Analysis of the Heterogeneities of First and Second Order of Cellulose Derivatives: A Complex Challenge

The complexity of the substituent distribution in polysaccharide derivatives is discussed and defined. The challenges regarding analytical characterization that results from various interrelated categories of distributions, including molecular weight, chemical composition, and microstructure, are outlined. Due to these convoluted levels of complexity, results should always be interpreted with carefulness. Various analytical approaches which have been applied to starch and cellulose derivatives are recapped, including enzymatic, mass spectrometric, and chromatographic methods. The relation of heterogeneities of first and second order among and along the polysaccharide chains is addressed. Finally, examples of own analytical work on cellulose ethers are presented, including the MS analysis of methyl cellulose (MC) blends and fractionation studies of fully esterified MC, especially its 4-methoxybenzoates by gradient HPLC on normal phase. Preparative fractionation according to the degree of substitution (DS) allows follow-up analysis in order to get more detailed information on the substituent distribution in such sub-fractions.

Methylcellulose–Cellulose Nanocrystal Composites for Optomechanically Tunable Hydrogels and Fibers

Chemical modification of cellulose offers routes for structurally and functionally diverse biopolymer derivatives for numerous industrial applications. Among cellulose derivatives, cellulose ethers have found extensive use, such as emulsifiers, in food industries and biotechnology. Methylcellulose, one of the simplest cellulose derivatives, has been utilized for biomedical, construction materials and cell culture applications. Its improved water solubility, thermoresponsive gelation, and the ability to act as a matrix for various dopants also offer routes for cellulose-based functional materials. There has been a renewed interest in understanding the structural, mechanical, and optical properties of methylcellulose and its composites. This review focuses on the recent development in optically and mechanically tunable hydrogels derived from methylcellulose and methylcellulose–cellulose nanocrystal composites. We further discuss the application of the gels for preparing highly ductile and strong fibers. Finally, the emerging application of methylcellulose-based fibers as optical fibers and their application potentials are discussed.

Free Volume and Water Sorption by Cellulose Esters

The results ofthe sorption properties of cellulose acetate (CA) with different degrees of substitution (SD) are summarised. It has been shown that the sorption capacity of CA in water vapour decreases naturally with increasing content of acetate groups in monomeric units of cellulose ethers. The experimental isotherms are analysed according to the double sorption model. Hydrate numbers of hydroxyl and acetate groups were determined. The paired parameters of the Flory–Huggins interaction were calculated. It is shown that the decrease of the Langmuir component is due to the replacement of hydroxyl groups by ester groups, whose local sorption capacity by water vapour is lower than the sorption capacity of OH groups. In the area of high humidity, there is an increase in vacancy sizes due to plasticisation of the sorbents.

Methylcellulose-Cellulose Nanocrystal Composites for Optomechanically Tunable Hydrogels and Fibers

Chemical modification of cellulose offers routes for structurally and functionally diverse biopolymer derivatives for numerous industrial applications. Among cellulose derivatives, cellulose ethers have found extensive use, such as emulsifiers, in food industries and biotechnology. Methylcellulose, one of the simplest cellulose derivatives, has been utilized for biomedical, construction materials and cell culture applications. Its improved water solubility, thermoresponsive gelation, and the ability to act as a matrix for various dopants also offer routes for cellulose-based functional materials. There has been a renewed interest in understanding the structural, mechanical, and optical properties of methylcellulose and its composites. This review focuses on the recent development in optically and mechanically tunable hydrogels derived from methylcellulose and methylcellulose-cellulose nanocrystal composites. We further discuss the application of the gels for preparing highly ductile and strong fibers. Finally, the emerging application of methylcellulose-based fibers as optical fibers and their application potentials are discussed.

Comparative Assessment of the Quality of Aerosol Filters for the Analysis of Ambient Air Pollution

Introduction. Atmospheric aerosols contain many carcinogenic and toxic substances, a significant part of which is represented by heavy metals. Traditionally, metal analysis is preceded by air sampling on AFA-HA-20 filters; yet, the lack of regulations on permitted background levels of trace elements in the filter material may limit reliability of measurements. Selection of filters with similar technological parameters can be a way to improve analytical accuracy. Objective: To determine contamination of different types of filters and to establish its effect on the results of spectral analysis of airborne metal concentrations in a large industrial city. Materials and methods: We analyzed unexposed AFA-HA-20 filters and Merck Millipore MF filters (n = 30 each) for the content of 13 heavy metals identified as priority pollutants within the Federal Clean Air Project. To assess the effect of filter contamination on the analytical error, air sampling was performed by exposing Merck Millipore MF filters at mobile monitoring stations in the city of Lipetsk. The filters were then analyzed by inductively coupled plasma mass spectrometry with prior microwave mineralization. Results: Our findings confirm the repeatedly obtained data on metal contents in null AFA-HA-20 filters and indicate significantly lower levels of contamination of unexposed Millipore MF filters made of mixed cellulose ethers. Conclusions: The risk of obtaining false positive and false negative results depends on the level and variability of the content of a particular trace metal in the filter. The AFA-HA-20 type of filters traditionally used for ambient air sampling may itself confound measurement result.

