Molecular Weight Distribution Research Articles

Evaluation of Grafting Parameters of Styrene onto Alkaline Modified Sugarcane Bagasse using Fe2+/H2O2 and Fe2+/H2O2-N2H4 initiator systems and Characterization of the Hydrolyzed Grafted Polystyrene Chains

Cellulose the most abundant natural fibre can be modified, via grafting with vinyl monomers, in homogenous or heterogeneous reaction medium. Therefore, the objective of this paper was to study the grafting parameters of styrene onto alkaline modified sugarcane bagasse using Fe2+/H2O2 and Fe2+/H2O2- N2H4 initiator systems and characterized the hydrolyzed grafted polystyrene chains for their viscometry and average molecular weight distributions using standard appropriate methods. The grafting parameters increases within 0.10-0.25 M styrene concentration in both initiator systems and initiator concentration within the range 1.0x10-3 to 6.0x10-3 for Fe2+/H2O2- N2H4 and 1.0x10-3 to 9.0x10-3 for Fe2+/H2O2 systems, albeit with higher values in the former system. These parameters decrease at higher monomer and initiator concentrations in both systems. The viscometry of hydrolyzed polystyrene chain prepared at optimum initiator concentrations and 0.10-0.30 M styrene concentration in both initiator systems are in the range (1.6416-4.5327 cP), (0.6416-3.5327 cP) and (73.2277-202.1927 cP) for relative, specific and inherent viscosities respectively, consistent with increases in activation energy of flow (1.24-5.30 KJmol-1) and average viscosity molecular weights (307.92-565.79 gmol-1) , these parameters decreases at higher monomer concentration in both initiator systems. The number and weight-average molecular weight distributions and polydispersity indices indicates that grafted polystyrene chains in Fe2+/H2O2 system are broader and more polydispersed than those for Fe2+/H2O2- N2H4 initiator system. The results showed that the hydrazine enhanced initiator system was more effective for the copolymerization reaction with polystyrene polydispersity indices comparable to those of synthetic chain-growth polymers.

Effects of Protein on Green Tea Quality in a Milk-Tea Model during Heat Treatment: Antioxidant Activity, Foaming Properties, and Unbound Small-molecule Metabolome

Tea drinks/beverage has a long history and milk is often added to enhance its taste and nutritional value, whereas the interaction between the tea bioactive compounds with proteins has not been systematically investigated. In this study, a milk-tea model was prepared by mixing green tea solution with milk and then heated at 100°C for 15 min. The milk tea was then measured using biochemical assay, antioxidant detection kit, microscopy as well as HPLC-QTOF-MS/MS after ultrafiltration. The study found that as the concentration of milk protein increased in the milk-tea system, the total phenol-protein binding rate raised from 19.63% to 51.08%, which led to a decrease in free polyphenol content. This decrease of polyphenol was also revealed in the antioxidant capacity, including 2,2-diphenyl-1-picrylhydrazyl radical scavenging ability and ferric ion reducing antioxidant power, in a dose-dependent manner. Untargeted metabolomics results revealed that the majority of small-molecule compounds/polyphenols in tea, such as epigallocatechin gallate, (-)-epicatechin gallate, and Catechin 5,7,-di-O-gallate, bound to milk proteins and were removed by ultrafiltration after addition of milk and heat treatment. The SDS-PAGE and Native-PAGE results further indicated that small molecule compounds in tea formed covalent and non-covalent complexes by binding to milk proteins. All above results partially explained that milk proteins form conjugates with tea small-molecule compounds. Consistently, the particle size of the tea-milk system increased as the tea concentration increased, but the polymer dispersity index decreased, indicating a more uniform molecular weight distribution of the particles in the system. Addition of milk protein enhanced foam ability in the milk-tea system but reduced foam stability. In summary, our findings suggest that the proportion of milk added to tea infusion needs to be considered to maintain the quality of milk-tea from multiple perspectives, including stability, nutritional quality and antioxidant activity.

