High Degree Of Polymerization Research Articles

Catalytic Effect of Potassium Xanthates and Related Compounds on Disulfide Bond Enrichment of Polyalkylene Sulfides Synthesized in the Course of Episulfide Polymerization.

The original method for the preparation of high-molecular-weight polyalkylene sulfides was reported. Assuming anomalous peculiarities of the reaction (high polymerization rates, high degrees of polymerization, and huge discrepancy between the expected Mn values and the experimentally obtained values), the priority task was set to study the mechanism underlying the observed new type of polymerization. Thus, it was demonstrated that xanthate and related molecules could act as pure catalysts, facilitating both the chain-growth polymerization (ring-opening of episulfides) realized via an anionic route and the direct attack of the sulfur atom of one episulfide molecule on the methylene carbon atom of the second (neighbor) episulfide molecule, accompanied by the subsequent formation of a stable thiiranium-based zwitterionic adduct. The role of xanthate and related compounds as catalysts and stabilizing particles was further supplemented by modeling the attack of thiolate on the sulfur atom of a thiiranium-based adduct. The xanthate molecule acting as a catalyst was found to be involved in all stages of the process discussed by sharing the potassium atom with the sulfur atoms of active components of the system (the initial episulfide molecule, thiolate, and the zwitterionic intermediate). The subsequent analysis revealed the exceptional transparency of the materials obtained, which was found to exceed 99%. The pronounced self-healing ability was also found to be a distinctive feature of the synthesized high-molecular-weight polyalkylene sulfides enriched with disulfide bonds.

The general glycan profiling of Dendrobium officinale and their protective effects on MIN6 cells via ERK signaling pathway

Based on structural elucidation of natural and hydrolyzed glycans, the general glycans profiling of D. officinale were unequivocally established for the first time as follows: [Display omitted] The results indicated that the structure of D. officinale glycans with low degree of polymerization (DP ≤ 22) was linear α-D-1,4-glucan, whereas the structure of glycans with high degree of polymerization (DP > 24) was linear acetylated 1,4-glucomannan. The content of acetyl groups and mannose to glucose (M/G) ratio increased with the degree of polymerization of D. officinale glycans. In addition, this study showed that natural D. officinale glycans protected pancreatic β-cell damage induced by glucotoxicity through the extracellular signal–regulated kinase (ERK)1/2 pathway.

The exploration of effect for nano-Al2O3 on solid waste based superfine tailings cemented paste backfill: Pyrolysis property, hydration mechanism and environmental risk

Resource utilization of superfine tailings has become a key research direction in filling mining. This study analyzes the mechanical properties, pyrolysis mechanism and hydration mechanism of nano-Al2O3(NA)-doped solid waste based superfine tailings cemented paste backfill (SWSCPB) by multiple microscopic characterization methods and pyrolysis kinetic theory. The results show that the main temperature interval for the pyrolysis of SWSCPB to happen is 280–900 °C, which is divided into two stages of dehydroxylation and decarbonization. The apparent activation energy(E) and pre-index factor(A) of pyrolysis are higher than those of NA0 and NA2 at 1 % NA dosage, indicating that NA increases the energy barrier of pyrolysis, the percentage of activated molecules, and the collision probability of hydration products in SWSCPB, but decreases due to agglomeration at exceeds 1 % NA dosage. NA can enhance macroscopic strength of SWSCPB, with the highest strength at 1 % NA dosage. Compared with NA0 and NA2, more hydration products such as AFt and C-(A)-S-H are present in NA1, and the distribution of Q2 and Q4 in C-(A)-S-H is more pronounced, with a higher degree of polymerization, a stronger tendency for the conversion of non-bridging to bridging oxygen bonds, and fewer pores in the microstructure of SWSCPB. The NA dosage can provide more nuclei for the formation of AFt, C-(A)-S-H in SWSCPB, and can also promote the replacement of Si by Al for the conversion of C-S-H to C-(A)-S-H with higher polymerization. In addition, the leaching risk and mechanism of heavy metal ions from SWSCPB are preliminarily explored in combination with leaching experiments. The results provide new insights and guidance for the application of SWSCPB in filling mining under cleaner production targets.