Viscoelasticity and Solution Stability of Cyanoethylcellulose with Different Molecular Weights in Aqueous Solution

Water-soluble cellulose ethers are widely used as stabilizers, thickeners, and viscosity modifiers in many industries. Understanding rheological behavior of the polymers is of great significance to the effective control of their applications. In this work, a series of cyanoethylcellulose (CEC) samples with different molecular weights were prepared with cellulose and acrylonitrile in NaOH/urea aqueous solution under the homogeneous reaction. The rheological properties of water-soluble CECs as a function of concentration and molecular weight were investigated using shear viscosity and dynamic rheological measurements. Viscoelastic behaviors have been successfully described by the Carreau model, the Ostwald-de-Waele equation, and the Cox–Merz rule. The entanglement concentrations were determined to be 0.6, 0.85, and 1.5 wt% for CEC-11, CEC-7, and CEC-3, respectively. All of the solutions exhibited viscous behavior rather than a clear sol-gel transition in all tested concentrations. The heterogeneous nature of CEC in an aqueous solution was determined from the Cox–Merz rule due to the coexistence of single chain complexes and aggregates. In addition, the CEC aqueous solutions showed good thermal and time stability, and the transition with temperature was reversible.

Decrease in Skin Prion-Seeding Activity of Prion-Infected Mice Treated with a Compound Against Human and Animal Prions: a First Possible Biomarker for Prion Therapeutics

Previous studies have revealed that the infectious scrapie isoform of prion protein (PrPSc) harbored in the skin tissue of patients or animals with prion diseases can be amplified and detected through the serial protein misfolding cyclic amplification (sPMCA) or real-time quaking-induced conversion (RT-QuIC) assays. These findings suggest that skin PrPSc-seeding activity may serve as a biomarker for the diagnosis of prion diseases; however, its utility as a biomarker for prion therapeutics remains largely unknown. Cellulose ethers (CEs, such as TC-5RW), widely used as food and pharmaceutical additives, have recently been shown to prolong the lifespan of prion-infected mice and hamsters. Here we report that in transgenic (Tg) mice expressing hamster cellular prion protein (PrPC) infected with the 263K prion, the prion-seeding activity becomes undetectable in the skin tissues of TC-5RW-treated Tg mice by both sPMCA and RT-QuIC assays, whereas such prion-seeding activity is readily detectable in the skin of untreated mice. Notably, TC-5RW exhibits an inhibitory effect on the in vitro amplification of PrPSc in both skin and brain tissues by sPMCA and RT-QuIC. Moreover, we reveal that TC-5RW is able to directly decrease protease-resistant PrPSc and inhibit the seeding activity of PrPSc from chronic wasting disease and various human prion diseases. Our results suggest that the level of prion-seeding activity in the skin may serve as a useful biomarker for assessing the therapeutic efficacy of compounds in a clinical trial of prion diseases and that TC-5RW may have the potential for the prevention/treatment of human prion diseases.

EFFECT OF MAGNETIC FIELD ON RHEOLOGICAL PROPERTIES OF CELLULOSE ETHERS SOLUTIONS

The rheological properties, structure and phase transitions of hydroxypropyl cellulose in ethanol, dimethyl sulfoxide, ethylene glycol solutions and ethylcellulose in dimethylformamide solutions are studied using viscometry, the cloud-point method, polarization microscopy, the optical interferometry and a polarization photoelectric apparatus in the temperature range 280-360 K. The temperature-concentration regions of isotropic and anisotropic phases are determined for all systems. The type of boundary curves of phase diagrams is compared with the chemical structure of macromolecules. It is shown that the constant magnetic field (3.6 kOe) leads to the orientation of macromolecules in solutions. The domain structure arising in solutions is fixed after evaporation of a solvent and shown in orientation of strips of the film relief. It was found that the flow curves of all solutions at 298 K in the range of shear rates from 0 to 15 s-1 are typically for the non-Newtonian liquids. It was found that the magnetic field leads to an increase in the viscosity of isotropic solutions and a decrease in the viscosity of anisotropic solutions. Both effects depend on the direction of the magnetic field lines. When the rotor-rotation axis is parallel to the direction of power lines of the magnetic field the change in the viscosity of solutions is greater than that at perpendicular orientation of the rotor-rotation axis and power lines of the magnetic field. The results are discussed using representations about the changes in the macromolecule conformation and in the size and shape of the supramolecular particles in the solutions during flow under a magnetic field with different orientation of the power lines.