Structural analysis and biological activity of cell wall polysaccharides and enzyme-extracted polysaccharides from pomelo (Citrus maxima (Burm.) Merr.)

Pomelo peel is a valuable source of pectin, but research on its cell wall polysaccharides is limited. This study compared the cell wall polysaccharides of pomelo peel, enzyme-extracted polysaccharides of pomelo peel, and enzyme-extracted polysaccharides of whole pomelo fruit. Cell wall polysaccharides, including water-soluble pectin (WSP), chelator-soluble pectin (CSP), sodium carbonate-soluble pectin (NSP), 1 mol/L KOH soluble hemicellulose (KSH-1), and 4 mol/L KOH soluble hemicellulose (KSH-2), were obtained by sequence-extraction method. Total polysaccharides from whole pomelo fruit (TP) and peel-polysaccharides from pomelo pericarps (PP) were obtained using enzyme-extraction method. The structural, thermal, rheological, antioxidant properties, and wound healing effect in vitro were described for each polysaccharide. WSP had a uniform molecular weight distribution and high uronic acid (UA) content, suitable for commercial pectin. NSP had the highest Rhamnose (Rha)/UA ratio and a rich side chain with highest viscosity and water retention. PP displayed the highest DPPH radical scavenging activity and reducing capacity at 0.1 to 2.0 mg/mL concentration range, with an IC50 of 1.05 mg/mL for DPPH free radicals. NSP also demonstrated the highest hydroxyl radical scavenging activity and promoted Human dermal keratinocyte proliferation and migration at 10 μg/mL, suggesting potential applications in daily chemical and pharmaceutical industries.

Evaluating the operational properties of concrete admixtures containing molecularly modified polycarboxylate superplasticizers

The objective of this study focused on the design and preparation of a molecularly modified polycarboxylate superplasticizer to develop concretes with enhanced engineering features. For this purpose, polyethylene glycol was chemically modified with maleic anhydride to give the mono polyethylene glycol maleate (MPEGM). Then, polycarboxylate superplasticizer comprising of isoprenyl oxy polyethylene glycol (TPEG) and acrylic acid (AA, PCE-1), and the synthesized MPEGM with TPEG and AA (PCE-2) were prepared through solution radical polymerization. Subsequently, concrete mixtures with different dosages (0, 0.1, 0.15, 0.2, 0.25, 0.3 wt%) of PCE-1 and PCE-2 were prepared. Chemical structure of the synthesized MPEGM and superplasticizers together with their copolymer composition were identified by FTIR and 1HNMR analyses. The molecular weights (Mw) and molecular weight distributions (PDI) of PCE-1 (8.74 × 104, 1.36) and PCE-2 (8.74 × 104, 2.19) were studied by GPC analysis, respectively. The zeta potential of cement particles (2.8 mV) becomes negative in the presence of 0.6 g/L of PCE-1 (− 7.8) and PCE-2 (− 9.5). This implies that electrostatic and steric hindrance forces of adsorbed superplasticizers synergistically provide a situation for appropriate dispersion of cement particles. The results of water-reducing percentage, fluidity, air content, bleeding water rate, initial and final setting times, wet density, flexural and compressive properties, and ultrasonic pulse velocity analyses exhibit significant enhancement on the features of concrete mixtures made of polycarboxylate superplasticizer. The superiority of PCE-2 to PCE-1 was connected to its adsorption-dispersibility potent induced by stronger electrostatic and steric repulsion forces, which result in quality and continuity enhancement in concretes.