Applications of regenerated bacterial cellulose: a review

AbstractWhilst synthetic polymers have changed the world in many important ways, the negative impacts associated with these materials are becoming apparent in waste accumulation and microplastic pollution due to lack of biodegradability. Society has become aware of the need to replace or substitute environmentally persistent synthetic polymers, and cellulose has received a large amount of attention in this respect. The mechanical properties of cellulose, its renewable nature and biodegradability are advantageous properties. Drawbacks exist for the use of plant cellulose (PC), including the water footprint of cotton, deforestation associated with wood/dissolving pulp, and the extensive processing required to refine plants and wood into pure cellulose. Bacterial cellulose (BC), also known as microbial cellulose, is gaining momentum in both academic and industry settings as a potential solution to the many drawbacks of plant-based cellulose. Compared to PC, BC has high purity, crystallinity and degree of polymerisation, and can be manufactured from waste in a way that yields more cellulose per hectare, per annum, and requires less intense chemical processing. Native bacterial cellulose can be formed and shaped to an extent and is found in a variety of commercial products. However, dissolving and regenerating bacterial cellulose is a potential avenue to broaden the applications available to this material. The aim of this study is to review the applications which utilize regenerated bacterial cellulose, with a focus on the dissolution/regeneration methods used and discussing the associated limitations and future outlook.

Ionic Covalent Organic Frameworks Consisting of Tetraborate Nodes and Flexible Linkers.

Covalent organic frameworks (COFs) have emerged as versatile materials with many applications, such as carbon capture, molecular separation, catalysis, and energy storage. Traditionally, flexible building blocks have been avoided due to their potential to disrupt ordered structures. Recent studies have demonstrated the intriguing properties and enhanced structural diversity achievable with flexible components by judicious selection of building blocks. This study presents a novel series of ionic COFs (ICOFs) consisting of tetraborate nodes and flexible linkers. These ICOFs use borohydrides to irreversibly deprotonate the alcohol monomers to achieve a high degree of polymerization. Structural analysis confirms the dia topologies. Reticulation is explored using various monomers and metal counterions. Also, these frameworks exhibit excellent stability in alcohols and coordinating solvents. The materials have been tested as single-ion conductive solid-state electrolytes. ICOF-203-Li displays one of the lowest activation energies reported for ion conduction. This tetraborate chemistry is anticipated to facilitate further structural diversity and functionality in crystalline polymers.

Novel Bis(4-aminophenoxy) Benzene-Based Aramid Copolymers with Enhanced Solution Processability.

Aramid copolymers have garnered significant interest due to their potential applications in extreme environments such as the aerospace, defense, and automotive industries. Recent developments in aramid copolymers have moved beyond their traditional use in high-strength, high-temperature resistant fibers. There is now a demand for new polymers that can easily be processed into thin films for applications such as electrical insulation films and membranes, utilizing the inherent properties of aramid copolymers. In this work, we demonstrate two novel aramid copolymers that are capable of polymerizing in polar organic solvents with a high degree of polymerization, achieved by incorporating flexible bis(4-aminophenoxy) benzene moieties into the chain backbone. The synthesized MBAB-aramid and PBAB-aramid have enabled the fabrication of exceptionally thin, clear films, with an average molecular weight exceeding 150 kDa and a thickness ranging from 3 to 10 μm. The dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) reveal that the thin films of MBAB-aramid and PBAB-aramid exhibited glass transition temperatures of 270.1 °C and 292.7 °C, respectively, and thermal decomposition temperatures of 449.6 °C and 465.5 °C, respectively. The mechanical tensile analysis of the 5 μm thick films confirmed that the tensile strengths, with elongation at break, are 107.1 MPa (50.7%) for MBAB-aramid and 113.5 MPa (58.4%) for PBAB-aramid, respectively. The thermal and mechanical properties consistently differ between the two polymers, which is attributed to variations in the linearity of the polymer structures and the resulting differences in the density of intermolecular hydrogen bonding and pi-pi interactions. The resulting high-strength, ultra-thin aramid materials offer numerous potential applications in thin films, membranes, and functional coatings across various industries.

