Molecular Characteristics and Antioxidant Activity of Spruce (Picea abies) Hemicelluloses Isolated by Catalytic Oxidative Delignification

Spruce (Piceaabies) wood hemicelluloses have been obtained by the noncatalytic and catalytic oxidative delignification in the acetic acid-water-hydrogen peroxide medium in a processing time of 3–4 h and temperatures of 90–100 °C. In the catalytic process, the H2SO4, MnSO4, TiO2, and (NH4)6Mo7O24 catalysts have been used. A polysaccharide yield of up to 11.7 wt% has been found. The hemicellulose composition and structure have been studied by a complex of physicochemical methods, including gas and gel permeation chromatography, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. The galactose:mannose:glucose:arabinose:xylose monomeric units in a ratio of 5:3:2:1:1 have been identified in the hemicelluloses by gas chromatography. Using gel permeation chromatography, the weight average molar mass Mw of hemicelluloses has been found to attain 47,654 g/mol in noncatalytic delignification and up to 42,793 g/mol in catalytic delignification. Based on the same technique, a method for determining the α and k parameters of the Mark–Kuhn–Houwink equation for hemicelluloses has been developed; it has been established that these parameters change between 0.33–1.01 and 1.57–472.17, respectively, depending on the catalyst concentration and process temperature and time. Moreover, the FTIR spectra of the hemicellulose samples contain all the bands characteristic of heteropolysaccharides, specifically, 1069 cm−1 (C–O–C and C–O–H), 1738 cm−1 (ester C=O), 1375 cm−1 (–C–CH3), 1243 cm−1 (–C–O–), etc. It has been determined by the thermogravimetric analysis that the hemicelluloses isolated from spruce wood are resistant to heating to temperatures of up to ~100 °C and, upon further heating, start destructing at an increasing rate. The antioxidant activity of the hemicelluloses has been examined using the compounds simulating the 2,2-diphenyl-2-picrylhydrazyl free radicals.

Ferulated Pectins from Sugar Beet Bioethanol Solids: Extraction, Macromolecular Characteristics, and Enzymatic Gelling Properties

Pectin from sugar beet (Beta vulgaris L.) (SBP) was extracted from a sugar beet waste (SBW) registering a 4.4% (w/w) yield. SBP presented a weight-average molar mass of 459 kDa, galacturonic acid content of 52.2%, and a low esterification degree (30%). The macromolecular characteristics of SBP revealed a flexible and extended coil chain conformation. The main neutral sugars in SBP were galactose (20.7%), mannose (5.0%), and arabinose (3.60%) while ferulic acid (FA) content was 2.1 µg·mg−1 sample. FA remained in the SBP chain mainly in RG I region even after suffering both, industrial processing and harsh weathering conditions. Consequently, SBP formed covalent gels induced by laccase. Covalent cross-linking content (dimers and trimer of FA) was 0.97 mg·g−1 SBP. The 8-5′, 5-5′, and 8-O-4′ dimers of FA isomers proportions were 75, 17, and 8%, respectively. SBP gels at 4% (w/v ) registered storage (G′) and loss (G″) moduli final values of 44 and 0.66 Pa, respectively. SBP gels were soft and adhesive according to texture profile analysis. Scanning electron microscopy analysis of SBP lyophilized gels revealed an imperfect honeycomb-like structure with 4.5 ± 1.4 µm average cavities diameter.

Functionalizable coaxial PLLA/PDLA nanofibers with stereocomplexes at the internal interface

Multifunctionality of electrospun polylactic acid (PLA) nonwovens was generated by the morphological design of nanofibers. Coaxial fibers with a lower number average molar mass Mn PLLA core and a higher Mn PDLA shell form PDLA–PLLA stereocrystals at the interface, induced by annealing. In tensile tests under physiological conditions, the core–shell fibers with higher crystallinity (22% compared to 11–14%) had lower Young’s moduli E (9 ± 1 MPa) and lower elongation at break εb (26 ± 3%) than PDLA alone (E = 31 ± 9 MPa, εb = 80 ± 5%), which can be attributed to simultaneous crystallization and relaxation effects. Gelatin incorporated in the PDLA phase was presented on the outer surface providing a biointerface putatively favorable for cell adherence. Gelatin incorporation did not influence the crystallization behavior but slightly lowered Tg (60 → 54 °C). Employing exclusively polymers established in the clinic, multifunctionality was generated by design. Graphic abstract

Characterisation of mass distributions of solvent-fractionated lignins using analytical ultracentrifugation and size exclusion chromatography methods