In vitro and in vivo effects of pectin‐type polysaccharides isolated from crabapples (Malus prunifolia) on inflammatory colitis models

SummaryThe aim of this study was to investigate the anti‐inflammatory effects of polysaccharides extracted from crabapples (Malus prunifolia; MP) in vitro and in vivo. Crabapples were subjected to hot water extraction to obtain MP‐HW, which was further separated into low (MP‐L) and high molecular weight (MW) (crude polysaccharide; MP‐CP) fractions by ethanol precipitation. Based on MW distribution, general composition, component sugars, and Fourier transform infrared spectroscopy, MP‐CP was identified as a pectin‐type polysaccharide rich in galacturonic acid with an MW of 106.2 kDa. MP‐CP inhibited the production and mRNA expression of proinflammatory factors in an IL‐1β‐treated intestinal epithelial cell model. In addition, MP‐CP significantly alleviated the body weight, disease activity index score, colon length, and spleen weight in mice with dextran sulfate sodium (DSS)‐induced colitis. The MP‐CP‐treated group showed effective regulation of the expression of pro‐ and anti‐inflammatory factors and immunoglobulin A than the DSS‐treated group. Haematoxylin and eosin and Alcian blue staining revealed that MP‐CP alleviated inflammatory manifestations and mucin expression in the intestinal lumen. Collectively, pectin‐type polysaccharides isolated from crabapples may be used as a new functional food and pharmaceutical agent for the prevention and treatment of inflammatory colitis.

Impact of Pretreatment With Acid and Ultrasound on the Production and Characteristics of Goat Skin Gelatin

Goat skin is a potential raw material source for gelatin production using acid-ultrasound pretreatment. The objective of this study was to investigate the use of ultrasound in combination with acid pretreatment for the preparation of goat skin gelatin. Gelatin was extracted from goat skin using different pretreatments: acetic acid (T1), acetic acid followed by ultrasound (20 kHz and 750 W) (T2), and without pretreatment (T0). The results showed that the combination of acetic acid and ultrasound pretreatment significantly impacted the quality of the resulting gelatin. The study results showed an increase in yield (9.24 to 25.48%), hydroxyproline content (102.07 to 231.31 mg/g), gel strength (4.76 to 197.62 g), viscosity (6.80 to 48.00 cP), melting point (32.47 to 35.85 oC), EAI (18.24 to 23.58 m2/g), and ESI (24.90 to 62.63 min). However, there was a decrease in pH, the value of color L*, and turbidity. The SDS-PAGE patterns showed differences in molecular weight distribution due to variations in pretreatment. All gelatin samples exhibited α1 and α2 chains as the predominant components. Interestingly, the ultrasound effect highlighted the β-chain more boldly compared to other pretreatments. FTIR spectroscopy analysis shows changes in molecular interactions due to acetic acid pretreatment followed by ultrasound, which results in shifts in the Amide A, Amide B, Amide I, Amide II, and Amide III groups. Ultrasonic treatment caused more dense and disturbed structures in the sample. Therefore, the combination of acetic acid and ultrasound pretreatment yielded the superior properties of goat skin gelatin.

In vitro antifungal activity and in vivo edible coating efficacy of insect-derived chitosan against Botrytis cinerea in strawberry

Strawberry is a perishable fruit, susceptible to development of rot by a range of fungi, in particular Botrytis cinerea. Chitosan represents an alternative to agrochemicals for improving shelf-life and fighting fungal pathogens. A chitosan-based coating derived from pupal exuviae of Hermetia illucens has been recently formulated for improving shelf-life of strawberry stored at 4 °C and mixed condition (4 °C and room temperature). The effects of a decolored (PEDEC) and not decolored (PEND) chitosan from the black soldier fly were evaluated and compared with commercial chitosans from crustaceans (CCs), in vitro and in vivo. An inhibition/reduction of fungal growth and a disturbance of normal fungal morphology were observed, being MIC of 0.5 mg mL−1 and 1 mg mL−1 and growth inhibition of 70 % and 4% for PEND and PEDEC, respectively. Both edible coatings distributed via aerograph showed equal or better potential application than CCs in controlling B. cinerea in strawberry post-harvest treated. Different effects for chitosans depended on their different molecular weight and deacetylation degree distributions, and the presence or absence of melanin pigments in their structure. PEND could act directly against the fungus, with effects predominantly associated with fungitoxic properties; PEDEC might principally provide viable alternatives, such as the elicitation of biochemical defense responses in fruits, for example through total phenols, in particular the flavonoids.

