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.

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.

Nanocellulose-based foam morphological, mechanical and thermal properties in relation to hydrogel precursor structure and rheology.

Foams were prepared from nanocellulose-based hydrogel precursors using a freeze-drying process. The work mainly aims at investigating the relationships between the mechanical and thermal properties of foams and the rheological properties of their hydrogel precursors, which were characterized in a previous paper. The structure of foams was characterized by SEM and confocal microscopy, their elasticity by compression tests, and their thermal conductivity by hot strip as well as transient pulsed techniques. A strong correlation was shown between the elastic properties of foams and those of their hydrogel precursors, and a minimum thermal conductivity was shown to appear at a cellulose volume fraction corresponding to a transition in viscoelastic properties of hydrogels. Results suggest that foams and hydrogels share common microstructural features, which makes it possible to tune the mechanical and thermal properties of foams by tuning the rheological properties of their hydrogel precursors.

Ultra-fast heat dissipating aerogels derived from polyaniline anchored cellulose nanofibers as sustainable microwave absorbers.

Electromagnetic (EM) pollution is ubiquitous and has soared to a great extent in the past few decades. The use of plant sourced cellulose nanofibers to fabricate sustainable and high performance electromagnetic shielding materials is foreseen as a green solution by the electronics industry to address this unseen pollutant. In this view, we report a facile and environmentally benign strategy to synthesize ultra-light and highly conductive aerogels derived from cellulose nanofibers (CNF) decorated with polyaniline (PANI) via a simple in-situ polymerization and subsequent freeze drying process devoid of any volatile organic solvents. The obtained conductive aerogels exhibited density as low as 0.01925 g/cc with a maximum EMI shielding value -32 dB in X band region. These porous shields demonstrated strong microwave absorption behavior (95 %) with minimal reflection (5 %) coupled with high specific EMI SE value ∼1667 dB.cm3. g-1 which make these aerogels a potential candidate for use in telecommunication, military and defense applications.

Robust Superhydrophobic Cellulose Nanofiber Aerogel for Multifunctional Environmental Applications.

The fabrication of superadsorbent for dye adsorption is a hot research area at present. However, the development of low-cost and highly efficient superadsorbents against toxic textile dyes is still a big challenge. Here, we fabricated hydrophobic cellulose nanofiber aerogels from cellulose nanofibers through an eco-friendly silanization reaction in liquid phase, which is an extremely efficient, rapid, cheap, and environmentally friendly procedure. Moreover, the demonstrated eco-friendly silanization technique is easy to commercialize at the industrial level. Most of the works that have reported on the hydrophobic cellulose nanofiber aerogels explored their use for the elimination of oil from water. The key novelty of the present work is that the demonstrated hydrophobic cellulose nanofibers aerogels could serve as superadsorbents against toxic textile dyes such as crystal violet dye from water and insulating materials for building applications. Here, we make use of the possible hydrophobic interactions between silane-modified cellulose nanofiber aerogel and crystal violet dye for the removal of the crystal violet dye from water. With a 10 mg/L of crystal violet (CV) aqueous solution, the silane-modified cellulose nanofiber aerogel showed a high adsorption capacity value of 150 mg/g of the aerogel. The reason for this adsorption value was due to the short-range hydrophobic interaction between the silane-modified cellulose nanofiber aerogel and the hydrophobic domains in crystal violet dye molecules. Additionally, the fabricated silane-modified cellulose nanofiber hydrophobic aerogels exhibited a lower thermal conductivity value of 0.037 W·m-1 K-1, which was comparable to and lower than the commercial insulators such as mineral wools (0.040 W·m-1 K-1) and polystyrene foams (0.035 W·m-1 K-1). We firmly believe that the demonstrated silane-modified cellulose nanofiber aerogel could yield an eco-friendly adsorbent that is agreeable to adsorbing toxic crystal violet dyes from water as well as active building thermal insulators.

Structure and rheology of aqueous suspensions and hydrogels of cellulose nanofibrils: Effect of volume fraction and ionic strength.