Lignins are valuable renewable resources for the potential production of a large array of biofuels, aromatic chemicals and biopolymers. Yet native and industrial lignins are complex, highly branched and heterogenous macromolecules, properties that have to date often undermined their use as starting materials in lignin valorisation strategies. Reliable knowledge of weight average molar mass, conformation and polydispersity of lignin starting materials can be proven to be crucial to and improve the prospects for the success of such strategies. Here we evaluated the use of commonly-used size exclusion chromatography (SEC)—calibrated with polystyrene sulphonate standards—and under-used analytical ultracentrifugation—which does not require calibration—to characterise a series of lignin fractions sequentially extracted from soda and Kraft alkaline lignins using ethyl acetate, methyl ethyl ketone (MEK), methanol and acetone:water (fractions F01–F04, respectively). Absolute values of weight average molar mass (Mw) determined using sedimentation equilibrium in the analytical ultracentrifuge of (3.0 ± 0.1) kDa and (4.2 ± 0.2) kDa for soda and Kraft lignins respectively, agreed closely with previous SEC-determined Mws and reasonably with the size exclusion chromatography measurements employed here, confirming the appropriateness of the standards (with the possible exceptions of fraction F05 for soda P1000 and F03 for Indulin). Both methods revealed the presence of low (~ 1 kDa) Mw material in F01 and F02 fractions followed by progressively higher Mw in subsequent fractions. Compositional analysis confirmed > 90% (by weight) total lignins successively extracted from both lignins using MEK, methanol and acetone:water (F02 to F04). Considerable heterogeneity of both unfractionated and fractionated lignins was revealed through determinations of both sedimentation coefficient distributions and polydispersity indices. The study also demonstrates the advantages of using analytical ultracentrifugation, both alongside SEC as well as in its own right, for determining absolute Mw, heterogeneity and conformation information for characterising industrial lignins.

Soft, Formstable (Co)Polyester Blend Elastomers

High crystallization rate and thermomechanical stability make polylactide stereocomplexes effective nanosized physical netpoints. Here, we address the need for soft, form-stable degradable elastomers for medical applications by designing such blends from (co)polyesters, whose mechanical properties are ruled by their nanodimensional architecture and which are applied as single components in implants. By careful controlling of the copolymer composition and sequence structure of poly[(L-lactide)-co-(ε-caprolactone)], it is possible to prepare hyperelastic polymer blends formed through stereocomplexation by adding poly(D-lactide) (PDLA). Low glass transition temperature Tg ≤ 0 °C of the mixed amorphous phase contributes to the low Young’s modulus E. The formation of stereocomplexes is shown in DSC by melting transitions Tm > 190 °C and in WAXS by distinct scattering maxima at 2θ = 12° and 21°. Tensile testing demonstrated that the blends are soft (E = 12–80 MPa) and show an excellent hyperelastic recovery Rrec = 66–85% while having high elongation at break εb up to >1000%. These properties of the blends are attained only when the copolymer has 56–62 wt% lactide content, a weight average molar mass >140 kg·mol−1, and number average lactide sequence length ≥4.8, while the blend is formed with a content of 5–10 wt% of PDLA. The devised strategy to identify a suitable copolymer for stereocomplexation and blend formation is transferable to further polymer systems and will support the development of thermoplastic elastomers suitable for medical applications.

Polyurethane cationomers containing fluorinated soft segments with hydrophobic properties

The synthesis of ecological waterborne polyurethane cationomers containing fluorinated polyol (0–20 wt.%) was successfully performed. FTIR and NMR analysis results confirmed the structure of the obtained polyurethane cationomers and incorporation of fluorinated component into the polyurethane chains. Average molar mass and phase structure of the obtained PU thin films were determined based on GPC, FTIR, WAXD and SEM-EDX results. The obtained cationomers have linear structures with clearly visible microphase separation of soft and hard segment domains; the presence of fluorinated polyol changes the strength of hydrogen bonds and in consequence degree of phase separation. The activation energy of glass transition was calculated based on multi-frequency DSC data. It has been shown that the presence of soft fluorinated segments in the cationomer structure strongly influences the hydrophobic, thermal and mechanical properties of the obtained films.