Preliminary Study on Polymerization between Hemoglobin and Enzymes during the Preparation of PolyHb-SOD-CAT-CA.

The objective of this study was to explore the influence of different factors on the aggregation effect on hemoglobin (Hb) and enzymes during the preparation of Polyhemoglobin-Superoxide dismutase-Catalase-Carbonic anhydrase (PolyHb-SOD-CAT-CA). Several factors including temperatures, pH values, Glutaraldehyde (GDA) amounts and enzymes amounts were investigated systematically to study their effects on the enzymes recoveries and polymerization rates including the Superoxide dismutase (SOD), Catalase (CAT) and Carbonic anhydrase (CA), as well as their effects on the molecular weight distribution of PolyHb-SOD-CAT-CA. Then the oxygen affinity and methemoglobin (MetHb) contents of obtained PolyHb-SOD-CAT-CA were measured to evaluate the effects of enzyme crosslinking on the properties of Polyhemoglobin (PolyHb) moieties in the molecular structure of obtained PolyHb-SOD-CAT-CA conjugate. The results showed that the enzyme recoveries and polymerization rates could be decreased with the temperatures increasing and could be generally kept stable in the physiological pH conditions, but presented only slight changes among the investigated enzyme amounts ranges. Although the GDA concentration increasing could promote the enzyme polymerization rates, the enzyme recoveries decreased in whole. The polymerization rate and molecular size of PolyHb-SOD-CAT-CA conjugate increased with the elevation of temperature and the concentration of GDA. Lastly, the P50 values, Hill coefficients, and MetHb contents of PolyHb-SOD-CAT-CA conjugate with different enzyme crosslinking degrees exhibited no obvious differences with each other. In conclusion, the polymerization reactions between enzymes and Hb molecules could be remarkably affected by temperatures, pH values, and GDA amounts, and the enzyme crosslinking presented no obvious effects on the Hb properties, especially about the oxygen affinity and oxidation degrees.

Characterisation, antibacterial activity, and prebiotic potential of dried Hermetia illucens L. larvae and of their fractions

Abstract In this study, black soldier fly (BSF) dried larvae were fractionated into their defatted, lipid, protein, and chitin-rich fractions. The samples were then characterised in terms of proximate composition, analysis of amino acids, analysis of the molecular weight distribution of proteins via gel electrophoresis, and fatty acids analysis of the lipid fraction. The antibacterial activity of all fractions was determined against Escherichia coli F4 and Streptococcus suis, two common swine pathogens. Finally, the prebiotic activity of the whole larvae and of their protein isolate and chitin-rich pellet was determined for Limosilactobacillus reuteri, a naturally occurring species in the gastro-intestinal tract of the pig. The results on amino acid profile showed that the protein extraction method used was not fully effective in cleaving chitin-bound proteins, as expected, as the true protein content of the chitin-rich sample was 48.5%. This was in accordance with the SDS-PAGE analysis, where the molecular weight distribution of proteins in the protein isolate sample did not show band at higher molecular weight, which were instead present in the chitin-rich sample. The analysis of fatty acid (FA) profile showed that lauric acid was the most abundant FA, in accordance with the literature. The results on microbiological analyses highlighted how all nitrogen-containing samples showed antibacterial activity against E. coli, the highest being the defatted fraction at 1% with a decrease of −0.77 log CFU/mL, while only the lipid fraction against S. suis (−0.48 log CFU/mL at 1%). All tested samples showed prebiotic activity for L. reuteri, but it was noticed that the increase in chitin concentration resulted in the decrease of the prebiotic effect. By combining the results of both antibacterial and prebiotic tests, it could be inferred that chitin might be considered as an antibacterial compound.

