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•13C CP-MAS NMR can be used to reliably quantify the composition of cellulose and polyester in textile blends.•Sigmoidal calibration functions describe the correlation between ...cellulose and polyester signals in the NMR spectrum.•It is also possible to apply solid-state NMR to determine the crystallinity of cellulose in cotton polyester blended textiles.
The valorization of cellulose rich textile waste is promoted by the development of a novel solid-state NMR method for the quantification of cellulose and polyester in textile blends. We applied 13C CP-MAS NMR as a tool for the quantification and structural characterization of cellulose in cotton polyester blends. Gaussian functions were used to integrate the spectra obtained from a set of calibration standards in order to calculate a sigmoidal calibration curve. Acid hydrolysis was chosen as a reference method. The results demonstrated that solid-state NMR enables a reliable determination of cellulose and polyester in both preconsumer and postconsumer waste textiles and suggests a possible extension of the concept to blends of man-made cellulose fibers (MMCFs) and polyester.
We show that composite hydrogels comprising methyl cellulose (MC) and cellulose nanocrystal (CNC) colloidal rods display a reversible and enhanced rheological storage modulus and optical ...birefringence upon heating, i.e., inverse thermoreversibility. Dynamic rheology, quantitative polarized optical microscopy, isothermal titration calorimetry (ITC), circular dichroism (CD), and scanning and transmission electron microscopy (SEM and TEM) were used for characterization. The concentration of CNCs in aqueous media was varied up to 3.5 wt % (i.e, keeping the concentration below the critical aq concentration) while maintaining the MC aq concentration at 1.0 wt %. At 20 °C, MC/CNC underwent gelation upon passing the CNC concentration of 1.5 wt %. At this point, the storage modulus ( G') reached a plateau, and the birefringence underwent a stepwise increase, thus suggesting a percolative phenomenon. The storage modulus ( G') of the composite gels was an order of magnitude higher at 60 °C compared to that at 20 °C. ITC results suggested that, at 60 °C, the CNC rods were entropically driven to interact with MC chains, which according to recent studies collapse at this temperature into ring-like, colloidal-scale persistent fibrils with hollow cross-sections. Consequently, the tendency of the MC to form more persistent aggregates promotes the interactions between the CNC chiral aggregates towards enhanced storage modulus and birefringence. At room temperature, ITC shows enthalpic binding between CNCs and MC with the latter comprising aqueous, molecularly dispersed polymer chains that lead to looser and less birefringent material. TEM, SEM, and CD indicate CNC chiral fragments within a MC/CNC composite gel. Thus, MC/CNC hybrid networks offer materials with tunable rheological properties and access to liquid crystalline properties at low CNC concentrations.
Fiber spinning of anionic TEMPO-oxidized cellulose (TOCN) nanofibrils with polycations by interfacial polyelectrolyte complexation is demonstrated. The formed fibers were mostly composed of cellulose ...nanofibrils and the polycations were a minor constituent, leading to yield and ultimate strengths of ca. 100 MPa and ca. 200 MPa, and Young's modulus of ca. 15 GPa. Stretching of the as-formed wet filaments of TOCN/polycation by 20% increased the Young's modulus, yield strength, and ultimate tensile strength by approximately 45, 36, and 26%, respectively. Importantly, feasibility of compartmentalized wound bicomponent fibers by simultaneous spinning of two fibers of different compositions and entwining them together was shown. This possibility was further exploited to demonstrate reversible shape change of a bicomponent fiber directly by humidity change, and indirectly by temperature changes based on thermally dependent humidity absorption. The demonstrated route for TOCN-based fiber preparation is expected to open up new avenues in the application of nanocelluloses in advanced fibrous materials, crimping, and responsive smart textiles.
Details of the phase separation of the poly(N-vinylcaprolactam) (PVCL) homopolymers and block copolymers of PVCL and poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) were studied in aqueous buffer ...solutions. Phase separation occurred at either one or two temperatures depending on pH. The lower critical solution temperature of PVCL can be fine-tuned by varying the molecular weight of the block, whereas the phase separation temperature of the PDMAEMA block is strongly dependent on pH. The enthalpies of the collapse of the PVCL homopolymer and PVCL-b-PDMAEMA block copolymers were measured and show that the blocks phase separate independently upon heating. PVCL is known to bind amphiphilic cations, and correspondingly, according to light scattering, the block copolymers dissolve as single molecules but also form aggregates at room temperature. At temperatures above the cloud points of both blocks, only homogeneous large aggregates were observed. Zeta potential measurements confirmed that, upon heating, PDMAEMA blocks turn out from the collapsed PVCL globule toward the aqueous phase.