The structure and rheology of TEMPO-oxidized cellulose nanofibrils (CNF) suspensions and hydrogels, used as precursors in the elaboration of bio-based aerogels for thermal insulation applications, were studied as a function of CNF volume fraction and ionic strength. The CNF geometry and rigidity were evaluated using AFM observations. Viscometric measurements, performed at very low CNF concentrations, highlighted the prominent role played by electroviscous effects, which can be modulated by ionic strength. Oscillatory measurements on semi-dilute CNF suspensions revealed the formation of a three-dimensional hydrogel network above a percolation fraction, which was shown to depend on the ionic strength. The rheological properties of CNF hydrogels were shown to depend on CNF fraction and ionic strength. In deionized water, the existence of two different concentration regimes was discussed in terms of network structural characteristics and CNF interactions.

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.

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.

FAK dimerization controls its kinase-dependent functions at focal adhesions.

Focal adhesion kinase (FAK) controls adhesion-dependent cell motility, survival, and proliferation. FAK has kinase-dependent and kinase-independent functions, both of which play major roles in embryogenesis and tumor invasiveness. The precise mechanisms of FAK activation are not known. Using x-ray crystallography, small angle x-ray scattering, and biochemical and functional analyses, we show that the key step for activation of FAK's kinase-dependent functions--autophosphorylation of tyrosine-397--requires site-specific dimerization of FAK. The dimers form via the association of the N-terminal FERM domain of FAK and are stabilized by an interaction between FERM and the C-terminal FAT domain. FAT binds to a basic motif on FERM that regulates co-activation and nuclear localization. FAK dimerization requires local enrichment, which occurs specifically at focal adhesions. Paxillin plays a dual role, by recruiting FAK to focal adhesions and by reinforcing the FAT:FERM interaction. Our results provide a structural and mechanistic framework to explain how FAK combines multiple stimuli into a site-specific function. The dimer interfaces we describe are promising targets for blocking FAK activation.

Characterization of phospholipid bilayer formation on a thin film of porous SiO2 by reflective interferometric Fourier transform spectroscopy (RIFTS).

Classical methods for characterizing supported artificial phospholipid bilayers include imaging techniques such as atomic force microscopy and fluorescence microscopy. The use in the past decade of surface-sensitive methods such as surface plasmon resonance and ellipsometry, and acoustic sensors such as the quartz crystal microbalance, coupled to the imaging methods, have expanded our understanding of the formation mechanisms of phospholipid bilayers. In the present work, reflective interferometric Fourier transform spectrocopy (RIFTS) is employed to monitor the formation of a planar phospholipid bilayer on an oxidized mesoporous Si (pSiO(2)) thin film. The pSiO(2) substrates are prepared as thin films (3 µm thick) with pore dimensions of a few nanometers in diameter by the electrochemical etching of crystalline silicon, and they are passivated with a thin thermal oxide layer. A thin film of mica is used as a control. Interferometric optical measurements are used to quantify the behavior of the phospholipids at the internal (pores) and external surfaces of the substrates. The optical measurements indicate that vesicles initially adsorb to the pSiO(2) surface as a monolayer, followed by vesicle fusion and conversion to a surface-adsorbed lipid bilayer. The timescale of the process is consistent with prior measurements of vesicle fusion onto mica surfaces. Reflectance spectra calculated using a simple double-layer Fabry-Perot interference model verify the experimental results. The method provides a simple, real-time, nondestructive approach to characterizing the growth and evolution of lipid vesicle layers on the surface of an optical thin film.

Transfer on hydrophobic substrates and AFM imaging of membrane proteins reconstituted in planar lipid bilayers.