Degradation of Unsintered Hydroxyapatite and Poly-L-Lactide Composite Sheets In Vivo and In Vitro.

Bioabsorbable sheet-shaped implants made of forged composites of unsintered hydroxyapatite and poly-L-lactide (F-u-HA/PLLA) have been used for orbital fracture repair with good results. This is the first report using multiple specimens implanted in the human orbit to demonstrate the biodegradation and loss of strength of F-u-HA/PLLA sheets. Among the patients who underwent various facial fracture repairs with F-u-HA/PLLA sheets implanted in their orbits, those whose sheets were subsequently extracted were included in the study. Viscosity-average molecular weight, crystallinity, and bending strength of the extracted implants were measured. An in vitro degradation test was also performed for comparison. Among the 111 patients who underwent F-u-HA/PLLA sheet implantation, 13 subsequently underwent surgical extraction of implants; the majority were due to secondary correction of complex fractures. One patient developed an infection; none developed foreign body reactions. Overall, 11 specimens from 10 patients with consent were examined. The time from implantation to extraction ranged from 43 to 632 days (median: 210d). Compared with the results of the in vitro degradation test, the viscosity-average molecular weight and bending strength had a slower decrease. The F-u-HA/PLLA sheets retained more than 50% of their initial bending strength after 12 months. Crystallinity varied widely. F-u-HA/PLLA sheets implanted in human orbits did not degrade faster than those of in vitro testing. Sheet-shaped implants made of forged composites of unsintered hydroxyapatite and poly-L-lactide can be considered appropriate reconstructive materials for orbital fractures as they retained sufficient strength to support the orbital contents at 12 months postoperatively, and no case of delayed foreign body reactions was observed.

Exploring the Bioactive Potential of Moroccan Lemon Grass (Cymbopogon citratus L.): Investigations on Molecular Weight Distribution and Antioxidant and Antimicrobial Potentials.

Research on lemon grass (Cymbopogon citratus L.) revealed a variety of active molecules and examined their biological characteristics. However, most of these studies were conducted on wild varieties, while cultivated plants were addressed less. This study aimed to characterize the biomolecules and biological activities of lemon grass growing under North African conditions in Morocco. Phenolic compound profiles of aqueous (AE), ethanol (EE), and methanol (ME) extracts and their fractions were obtained with steric exclusion chromatography on Sephadex G50 gel and identified by LC-MS/MS. Then, total polyphenols (TPC), flavonoids (TFC), and antioxidant activities (FRAP: scavenging value and TAC: Total Antioxidant Capacity) of the fraction were evaluated, as well as the antimicrobial activity. The obtained results showed that the ME contained eight major compounds (i.e., apigenine-7-O-rutinoside and myricitine-3-O-rutinoside). The AE showed the presence of five molecules (i.e., kaempferol-3-O-glucuronide), while EE showed the presence of three molecules (i.e., quercetine-3-O-rutinoside). Regarding the chemical characterization, the highest value of total phenolic content (TPC) was obtained in AE (25) (4.60 ± 0.29 mg/g), and the highest value of total flavonoid content (TFC) was obtained in ME (29) (0.7 ± 0.08 mg/g). Concerning the antioxidant activity, the highest FRAP was obtained in ME (29) (97.89%), and the highest total antioxidant capacity (TAC) was obtained in ME (29) (89.89%). Correlation between FRAP, TPC, and TFC was noted only in fractions of AE and ME. All tested extracts of C. citratus and their fractions showed a significant antimicrobial effect. The lowest minimum inhibitory concentration (MIC) was recorded for ME against E. coli. Extracts' biological activities and their fractions were governed by their active molecules. These data are new and clarify a novel aspect of bioactive molecules in the extracts of cultivated C. citratus. Equally, throughout this research, we clarified the relationship between identified molecules and their biological properties, including antioxidant and anti-microbial activities, which is new for the study area. This study is suggested as a reference for comparative studies and other assays of other biological activities for the study plant.