•10–100 mL ultrasonic standing wave chamber with an acoustically soft reflecting boundary for oleogel structural modification was developed.•Bulk and local mechanical properties of modified oleogels ...were studied by uniaxial compression tests and by scanning acoustic microscopy.•Structural properties of oleogels were elucidated by fitting a hyperelastic foam model on uniaxial compression data.•The stability of modified oleogels was compared to control samples using an automated image analysis oil-release method.
Lipid-based materials, such as substitutes for saturated fats (oleogels) structurally modified with ultrasonic standing waves (USW), have been developed by our group. To enable their potential application in food products, pharmaceuticals, and cosmetics, practical and economical production methods are needed. Here, we report scale-up of our procedure of structurally modifying oleogels via the use of USW by a factor of 200 compared to our previous microfluidic chamber. To this end, we compared three different USW chamber prototypes through finite element simulations (FEM) and experimental work. Imaging of the internal structure of USW-treated oleogels was used as feedback for successful development of chambers, i.e., the formation of band-like structures was the guiding factor in chamber development. We then studied the bulk mechanical properties by a uniaxial compression test of the sonicated oleogels obtained with the most promising USW chamber, and sampled local mechanical properties using scanning acoustic microscopy. The results were interpreted using a hyperelastic foam model. The stability of the sonicated oleogels was compared to control samples using automated image analysis oil-release tests. This work enabled the effective mechanical-structural manipulation of oleogels in volumes of 10–100 mL, thus paving the way for USW treatments of large-scale lipid-based materials.
This study aims at extending the understanding of the toxicity mechanism of ionic liquids (ILs) using various analytical methods and cytotoxicity assays. The cytotoxicity of eight ILs and one ...zwitterionic compound was determined using mammalian and bacterial cells. The time dependency of the IL toxicity was assessed using human corneal epithelial cells. Hemolysis was performed using human red blood cells and the results were compared with destabilization data of synthetic liposomes upon addition of ILs. The effect of the ILs on the size and zeta potential of liposomes revealed information on changes in the lipid bilayer. Differential scanning calorimetry was used to study the penetration of the ILs into the lipid bilayer. Pulsed field gradient nuclear magnetic resonance spectroscopy was used to determine whether the ILs occurred as unimers, micelles, or if they were bound to liposomes. The results show that the investigated ILs can be divided into three groups based on the cytotoxicity mechanism: cell wall disrupting ILs, ILs exerting toxicity through both cell wall penetration and metabolic alteration, and ILs affecting solely on cell metabolism.
Ionic liquids: The toxicity of ionic liquids is predicted using biomimicking‐liposomes instead of living organisms and the results are in a good agreement with the cytotoxicity results obtained using various cell lines.
Stabilization of the enzymes under stress conditions is of special interest for modern biochemistry, bioengineering, as well as for formulation and target delivery of protein-based drugs. Aiming to ...achieve an efficient stabilization at elevated temperature with no influence on the enzyme under normal conditions, we studied chaperone-like activity of thermoresponsive polymers based on poly(dimethylaminoethyl methacrylate) (PDMAEMA) toward two different proteins, glyceraldehyde-3-phosphate dehydrogenase and chicken egg lysozyme. The polymers has been shown to do not interact with the folded protein at room temperature but form a complex upon heating to either protein unfolding or polymer phase transition temperature. A PDMAEMA-PEO block copolymer with a dodecyl end-group (d-PDMAEMA-PEO) as well as PDMAEMA-PEO without the dodecyl groups protected the denatured protein against aggregation in contrast to PDMAEMA homopolymer. No effect of the polymers on the enzymatic activity of the client protein was observed at room temperature. The polymers also partially protected the enzyme against inactivation at high temperature. The results provide a platform for creation of artificial chaperones with unfolded protein recognition which is a major feature of natural chaperones.
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