Possibilities For Using Ionic Liquids In The Polymerization Process

Abstract The paper investigates the polymerization of various methacrylate esters in different ionic liquids (ILs) and compares the results with those obtained in traditional organic solvents, particularly benzene. The study highlights the influence of ILs on the polymerization process, focusing on factors such as polymer yield, average molecular weight, and thermal stability. The results indicate a relatively higher degree of polymerization in ILs compared to benzene under identical conditions. Additionally, polymers synthesized in ILs exhibit higher average molecular weights and thermal stability. The observed differences are attributed to the unique properties of ILs, such as low chain transfer rate constants and the ability to stabilize active radicals during polymerization. The findings underscore the potential of ILs as promising reaction media for polymer synthesis, offering improved efficiency and polymer properties compared to conventional organic solvents.

The influence of polyphenols on the hydrolysis and formation of volatile esters in wines during aging: An insight of kinetic equilibrium reaction

The evolution of volatile esters leads to changes in wine aroma during aging. In this study, polyphenol effect on ester equilibrium in wines was investigated through three aging experiments. Kinetic parameters of esters were calculated in four red wines. Results showed that the reaction rate constant (kobsd) was mainly determined by the molar concentration ratio of alcohols or acids to the corresponding esters. Phenolic matrix was more likely to influence the activation energy (Ea). Higher contents of total polyphenol led to the increase of Ea, resulting in the reactions less prone to happen but more susceptible to temperature changes. Combined with the practical wine aging and exogenous polyphenol addition experiments, the impact of polyphenol composition was revealed. Flavanols with higher polymerization degrees were found more beneficial for ester preservation than monomer flavanols or anthocyanins. This work could provide theoretical guidance in enhancing fruity aroma in wines via modulating phenolic matrix.

Efficient separation of coal gasification fine slag from Texaco gasifier and microstructures and elemental characteristics of separated components

ABSTRACT Coal gasification fine slag (CGFS) is one of the by-products of coal gasification process, which is mainly composed of inorganic minerals and residual carbon. The key to realize the high-value utilization of CGFS is separating the residual carbon and mineral in CGS effectively. Owing to irregular distribution of carbon in different size of CGFS, which could not be enriched by simple grinding and screening for component enrichment. In this paper, the enrichment of CGFS was carried out by the float-sink method, which is low-cost and does not result in the loss of raw materials. The carbon-rich particles (CRP, ash: 27.89%) and mineral-rich particles (MRP, ash: 78.01%) were obtained, where CRP contains a large amount of amorphous carbon with rich porous structure, while MRP is a heterogeneous material containing not only inorganic minerals but also organic carbon with low porosity. The mineral particles exist as aluminosilicates with a high degree of polymerization. The results of this paper will provide theoretical and technical support for the high-value utilization of CGFS.

Enhanced humification attributed by the integration of Fenton reagent and oxalic acid during a co-composting of swine manure and corn straw: Impacts and the possible mechanisms

