AFM force spectroscopy.

By performing Atomic Force Microscopy measurements of pull-off force as a function of the temperature, we were able to probe the dynamic of supported thin polystyrene (PS) films. Thermal transitions induce modifications in the surface energy, roughness and surface modulus that are clearly detected by AFM and related to PS chain relaxation mechanisms. We demonstrated the existence of three transition temperatures that can be associated to the relaxation of polymer chains located at different depth regions within the polymer film. Independently of the film thickness, we have confirmed the presence of a region of high mobility for the polymer chains at the free interface. The thickness of this region is estimated to be above 7nm. The detection of a transition only present for film thicker than the gyration radius Rg is linked to the dynamics of polymer chains in a bulk conformation (i.e. not in contact with the free interface). We claim here that our results demonstrate, in agreement with other techniques, the stratification of thin polymer film depth profile in terms of relaxation behavior.

Wound healing in urology.

Wound healing is a dynamic and complex phenomenon of replacing devitalized tissues in the body. Urethral healing takes place in four phases namely inflammation, proliferation, maturation and remodelling, similar to dermal healing. However, the duration of each phase of wound healing in urology is extended for a longer period when compared to that of dermatology. An ideal wound dressing material removes exudate, creates a moist environment, offers protection from foreign substances and promotes tissue regeneration. A single wound dressing material shall not be sufficient to treat all kinds of wounds as each wound is distinct. This review includes the recent attempts to explore the hidden potential of growth factors, stem cells, siRNA, miRNA and drugs for promoting wound healing in urology. The review also discusses the different technologies used in hospitals to treat wounds in urology, which make use of innovative biomaterials synthesised in regenerative medicines like hydrogels, hydrocolloids, foams, films etc., incorporated with growth factors, drug molecules or nanoparticles. These include surgical zippers, laser tissue welding, negative pressure wound therapy, and hyperbaric oxygen treatment.

Antibacterial and wound healing analysis of gelatin/zeolite scaffolds.

In this article, gelatin/copper activated faujasites (CAF) composite scaffolds were fabricated by lyophilisation technique for promoting partial thickness wound healing. The optimised scaffold with 0.5% (w/w) of CAF, G (0.5%), demonstrated pore size in the range of 10-350 µm. Agar disc diffusion tests verified the antibacterial role of G (0.5%) and further supported that bacterial lysis was due to copper released from the core of CAF embedded in the gelatin matrix. The change in morphology of bacteria as a function of CAF content in gelatin scaffold was studied using SEM analysis. The confocal images revealed the increase in mortality rate of bacteria with increase in concentration of incorporated CAF in gelatin matrix. Proficient oxygen supply to needy cells is a continuing hurdle faced by tissue engineering scaffolds. The dissolved oxygen measurements revealed that CAF embedded in the scaffold were capable of increasing oxygen supply and thereby promote cell proliferation. Also, G (0.5%) exhibited highest cell viability on NIH 3T3 fibroblast cells which was mainly attributed to the highly porous architecture and its ability to enhance oxygen supply to cells. In vivo studies conducted on Sprague Dawley rats revealed the ability of G (0.5%) to promote skin regeneration in 20 days. Thus, the obtained data suggest that G (0.5%) is an ideal candidate for wound healing applications.

Faujasites incorporated tissue engineering scaffolds for wound healing: in vitro and in vivo analysis.

Exploring the possibility of using inorganic faujasites in tissue engineering scaffolds is a prospective approach in regenerative medicine. Novel gelatin/hyaluronic acid (HA)/faujasite porous scaffolds with low surface energy were fabricated by lyophilization. The pore size of gelatin/HA scaffold was 50-2000 µm, whereas it was greatly reduced to 10-250 µm after incorporation of 2.4% (w/w) of faujasites in polymer matrix, GH(2.4%). Micro computed tomography analysis showed that the porosity of GH(2.4%) was 90.6%. The summative effect was ideal for growth of dermal fibroblasts and cellular attachment. XRD analysis revealed that the embedded faujasites maintained their crystallinity in the polymer matrix even though they interacted with the polymers as indicated by FT-IR analysis. Coupling with effective reinforcement of faujasites, GH(2.4%) demonstrated compression modulus of 929 ± 7 Pa and glass transition temperature of 31 ± 0.05 °C. It exhibited controlled swelling and degradation, allowing sufficient space for tissue regrowth. The latter is further supported by capability of faujasites to provide efficient oxygen supply to fibroblast cells. GH(2.4%) showed a cell viability of 91 ± 8% on NIH 3T3 fibroblast cell lines. The in vivo studies on Sprague-Dawley rats revealed its ability to enhance wound healing by accelerating re-epithelization and collagen deposition. These findings indicated its potential as excellent wound dressing material.

Pectin/carboxymethyl cellulose/microfibrillated cellulose composite scaffolds for tissue engineering.

Highly porous three-dimensional scaffolds made of biopolymers are of great interest in tissue engineering applications. A novel scaffold composed of pectin, carboxymethyl cellulose (CMC) and microfibrillated cellulose (MFC) were synthesised using lyophilisation technique. The optimised scaffold with 0.1% MFC, C(0.1%), showed highest compression modulus (~3.987 MPa) and glass transition temperature (~103 °C). The pore size for the control scaffold, C(0%), was in the range of 30-300 µm while it was significantly reduced to 10-250 µm in case of C(0.1%). Using micro computed tomography, the porosity of C(0.1%) was estimated to be 88%. C(0.1%) showed excellent thermal stability and lower degradation rate compared to C(0%). The prepared samples were also characterised using XRD and FTIR. C(0.1%) showed controlled water uptake ability and in vitro degradation in PBS. It exhibited highest cell viability on NIH3T3 fibroblast cell line. These results suggest that these biocompatible composite scaffolds can be used for tissue engineering applications.

Linear rheological properties of low molecular weight polyethylene glycol solutions.

This experimental study of the linear viscoelastic properties of PEG600 aqueous solutions at various concentrations and temperatures mainly aims at getting a better understanding, in concentrated regimes, of the role played on the structural and rheological properties by PEG assembly properties previously evidenced in the dilute regime. The results indicate a peculiar and unique viscoelastic behavior: the elastic modulus versus frequency curves are nearly the same for all concentrations and temperatures investigated. The key role played by hydrogen bonds in the rheological properties of PEG solutions is highlighted. The relaxation on long time scales is indicative of large scale complex associative polymeric structures. A schematic complete phase diagram of PEG600 in water is finally proposed.

Polyethylene glycol aggregates in water formed through hydrophobic helical structures.

The present study was aimed at elucidating the mechanism of aggregation in water of hydroxyl-terminated polyethylene glycol (PEG) of low molecular weight (600 g/mol). The results from fluorescence spectroscopy at different temperatures were consistent with surface tension measurements, suggesting aggregate formation. Indeed, the process of aggregation is accompanied by an increase in the fluorescence emission of a hydrophobic probe. So, PEG aggregates in the form of internal hydrated helices covered with CH(2) groups are shown to yield hydrophobic regions. These regions created upon PEG aggregation in water and at a temperature close to 35°C result from a balance between H bonding and entropic effects. By providing the first experimental evidence for hydrophobic mediation of aggregation with OH-terminated oxy-ethylene chains of low molecular weight, this study highlights their surfactant-like behaviour.