The lipid-layer technique allows reconstituting transmembrane proteins at a high density in microns size planar membranes and suspended to a lipid monolayer at the air/water interface. In this paper, we transferred these membranes onto two hydrophobic substrates for further structural analysis of reconstituted proteins by Atomic Force Microscopy (AFM). We used a mica sheet covered by a lipid monolayer or a sheet of highly oriented pyrolytic graphite (HOPG) to trap the lipid monolayer at the interface and the suspended membranes. In both cases, we succeeded in the transfer of large membrane patches containing densely packed or 2D-crystallized proteins. As a proof of concept, we transferred and imaged the soluble Shiga toxin bound to its lipid ligand and the ATP-binding cassette (ABC) transporter BmrA reconstituted into a planar bilayer. AFM imaging with a lateral resolution in the nanometer range was achieved. Potential applications of this technique in structural biology and nanobiotechnology are discussed.

Preferential insertion of lactose permease in phospholipid domains: AFM observations.

We report the insertion of a transmembrane protein, lactose permease (LacY) from Escherichia coli (E. coli), in supported lipid bilayers (SLBs) of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol (POPG), in biomimetic molar proportions. We provide evidence of the preferential insertion of LacY in the fluid domains. Analysis of the self-assembled protein arrangements showed that LacY: (i) is inserted as a monomer within fluid domains of SLBs of POPE:POPG (3:1, mol/mol), (ii) has a diameter of approx. 7.8nm; and (iii) keeps an area of phospholipids surrounding the protein that is compatible with shells of phospholipids.

The gelsolin:calponin complex nucleates actin filaments with distinct morphologies.

Gelsolin and calponin are cytoskeletal and signalling proteins that form a tight 1:1 complex (GCC). We show that calponin within the GCC inhibits the rate of gelsolin mediated nucleation of actin polymerization. The actin-binding function of calponin is ablated within the GCC as the actin-binding site overlaps with one of the gelsolin binding sites. The structure of filaments that result from nucleation by GCC are different to those nucleated by gelsolin alone in that they are longer, loosely bundled and stain heterogeneously with phalloidin. GCC nucleated filaments appear contorted and wrap around each to form the loose bundles.

Calcium-induced formation of subdomains in phosphatidylethanolamine-phosphatidylglycerol bilayers: a combined DSC, 31P NMR, and AFM study.

We study the effect of Ca(2+) on the lateral segregation of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol (POPG) (3:1, mol/mol). Supported lipid bilayers (SLBs) were observed by atomic force microscopy (AFM). Since SLBs are formed from liposomes of POPE:POPG, we examined the effect of calcium on these suspensions by differential scanning calorimetry (DSC) and (31)P nuclear magnetic resonance spectroscopy ((31)P NMR). AFM images revealed the existence of two separated phases, the higher showing a region with protruding subdomains. Force spectroscopy (FS) was applied to clarify the nature of each phase. The values of breakthrough force (F(y)), adhesion force (F(adh)), and height extracted from the force curves were assigned to the corresponding gel (L(beta)) and fluid (L(alpha)) phase. The endotherms obtained by DSC suggest that, in the presence of Ca(2+), phase separation already exists in the suspensions of POPE:POPG used to form SLBs. Due to the temperature changes applied during preparation of SLBs a (31)P NMR study was performed to assess the lamellar nature of the samples before spreading them onto mica. With in situ AFM experiments we showed that the binding of Ca(2+) to POPG-enriched domains only induces the formation of subdomains in the L(beta) phase.

Influence of mono- and divalent ions on the formation of supported phospholipid bilayers via vesicle adsorption.

We have used the quartz crystal microbalance with dissipation monitoring (QCM-D) technique to investigate how mono- and divalent cations influence the formation of supported (phospho)lipid bilayers (SPB, SLB), occurring via deposition of nanosized palmitoyloleoyl phosphatidylcholine (POPC) vesicles on a SiO2 support. This process is known to proceed via initial adsorption of intact vesicles until a critical surface coverage is reached, where the combination of vesicle-surface and vesicle-vesicle interaction causes the vesicles to rupture. New vesicles then rupture and the lipid fragments fuse until a final continuous bilayer is formed. We have explored how this process and the critical coverage are influenced by different mono- and divalent ions and ion concentrations, keeping the anions the same throughout the experiments. The same qualitative kinetics is observed for all cations. However, different ions cause quite different quantitative kinetics. When compared with monovalent ions, even very small added concentrations of divalent cations cause a strong reduction of the critical coverage, where conversion of intact, adsorbed vesicles to bilayer occurs. This bilayer promoting effect increases in the order Sr2+Na+>K+. The results are of practical value for preparation of lipid bilayers and help shed light on the role of ions and on electrostatic effects at membrane surfaces/interfaces.