To illustrate the role and mechanism of using oxalic acid (OA) and Fenton reagent to enhance carbon transformation and humification in the co-composting of swine manure and corn straw, four different treatments, SW1 (Control), SW2 (Fenton reagent), SW3 (10 % OA), and SW4 (Fenton reagent + 10 % OA) were set up for an 80-day pilot-scale composting. Compared with the Fenton pretreatment, the contents of Fe (II) and hydroxyl radicals (·OH) in the SW4 treatment increased by 20.25 %-54.55 % and 6.39 %-71.00 %, respectively. This confirmed the role of OA in protecting Fe (II) and maintaining the generation of ·OH during the composting. Compared with Control, Fenton-like reagent amendment facilitated decomposition of dissolved organic carbon and total organic matter by 20.53 % and 25.37 %, respectively, which led to a higher content of humic substances (141.81 mg/g) and a higher degree of polymerization (3.51) in SW4. Among all, the dissolved organic carbon in the compost substrate of SW4 treatment showed the highest level of aromatization and more refractory organic matter decomposition. The compact microbial co-occurrence network analysis exhibited the high-metabolic activity in Fenton-like treatment (SW4). Therefore, the probable mechanism of humification facilitation by Fenton-like reagent amendment in co-composting could be controlled by several processes: 1) generation of ·OH for facilitating the decomposition of organic matter, 2) disintegration of refractory lignocellulose substances by promoting the lignin pathway of humification, and 3) increasing the quantity and activity of microbes (i.e., Proteobacteria, Actinobacteriota, Chloroflexi, Ascomycota and Basidiomycota) involved in humification. This study provided a profound understanding of Fenton-like reagent amendments in co-composting of agricultural solid wastes and proposes a solution for enhancing the humification degree of compost products for agricultural use.

Characterisation of chicken breast and soy proteins glycated with konjac glucomannan hydrolysate

SummaryThis study investigated the enhancement of food proteins through glycation with bioactive saccharides derived from Konjac glucomannan hydrolysate (KGMH) via the Maillard reaction. The focus was on how the degree of polymerisation (DP) of KGMH influences the glycation process and the properties of conjugates with chicken breast and soy proteins. KGMH samples with low, medium, and high DPs (4.20, 5.21, and 6.11, respectively) were glycated under wet‐heating conditions with varying pH levels (8, 9, and 10) at 70 °C for 15 min to 6 h. Results demonstrated that higher pH and longer reaction times significantly enhanced (P < 0.05) glycation and browning, particularly with lower DP saccharides. The optimal conjugates markedly improved protein solubility (1.3 to 1.9 times), heat stability (1.1 to 2.4 times), and emulsification properties (1.2 to 1.5 times), with the highest DP showing the strongest correlation. Additionally, these conjugates exhibited significantly enhanced in vitro bioaccessibility (58.69% to 66.65%) and antioxidant activity (P < 0.05). This study highlights the novel potential of KGMH‐protein conjugation through the Maillard reaction for developing functional food ingredients with superior quality.

Advancing Thermal Stability in Natural Ester Oil-Paper Insulation Systems via Precision Nanostructuring with Parylene Films: Experimental and Molecular-Level Comprehensive Assessment

The oil-paper insulation system in eco-friendly fire-retardant transformers depends on hydrophilic natural ester insulating oil. Moisture within the system synergistically interacts with aging, worsening oil-paper insulation degradation and hastening overall system aging. Chemical vapor deposition was used to create parylene surface-modified insulating paper as a strategy to inhibit moisture-induced aging in natural ester oil-paper insulation. The effectiveness of the approach was identified by a comprehensive assessment of the physicochemical and electrical properties of the parylene surface-modified insulating paper. The findings from accelerated thermal aging at 130 °C for 90 days on the natural ester oil-paper insulation system reveal the outstanding lipophilic and hydrophobic properties while maintaining electrical characteristics of the parylene surface-modified insulating paper. After 90 days of aging, the parylene surface-modified insulating paper exhibited a 56.76% higher degree of polymerization and a 19.36% significantly lower moisture content than conventional cellulose insulating paper. In the natural ester oil-paper insulation system, the parylene surface-modified insulating paper led to a notable 63% reduction in insulating oil acid value, a 60.50% decrease in dielectric loss, and a substantial 20.35% increase in AC breakdown voltage. Molecular-level investigations revealed the inhibitory mechanism of the parylene film, offering a promising solution to enhance the thermal stability and aging resistance of natural ester oil-paper insulation systems.