Genetic and Environmental Variation in Starch Content, Starch Granule Distribution and Starch Polymer Molecular Characteristics of French Bread Wheat

This study investigates genetic and environmental variation in starch content and characteristics of 14 French bread cultivars. Understanding the impact of these factors on wheat quality is important for processors and especially bakers to maintain and meet the requirements of industrial specifications. Different traits were evaluated: starch content, distribution of starch granules, percentage of amylose and amylopectin and their molecular characteristics (weight-average molar mass, number-average molar mass, polydispersity and gyration radius). Genetic, environment and their interaction had significant effects on all parameters. The relative magnitude of variance attributed to growth conditions, for most traits, was substantially higher (21% to 95%) than that attributed to either genotype (2% to 73%) or G × E interaction (2% to 17%). The largest environmental contribution (95%) to total variance was found for starch dispersity. The highest genetic influence was found for the percentage of A-type starch granules. G × E interaction had relatively little influence (≈7%) on total phenotypic variance. All molecular characteristics were much more influenced by environment than the respective percentages of amylose and amylopectin were. This huge difference in variance between factors obviously revealed the importance of the effect of growing conditions on characteristics of cultivars.

Experimental Investigation of Methyl Methacrylate in Stirred Batch Emulsion Reactor: AGET ATRP Approach

This study examines the ab initio emulsion atom transfer radical polymerization (ATRP) initiated by an eco-friendly reducing agent to produce poly(methyl methacrylate) (PMMA) polymer with controlled characteristics in a 2 L stirred batch reactor. The effect of the reaction temperature, surfactant concentration, monomer to water ratio, and stirring speed was thoroughly investigated. The results showed that PMMA coagulation becomes quite severe at a certain temperature threshold. However, the coagulation could be avoided at mild reaction temperature, since the outcomes showed that loading more surfactant to the system under high mixing speed has balanced the polymer mixture and yielded high monomer conversion. The PMMA product was analyzed by gravimetry and GPC measurements and after 5 h of polymerization at a reaction temperature of 50 °C, monomer conversion of 64.1% was obtained, and PMMA polymer samples produced had an average molar mass of 4.5 kg/mol and a polydispersity index of 1.17. The structure of the PMMA polymer was successfully proved by FTIR and nuclear magnetic resonance (NMR) spectroscopy. The results confirm the living feature of MMA AGET ATRP in emulsion medium and recommend further investigation for other types of surfactant.

Hyaluronic Acid in the Intestinal Tract: Influence of Structure, Rheology, and Mucoadhesion on the Intestinal Uptake in Rats

Oral hyaluronic acid (HA) is a ubiquitous biopolymer that has gained attention as a treatment for local or systemic diseases. Here, we prepared and characterized structures of free HA (f-HA) with a high (>105 Da), intermediate (≤105 Da), and low (≤104 Da) average molar mass (MM); nanoparticles crosslinked with adipic dihydrazide (n-HA); and mixed formulations (mixed-HA) containing f-HA and n-HA. MM distribution determined the structure, hydrodynamic diameter, and zeta potential of the f-HAs. Crosslinking changed the physicochemical properties in n-HA. In vitro tack adhesion assays, using mucin tablets or a viable rat intestinal mucosa, showed better mucoadhesion with f-HA (intermediate MM) and mixed-HA (25% n-HA), especially in the jejunum segment. High MM f-HA presented negligible mucoadhesion. n-HA showed the deepest diffusion into the porous of the membranes. In vivo results showed that, except for high MM f-HA, there is an inverse relationship between rheological changes in the intestinal membrane macerates resulting from mucoadhesion and the effective intestinal permeability that led to blood clearance of the structures. We conclude that the n-HA formulations are promising for targeting other tissues, while formulations of f-HA (intermediate MM) and mixed-HA are better for treating dysbiosis.

On the Formation and Stability of Chitosan/Hyaluronan-Based Complex Coacervates

This contribution is aimed at extending our previous findings on the formation and stability of chitosan/hyaluronan-based complex coacervates. Colloids are herewith formed by harnessing electrostatic interactions between the two polyelectrolytes. The presence of tiny amounts of the multivalent anion tripolyphosphate (TPP) in the protocol synthesis serves as an adjuvant “point-like” cross-linker for chitosan. Hydrochloride chitosans at different viscosity average molar mass, M v ¯ , in the range 10,000–400,000 g/mol, and fraction of acetylated units, FA, (0.16, 0.46 and 0.63) were selected to fabricate a large library of formulations. Concepts such as coacervate size, surface charge and homogeneity in relation to chitosan variables are herein disclosed. The stability of coacervates in Phosphate Buffered Saline (PBS) was verified by means of scattering techniques, i.e., Dynamic Light Scattering (DLS) and Small-Angle X-ray Scattering (SAXS). The conclusions from this set of experiments are the following: (i) a subtle equilibrium between chitosan FA and M v ¯ does exist in ensuring colloidal stability; (ii) once diluted in PBS, osmotic swelling-driven forces trigger the enlargement of the polymeric mesh with an ensuing increase of coacervate size and porosity.