Construction of thermostable and temperature-responsive emulsion gels using gelatin: A novel strategy for replacing animal fat

The growing demand from consumers for reduced levels of saturated fat in food has prompted researchers' enthusiasm to develop animal fat substitutes. However, none of the animal fat replacers exhibit similar thermal responsiveness to animal fat yet. In this study, gelatin with varying bloom numbers (B) were utilized to stabilize high internal phase emulsions (HIPEs), and thermally stable and responsive animal fat replacer were created. The emulsion gels (EGs) stabilized by gelatins of 120 B (EG120), 160 B (EG160), and 200 B (EG200) return to initial state after cooling to room temperature. During the 4-80-4 °C cycle, the storage modulus (G′) recovery rates of EG160 and EG200 were 94.79% and 93.34% respectively, demonstrating temperature response characteristics. EG160, EG200, and lard exhibited no significant difference in terms of hardness, springiness, cohesiveness and chewiness. The microstructure investigation revealed that the continuous phase of gelatin generates a dense three-dimensional network structure. 160 B and 200 B exhibited superior emulsifying ability and surface hydrophobicity, suitable molecular weight distribution and an appropriate amount of hydrogen bonds. These factors promoted the formation of a uniform and dense gel network in EGs. This work offered a temperature-responsive EGs based on gelatin, for replacing animal fat in food processing.

A mechanistic study on the alleged cellulose cross-linking system: Maleic acid/sodium hypophosphite

A combination of maleic acid and sodium hypophosphite as a durable press finishing agent has been reported as a safer but equally effective alternative to conventional formaldehyde-based cross-linking agents for applications in cellulose-based fiber and textile finishing. However, the mechanistic details of this system have not yet been fully elucidated to allow optimization of the conditions. Effective cross-linking treatment requires high curing temperatures of ≥160 °C, which enhances oxidative and thermal degradation of cellulose. In this work, the sequential steps of the cross-linking mechanism were investigated both with model compounds and cellulosic substrates. Extensive NMR studies on model compounds revealed several side reactions alongside the synthesis of the targeted cross-linkable moiety. As an alternative, to circumvent side reactions, a two-step procedure was used by synthesizing the cross-linker sodium 2-[(1,2-dicarboxyethyl)phosphinate]succinic acid in a well-defined pre-condensation reaction before application onto the cellulosic substrate. Further, the effect of the cross-linking treatment on the molecular weight distribution of cellulose was studied by gel permeation chromatography, which showed degradation due to maleic acid/sodium hypophosphite treatment. By using sodium 2-[(1,2-dicarboxyethyl)phosphinate]succinic acid and sodium hypophosphite, this degradation could be significantly limited.

Effect of branch length of cluster dextrin on the textural and rheological properties of κ-carrageenan emulsion gels

In this paper, a range of novel cluster dextrins (CDs) with high molecular weight (∼105 g/mol) and narrow molecular weight distribution were fabricated by α-amylase and branching enzyme (BE, EC 2.4.1.18). The influence of CDs on the physicochemical properties of κ-carrageenan (KC) emulsion gels was investigated. The average particle size of the composite emulsion gels containing CD was decreased by 7.85–12.66 μm, and the gel network was more uniform and denser, owing to stronger non-covalent interactions in the composite sample system. Textural results demonstrated that the composite emulsion gels exhibited higher hardness and springiness, but lower cohesiveness. CDs hindered the formation and aggregation of KC double helices, as evidenced by reducing the intensity of the sulfate group peak at 1223 cm−1. Furthermore, CDs increased the apparent viscosity, storage modulus (G'), and melting temperature (Tm) of emulsion gels, based on rheological results. CDs with longer branch lengths were more prone to entangle with KC chains to optimize the gel structure, exhibiting a more significant effect on the physicochemical properties of emulsion gels. The present study provided a new insight for constructing a new energy delivery system.