Conformational preferences of cocoa oligomeric proanthocyanidins and their influence on polarity

Proanthocyanidins (OPACs) are the second largest class of plant metabolites after lignans. Although knowledge of their 3D conformations would add greatly to our understanding of their biological properties, very little has been published on the conformations of OPACs with a degree of polymerization (DP) above 4. We investigated the conformations of the linear epicatechin oligomers, prominent representatives of OPACs prevalent in apples and cocoa, where the epicatechin units are interconnected through the 4β-8 bonds. For DP-2 to DP-10 oligomers, conformational preferences reflected in the arrangement of consecutive flavan-3-ol units, are characterized by the φ torsion. For dimers, there are two energy wells corresponding to two preferred φ torsions, designated as compact and extended form. This behaviour is preserved in OPACs with higher DPs, but the most energetically favoured conformations are a combination of both, with compact-only or extended-only conformations being very unlikely. Thus, oligomers with DP ≥ 7 tend to assume an overall conformation approximating a spherical shape. This shape has a significant influence on the polarity of the OPAC oligomers expressed as 3D polar surface area, calculated using Spartan software for geometry-optimized 3D models, and possibly on other physicochemical properties. The results of polarity calculations provide a molecular-level rationale for the polarity-based chromatographic separation of the cocoa B-type procyanidins with DP range 4 to 10. In our experiments, using centrifugal partition chromatography (CPC) (a solvent system consisting of EtOAc-EtOH-water (6:1:5) v/v/v with aqueous phase stationary and upper phase mobile) we found that an enriched mixture of proanthocyanidins eluted first DP-1 (epicatechin) followed by consecutive elution of the DP-2 to DP-10 in the linear 4β-8 form. We demonstrated that such separation would not be possible if compact-only or extended-only conformations were present in solution. However, for the energy-favoured, spherically shaped conformations, the observed CPC elution order is fully justified.

Using waste to improve the weak: Recycled seashell as an ideal way to regulate the interfacial transition zone in biochar-cement composites

The strategy of partially substituting cement with carbon-negative biochar to fabricate biochar-cement composites can represent a promising approach to reducing the carbon emissions of the construction industry. However, the detrimental impact on strength development from excessive biochar incorporation remains a significant challenge. To address this issue, this study pioneers a strategy to modify wood waste-derived biochar using seashell waste for enhancing its binding with the cement matrix. Employing a mechanochemical process, the shell-modified biochar was synthesized using oyster shell (OS) and wood waste (WW). The compressive strength of cement composites incorporating 5 wt% modified biochar improved by 3.9–17% compared to the referenced biochar. Even with high biochar incorporation (30 wt%), the compressive strength increased by 58.2% upon modifying the biochar at the OS/WW ratio of 1:9 (10SBC). The modified biochar refined the pore structures, accelerated the hydration kinetics, improved the degree of hydration, and fostered the development of the C-S-H gel network with a longer silicate chain and a higher polymerization degree. Furthermore, the strength enhancement of the biochar-cement composites was attributed to the improved micro-mechanical properties at the interfacial transition zone (ITZ), which increased the volume fraction of high-density C-S-H by 64.4–112% and decreased the low-density C-S-H fraction by 41.8–52.6%. Notably, 10SBC demonstrated a superior improvement due to its cohesive bond with the C-S-H gel and the concurrent densification of C-S-H in the ITZ, which was facilitated by the growth of Ca-/Al-rich hydration products. Overall, this study synergistically upcycled wood and seashell waste into value-added cement additives, thereby achieving strength enhancement of the cement composites.

Integrative experimental and computational analysis of the impact of KGM's polymerization degree on wheat starch's pasting and retrogradation characteristics

This study investigated the influence of Konjac Glucomannan (KGM) with varying degrees of polymerization (DKGMx) on the gelatinization and retrogradation characteristics of wheat starch, providing new insights into starch-polysaccharide interactions. This research uniquely focuses on the effects of DKGMx, utilizing multidisciplinary approaches including Rapid Visco Analysis (RVA), Differential Scanning Calorimetry (DSC), rheological testing, Low-Field Nuclear Magnetic Resonance (LF-NMR), and molecular simulations to assess the effects of DKGMx on gelatinization temperature, viscosity, structural changes post-retrogradation, and molecular interactions. Our findings revealed that higher degrees of polymerization (DP) of DKGMx significantly enhanced starch's pasting viscosity and stability, whereas lower DP reduced viscosity and interfered with retrogradation. High DP DKGMx promoted retrogradation by modifying moisture distribution. Molecular simulations revealed the interplay between low DP DKGMx and starch molecules. These interactions, characterized by increased hydrogen bonds and tighter binding to more starch chains, inhibited starch molecular rearrangement. Specifically, low DP DKGMx established a dense hydrogen bond network with starch, significantly restricting molecular mobility and rearrangement. This study provides new insights into the role of the DP of DKGMx in modulating wheat starch's properties, offering valuable implications for the functional improvement of starch-based foods and advancing starch science.

