Recovery of Bioactive Compounds from Hazelnuts and Walnuts Shells: Quantitative–Qualitative Analysis and Chromatographic Purification

Hazelnut (HS) and walnut (WS) shells, an abundant by-product of the processing industries of these edible nuts, are traditionally considered as a low-value waste. However, they are a source of valuable compounds with an interesting chemical profile for the chemical and pharmaceutical sectors. In this study, the lipophilic and hydrophilic extracts present in HS and WS were quantified and identified, then the polar fractions were chromatographically separated, and their antioxidant capacity was studied. The experimental work includes the isolation of crude lipophilic and hydrophilic extracts by an accelerated extraction process, chromatographic analysis (gas chromatography-flame ionization (GC-FID), GC-mass spectroscopy (GC-MS), high-performance size-exclusion chromatography (HPSEC), thin-layer chromatography (TLC)), and quantification of the components. In addition, a thorough compositional characterization of the subgroups obtained by flash chromatography and their antioxidant capacity was carried out. The gravimetric concentrations showed different lipophilic/hydrophilic ratios (0.70 for HS and 0.23 for WS), indicating a higher proportion of polar compounds in WS than in HS. Moreover, the lipophilic extracts were principally composed of short-chain fatty acids (stearic, palmitic, and oleic acid), triglycerides, and sterols. The polar fractions were screened by thin-layer chromatography and then separated by flash chromatography, obtaining fractions free of fatty acids and sugar derivatives (97:3 in HS and 95:5 in WS), and mixtures richer in phenolic compounds and flavonoids such as guaiacyl derivatives, quercetin, pinobanksin, and catechin. The most polar fractions presented a higher antioxidant capacity than that of the crude extracts.This work was supported by the Basque Government (Grupos Consolidados IT-1264-19). U.G.-G. was supported by Fundación Biofísica Bizkaia. A.B.-V. was supported by Programa de especialización de Personal Investigador Doctor en la UPV/EHU (2019) 2019–2020. S.J.-B. and A.L.-S. were supported by a grant PIF (2017–2018) and (2019–2020), Gobierno Vasco, respectively. A.L.-S. was partially supported by Fundación Biofísica Bizkaia

Comparison of Polysaccharides Extracted from Cultivated Mycelium of Inonotus obliquus with Polysaccharide Fractions Obtained from Sterile Conk (Chaga) and Birch Heart Rot

The polysaccharides of the sterile conk of Inonotus obliquus (Chaga) have demonstrated multiple bioactivities. The mycelium of this basidiomycete, obtained after submerged cultivation, has been considered a feasible alternative to the sterile conk for the production of polysaccharides. However, previous research has paid little attention to the differences in the structures of polymers obtained from the different resources. Moreover, the birch wood colonized by I. obliquus has never been investigated as a source of bioactive polysaccharides. In the present study, polysaccharide fractions produced from cultivated mycelium, sterile conks of different geographical origins, and birch heart rot were investigated. High amounts of phenolic compounds, possibly lignans, were bound to the sterile conk polysaccharides. Mycelial polysaccharides were rich in alpha- and beta-glucans and had high (10(5) Da) and low (10(4) Da) molecular weight populations. On the other hand, sterile conk polysaccharides were mainly beta-glucan of lower and monodispersed molecular weight (10(3) Da). Heart rot polysaccharides were comprised mainly of low molecular weight (10(3) Da) hemicelluloses. Nevertheless, fungal polysaccharides were identified in the extracts. The differences in structure and molecular properties among the polysaccharide fractions of mycelium, heart rot, and sterile conk are likely associated with differences in bioactivities and, therefore, in nutraceutical potential

Effect of Hybrid Type and Harvesting Season on Phytochemistry and Antibacterial Activity of Extracted Metabolites from Salix Bark

Hundreds of different fast-growing Salix hybrids have been developed mainly for energy crops. In this paper, we studied water extracts from the bark of 15 willow hybrids and species as potential antimicrobial additives. Treatment of ground bark in water under mild conditions extracted 12-25% of the dry material. Preparative high-performance liquid chromatography is proven here as a fast and highly efficient tool in the small-scale recovery of raffinose from Salix bark crude extracts for structural elucidation. Less than half of the dissolved material was assigned by chromatographic (gas chromatography and liquid chromatography) and spectroscopic (mass spectrometry and nuclear magnetic resonance spectroscopy) techniques for low-molecular-weight compounds, including mono- and oligosaccharides (sucrose, raffinose, and stachyose) and aromatic phytochemicals (triandrin, catechin, salicin, and picein). The composition of the extracts varied greatly depending on the hybrid or species and the harvesting season. This information generated new scientific knowledge on the variation in the content and composition of the extracts between Salix hybrids and harvesting season depending on the desired molecule. The extracts showed high antibacterial activity on Staphylococcus aureus with a minimal inhibitory concentration (MIC) of 0.6-0.8 mg/mL; however, no inhibition was observed against Escherichia coli, Enterococcus faecalis, and Salmonella typhimurium. MIC of triandrin (i.e., 1.25 mg/mL) is reported for the first time. Although antibacterial triandrin and (+)-catechin were present in extracts, clear correlation between the antibacterial effect and the chemical composition was not established, which indicates that antibacterial activity of the extracts mainly originates from some not yet elucidated substances. Aquatic toxicity and mutagenicity assessments showed the safe usage of Salix water extracts as possible antibacterial additives.Peer reviewe