Anionic ring-opening polymerization of ferrocenylcyclosiloxanes: a comprehensive structural study

In this study, a comprehensive structural analysis of the linear redox-active ferrocenyl-containing polysiloxanes (FPSs) was performed by the liquid-state 1H, 13C, and 29Si nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), and cyclic voltammetry. FPSs with tunable Fc unit content ranging from 20 to 100 mol% were obtained by anionic ring-opening polymerization (AROP). The 29Si NMR spectroscopy indicates the successful anionic homopolymerization of the mono- and tetraferrocenyl-substituted cyclotetrasiloxanes (Fc4D4 and Fc1D4) by appearance of new signals of Si atoms corresponding to a polymer backbone. An analysis of pentad assignments in 29Si NMR determined the anionic copolymerization of Fc4D4 with D4 by indicating signals of neighboring Si atoms from different types of polymer units (DF and D), which differ from the signals of homopolymers. The Mayo-Lewis copolymerization constants of Fc4D4 and D4 were determined by the Fineman–Ross method. The molecular masses and unimodal molecular weight distribution of FPSs were estimated by using GPC. FPSs possess redox-activity. Thus, the proposed comprehensive approach analyzes structural features of the functional silicones with enhanced redox properties, which can be applied in (opto)electronics, coatings, and biomedicine.

Tracking Chain Populations and Branching Structure during Polyethylene Deconstruction Processes.

Catalytic deconstruction has emerged as a promising solution to valorize polyethylene (PE) waste into valuable products, such as oils, fuels, surfactants, and lubricants. Unfortunately, commercialization has been hampered by inadequate optimization of PE deconstruction due to an inability to either truly characterize the polymer transformations or adjust catalytic conditions to match the ever-evolving product distribution and associated property changes. To address these challenges, a detailed analysis of molar mass distributions and thermal characterization was developed herein and applied to low-density polyethylene (LDPE) deconstruction to enable more thorough identification of polymer chain characteristics within the solids (e.g., changes in molar mass or branching structure). For example, LDPE hydrocracking exhibited comparable rates of polymer chain isomerization and C-C bond scission, and the solids generated possessed a broadened molar mass distribution with a disappearance of a significant fraction of highly linear segments, indicating polymer-structure-dependent interactions with the catalyst. Solids analysis from pyrolysis yielded starkly different results, as the resulting solids were devoid of unreacted polymer chains and had a narrowed molar mass distribution even at short times (e.g., 0.2 h). By tracking the polymeric deconstruction behavior as a function of reaction type, time, and catalyst design, we mapped critical pathways toward PE valorization.

Antioxidant Marine Hydrolysates Isolated from Tuna Mixed Byproducts: An Example of Fishery Side Streams Upcycling.

The aim of this research is to propose simple and scalable processes to obtain bioactive peptides extensively hydrolyzed starting from a tuna mixed biomass. The upcycling of this powdered biomass is challenging since it comes from the unsorted industrial side streams of the tuna canning process (cooked residues from fillet trimming) after a patented mild dehydration useful for preventing its degradation until its exploitation. Two different protocols were proposed, with and without the inclusion of an exogenous enzyme (Enzymatic-Assisted Extraction, EAE), with no relevant differences in yields (24% vs. 22%) and a comparable amino acid composition. Nevertheless, the former protocol (with EAE) provided peptides with an average molecular weight of 1.3 kDa, and the second one (without EAE) provided peptides with an average molecular weight of 2.2 kDa. The two corresponding types of tuna protein hydrolysates (Enzymatic Hydrolysates (EH) and Non-Enzymatic Hydrolysates (NEH)) were characterized by proximate compositions, pH, color profile, amino acid analysis, FTIR spectra, and molecular weight distribution. In addition, several biological analyses were performed to assess their potential use as nutraceutical supplements: special attention has been paid to antioxidant activity using three different methods to quantify it. EH showed the most promising antioxidant activity which could be exploited also in other fields (e.g., biomaterials, cosmetics).