Structure-Assisted Design of Chitosanase Product Specificity for the Production of High-Degree Polymerization Chitooligosaccharides.

Chitosanases are valuable enzymatic tools in the food industry for converting chitosan into functional chitooligosaccharides (COSs). However, most of the chitosanases extensively characterized produced a low degree of polymerization (DP) COSs (DP = 1-3, LdpCOSs), indicating an imperative for enhancements in the product specificity for the high DP COS (DP >3, HdpCOSs) production. In this study, a chitosanase from Methanosarcina sp. 1.H.T.1A.1 (OUC-CsnA4) was cloned and expressed. Analysis of the enzyme-substrate interactions and the subsite architecture of the OUC-CsnA4 indicated that a Ser49 mutation could modify its interaction pattern with the substrate, potentially enhancing product specificity for producing HdpCOSs. Site-directed mutagenesis provided evidence that the S49I and S49P mutations in OUC-CsnA4 enabled the production of up to 24 and 26% of (GlcN)5 from chitosan, respectively─the wild-type enzyme was unable to produce detectable levels of (GlcN)5. These mutations also altered substrate binding preferences, favoring the binding of longer-chain COSs (DP >5) and enhancing (GlcN)5 production. Furthermore, molecular dynamics simulations and molecular docking studies underscored the significance of +2 subsite interactions in determining the (GlcN)4 and (GlcN)5 product specificity. These findings revealed that the positioning and interactions of the reducing end of the substrate within the catalytic cleft are crucial factors influencing the product specificity of chitosanase.

Enzymatic synthesis of biobased aliphatic-hetero-aromatic furanic copolyesters: Influence of furan dimethyl ester isomerism

Due to environmental concerns, there is a growing demand for more sustainable materials. As a result, the renewability of the raw materials and catalysts involved in production is important for rendering sustainable and circular polymers. Due to its environmentally friendly nature and high selectivity, enzymatic polymerization is a viable approach for producing such polymers. Recent developments in the field of biobased furan building blocks have led to renewed interest in 2,4-furandicarboxylic acid (2,4-FDCA) and 3,4-FDCA. Furthermore, far too little attention has been given to 2,5-bis(hydroxymethyl)furan (2,5-BHMF), another class of hetero-aromatic diol that can be derived from carbohydrates. These furan monomers are attractive due to their potential for producing novel biobased polyesters with interesting properties. To date, however, there has been little discussion about the use of these materials for polymerization via enzymatic approaches. Hence, a comparative study of CALB-catalyzed copolymerization involving two FDCA dimethyl ester isomers, either 2,4- or 3,4-DMFDCA, with 2,5-BHMF and various aliphatic diols has been carried out. This provides further insight into the regioselectivity promoted by CALB for asymmetrical 2,4-DMFDCA over symmetrical 3,4-DMFDCA. This is evidenced by the high degree of polymerization achieved with a weight-average molecular weight of up to 14 kg mol−1. In agreement with previous findings, a preference for the formation of cyclic species from symmetrical monomers catalyzed by CALB was observed. Structural characterization and thermal and crystallinity analyses were used to assess the correlation between structure and material properties.

High Degree of Polymerization of Chitin Oligosaccharides Produced from Shrimp Shell Waste by Enrichment Microbiota Using Two-Stage Temperature-Controlled Technique of Inducing Enzyme Production and Metagenomic Analysis of Microbiota Succession.