Temperature-dependent imaging of living cells by AFM.

Characterization of lateral organization of plasma membranes is a prerequisite to the understanding of membrane structure-function relationships in living cells. Lipid-lipid and lipid-protein interactions are responsible for the existence of various membrane microdomains involved in cell signalization and in numerous pathologies. Developing approaches for characterizing microdomains associate identification tools like recognition imaging with high-resolution topographical imaging. Membrane properties are markedly dependent on temperature. However, mesoscopic scale topographical information of cell surface in a temperature range covering most of cell biology experimentation is still lacking. In this work we have examined the possibility of imaging the temperature-dependent behavior of eukaryotic cells by atomic force microscopy (AFM). Our results establish that the surface of living CV1 kidney cells can be imaged by AFM, between 5 and 37 degrees C, both in contact and tapping modes. These first temperature-dependent data show that large cell structures appeared essentially stable at a microscopic scale. On the other hand, as shown by contact mode AFM, the surface was highly dynamic at a mesoscopic scale, with marked changes in apparent topography, friction, and deflection signals. When keeping the scanning conditions constant, a progressive loss in the image contrast was however observed, using tapping mode, on decreasing the temperature.

Influence of nanotopography on phospholipid bilayer formation on silicon dioxide.

We have investigated the effect of well-defined nanoscale topography on the 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) lipid vesicle adsorption and supported phospholipid bilayer (SPB) formation on SiO2 surfaces using a quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). Unilamellar lipid vesicles with two different sizes, 30 and 100 nm, were adsorbed on pitted surfaces with two different pit diameters, 110 and 190 nm, as produced by colloidal lithography, and the behavior was compared to results obtained on flat surfaces. In all cases, complete bilayer formation was observed after a critical coverage of adsorbed vesicles had been reached. However, the kinetics of the vesicle-to-bilayer transformation, including the critical coverage, was significantly altered by surface topography for both vesicle sizes. Surface topography hampered the overall bilayer formation kinetics for the smaller vesicles, but promoted SPB formation for the larger vesicles. Depending on vesicle size, we propose two modifications of the precursor-mediated vesicle-to-bilayer transformation mechanism used to describe supported lipid bilayer formation on the corresponding flat surface. Our results may have important implications for various lipid-membrane-based applications using rough or topographically structured surfaces.

Characterizing the interactions between GPI-anchored alkaline phosphatases and membrane domains by AFM.

In plasma membranes, most glycosylphosphatidylinositol-anchored proteins (GPI proteins) would be associated with ordered microdomains enriched in sphingolipids and cholesterol. Debates on the composition and the nano- or mesoscales organization of these membrane domains are still opened. This complexity of biomembranes explains the use, in the recent years, of both model systems and atomic force microscopy (AFM) approaches to better characterize GPI proteins/membranes interactions. So far, the studies have mainly been focused on alkaline phosphatases of intestinal (BIAP) or placental (PLAP) origins reconstituted in model systems. The data show that GPI-anchored alkaline phosphatases (AP-GPI) molecules inserted in supported membranes can be easily imaged by AFM, in physiological buffer. They are generally observed in the most ordered domains of model membranes under phase separation, i.e. presenting both fluid and ordered domains. This direct access to the membrane structure at a mesoscopic scale allows establishing the GPI protein induced changes in microdomains size. It provides direct evidence for the temperature-dependent distribution of a GPI protein between fluid and ordered membrane domains. Origins of reported differences in the behavior of BIAP and PLAP are discussed. Finally, advantages and limits of AFM in the study of GPI proteins/membrane domains interactions are presented in this review.