Extraction and characterisation of sodium alginate from the Southern African seaweed Ecklonia maxima

Abstract Ecklonia maxima is an endemic South African seaweed with numerous commercially valuable compounds, including sodium alginate. This polysaccharide contains 1,4-linked β-d-mannuronic (M) and α-l-guluronic acid (G) residues, and has enormous health and food applications and benefits for biomedicine. In this study, acid extraction of sodium alginate from Ecklonia maxima was performed, and its chemical and physical properties were compared with commercial sodium alginate. A yield of 58.7 % (w/w of dry alga) sodium alginate was recovered from the seaweed. As expected, Fourier-transform infrared spectroscopy and nuclear magnetic resonance spectroscopic analyses of sodium alginate revealed the presence of M and G residues in the polysaccharide. Circular dichroism (CD) spectroscopy revealed an M/G ratio of 1.86 from the extracted sodium alginate. The viscosity average molecular weight of sodium alginate was 429 kDa using the Mark–Houwink–Sakurada equation. Three-dimensional conformational analysis by Congo red and CD spectroscopy suggested that sodium alginate exhibits a triple-helix conformation in solution. Furthermore, X-ray powder diffraction analysis confirmed that the alginate has an amorphous structure. Sodium alginate extracted from E. maxima found on the coasts of Southern Africa exhibits a high mannuronic content and high viscosity, potentially beneficial for drug delivery and biomedical applications.

A highly efficient oxygen tolerant visible-light mediated RAFT polymerization

Recently, oxygen-tolerant reversible addition-fragmentation chain transfer (RAFT) polymerization has attracted increasing attention in polymer chemistry. Inspired by the monomers containing glycol ethers group have high polymerization rates and even achieved a desirable oxygen tolerance. Herein, we proposed a simple, effective, low-cost, and eco-friendly strategy to accomplish the oxygen-tolerant visible-light activated RAFT polymerization of acrylates and acrylamides in a mixed solution of glycol ether and water at ambient temperature. This photo-mediated RAFT polymerization does not require additives, prior deoxygenation, or inert gas protection. The acrylates and acrylamides with high conversion under irradiation for 2 h, and the resulting polymers were narrow unimodal and narrow molecular weight distributions (PDI<1.3). In addition, the “living” and well-controlled behaviors of this oxygen-tolerant photo-mediated RAFT polymerization were demonstrated through water content in solvents, headspace, initial concentration of monomers, various monomers, chain lengths, light ON/OFF experiment, and high-end group fidelity of block copolymers. This RAFT polymerization also opens up a wide avenue for the industrial production of functional polymeric materials via an in situ chain extension strategy. These results indicate that the mixed solution of glycol ethers and water are effective green media for promoting photo-mediated RAFT polymerization without additives or tedious degassing processes.

Effects of molecular structure and temperature field on the crystallization behavior of poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether)

Despite the wide industrial application of poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether) (PFA) in semiconductor processing, its crystallization behavior has little been studied. In this work, three PFA resins with similar molecular weight but different comonomer content and distribution were synthetized. Then the non-isothermal crystallization kinetics and crystalline structures were studied by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction systematically. It is found that the incorporation of comonomers destroys the chain regularity and reduces the crystallizability of PFA thermodynamically, while the comonomer insertion improves the chain flexibility to accelerate the crystal growth dynamically. When the comonomer content of PFA is low, both the nucleation and growth rates are quite fast, which is favorable for the formation of spherulite. As the comonomer content increases or distribute uniformly in the chain, the nucleation rate declines notably and the side groups distort the crystal cell to increase the spacing of [100] plane. Moreover, two-dimensional growth mode is dominant to form bundle-like structure when crystallizing at slow cooling, where nucleation is suppressed by growth. But three-dimensional symmetrical spherulite can be activated and perfected at high cooling rate due to the initiation of substantial nucleation sites. This unique crystallization behavior is opposite to that of conventional polymers, providing a guidance for the polymerization and processing of PFA.