The direct enzymatic conversion of untreated waste shrimp and crab shells has been a key problem that plagues the large-scale utilization of chitin biological resources. The microorganisms in soil samples were enriched in two stages with powdered chitin (CP) and shrimp shell powder (SSP) as substrates. The enrichment microbiota XHQ10 with SSP degradation ability was obtained. The activities of chitinase and lytic polysaccharide monooxygenase of XHQ10 were 1.46 and 54.62 U/mL. Metagenomic analysis showed that Chitinolyticbacter meiyuanensis, Chitiniphilus shinanonensis, and Chitinimonas koreensis, with excellent chitin degradation performance, were highly enriched in XHQ10. Chitin oligosaccharides (CHOSs) are produced by XHQ10 through enzyme induction and two-stage temperature control technology, which contains CHOSs with a degree of polymerization (DP) more significant than ten and has excellent antioxidant activity. This work is the first study on the direct enzymatic preparation of CHOSs from SSP using enrichment microbiota, which provides a new path for the large-scale utilization of chitin bioresources.

Pulsed Electric Field-Assisted Extraction of Inulin from Ecuadorian Cabuya (Agave americana).

Inulin is a carbohydrate that belongs to fructans; due to its health benefits, it is widely used in the food and pharmaceutical industries. In this research, cabuya (Agave americana) was employed to obtain inulin by pulsed electric field-assisted extraction (PEFAE) and FTIR analysis confirmed its presence. The influence of PEFAE operating parameters, namely, electric field strength (1, 3 and 5 kV/cm), pulse duration (0.1, 0.2 and 0.5 ms), number of pulses (10,000, 20,000 and 40,000) and work cycle (20, 50 and 80%) on the permeabilization index and energy expenditure were tested. Also, once the operating conditions for PEFAE were set, the temperature for conventional extraction (CE) and PEFAE were defined by comparing extraction kinetics. The cabuya meristem slices were exposed to PEFAE to obtain extracts that were quantified, purified and concentrated. The inulin was isolated by fractional precipitation with ethanol to be characterized. The highest permeabilization index and the lowest energy consumption were reached at 5 kV/cm, 0.5 ms, 10,000 pulses and 20%. The same extraction yield and approximately the same amount of inulin were obtained by PEFAE at 60 °C compared to CE at 80 °C. Despite, the lower amount of inulin obtained by PEFAE in comparison to CE, its quality was better because it is mainly constituted of inulin of high average polymerization degree with more than 38 fructose units. In addition, TGA analyses showed that inulin obtained by PEFAE has a lower thermal degradation rate than the obtained by CE and to the standard.

Regiocontrol of the Bulk Polymerization of Lysine Ethyl Ester by the Selection of Suitable Immobilized Enzyme Catalysts.

The development of a green and facile method for the controlled synthesis of functional polypeptides is desired for sustainable material applications. In this study, the regioselective synthesis of poly(l-lysine) (polyLys) via enzyme-catalyzed aminolysis was achieved by bulk polymerization of l-lysine ethyl ester (Lys-OEt) using immobilized Candida antarctica lipase Novozym 435 (IM-lipase) or trypsin (IM-trypsin). Structural characterization of the obtained polyLys revealed that IM-lipase resulted solely in ε-linked amide bond formation, whereas IM-trypsin predominantly provided α-linked polyLys. Optimization of the conditions for the bulk polymerization using immobilized enzymes resulted in high monomer conversion and a high degree of polymerization, with excellent regioselectivity. Molecular docking simulations revealed different binding conformations of Lys-OEt to the catalytic pockets of lipase and trypsin, which putatively resulted in different amino moieties being used for amide bond formation. The immobilized enzymes were recovered and recycled for bulk polymerization, and the initial activity was maintained in the case of IM-trypsin. The obtained α- and ε-linked polyLys products exhibited different degradability against proteolysis, demonstrating the possibility of versatile applications as sustainable materials. This enzymatic regioregular control enabled the synthesis of well-defined polypeptide-based materials with a diverging structural variety.