Fractionation of Lignin with Decreased Heterogeneity: Based on a Detailed Characteristics Study of Sequentially Extracted Softwood Kraft Lignin

Industrial lignin fractionation is attracting increasing interest due to its enormous potential in the development of high value-added materials. However, the widely reported fractionation approaches are primarily focused on the separation of fractions with a low polydispersity index (PDI). In this study, based on the detailed characteristic examination of carefully sequential-extracted softwood Kraft lignin fractions, a novel method to isolate lignin fraction with decreased heterogeneity (LGF-dh), was established in consideration of impurities, elemental composition, molar mass distribution, carbohydrate content, functional hydroxyl content, and the content of lignin-relevant aromatic units. To characterize the mentioned properties, an elemental analyzer, SEC-MALS, GC-MS, GC-FID, Py/GCMS, P-31-NMR, and HSQC-NMR were used to compare the differences of the sequential lignin fractions that were obtained by methyl tert-butyl ether (MTBE), ethyl acetate (EtOAc), ethanol (EtOH), methanol (MeOH), acetone, and dioxane. Moreover, a practical and feasible three-step extraction process was proposed to separate the low heterogeneity lignin fraction from industrial lignin according to the different solubilities of each fraction in the green cosolvent system of EtOH/water, MeOH/water, and acetone/water. Overall, this work presented a comprehensive study on the properties of softwood lignin as well as proposed a feasible and convenient method to reduce the heterogeneity of lignin, which would promote its valorization

Environmentally-compatible alkyd paints stabilized by wood hemicelluloses

Wood biorefining currently involves large-scale industrial processes where a notable portion of raw materials, namely hemicelluloses and lignin, are either lost with the process water, degraded, or burnt for energy. Value added utilization of polymeric hemicelluloses is challenging due to their intermediate molar mass and the presence of other wood components, such as phenolic residues or wood extractives. Oil-in-water (O/W) emulsions represent a diverse and abundant class of applications in which the natural properties of wood hemicelluloses are beneficial. In the current work, we present highly promising new technical alkyd paint emulsion systems stabilized with hardwood glucuronoxylans (GX) and softwood galactoglucomannans (GGM). Samples from three isolation methods and their further fractionation by ethanol precipitation were systematically compared with regard to hemicellulose composition, interfacial activity, and functionality in emulsions. Emulsification of alkyd resins was successful with both GX and GGM obtained by various biorefining strategies. The highest emulsion stability over storage was achieved using crude non-purified GX and GGM fractions, and was correlated with the presence of phenolic compounds and extractives, interfacial activity, and small droplet size. Hardwood GX and softwood GGM are envisioned as natural emulsifiers of alkyd O/W emulsions, which are examples of diverse and abundantly-used technical dispersions. This study can be utilized as a guideline for targeted extraction of hemicelluloses with desired functionality, and as a protocol for developing environmentally-compatible industrial dispersions.Peer reviewe

A model of access combining triage with initial management reduced waiting time for community outpatient services: a stepped wedge cluster randomised controlled trial

BACKGROUND: Long waiting times are associated with public community outpatient health services. This trial aimed to determine if a new model of care based on evidence-based strategies that improved patient flow in two small pilot trials could be used to reduce waiting time across a variety of services. The key principle of the Specific Timely Appointments for Triage (STAT) model is that patients are booked directly into protected assessment appointments and triage is combined with initial management as an alternative to a waiting list and triage system. METHODS: A stepped wedge cluster randomised controlled trial was conducted between October 2015 and March 2017, involving 3116 patients at eight sites across a major Australian metropolitan health network. RESULTS: The intervention reduced waiting time to first appointment by 33.8% (IRR = 0.663, 95% CI 0.516 to 0.852, P = 0.001). Median waiting time decreased from a median of 42 days (IQR 19 to 86) in the control period to a median of 24 days (IQR 13 to 48) in the intervention period. A substantial reduction in variability was also noted. The model did not impact on most secondary outcomes, including time to second appointment, likelihood of discharge by 12 weeks and number of appointments provided, but was associated with a small increase in the rate of missed appointments. CONCLUSIONS: Broad-scale implementation of a model of access and triage that combined triage with initial management and actively managed the relationship between supply and demand achieved substantial reductions in waiting time without adversely impacting on other aspects of care. The reductions in waiting time are likely to have been driven, primarily, by substantial reductions for those patients previously considered low priority. TRIAL REGISTRATION: Australian New Zealand Clinical Trials Registry ACTRN12615001016527 registration date: 29/09/2015

Sugarcane bagasse valorization by fractionation using a water-based hydrotropic process

Sugarcane bagasse is abundant agro-industrial waste that can be potentially utilized as a source of valuable compounds and biopolymers. In the present study, sugarcane bagasse from Brazil was fractionated employing an environmentally friendly hydrotropic process. Several treatments were carried out at 150 and 170 °C and dwell times of 60 and 120 min using unmodified 30% hydrotropic solutions as well as the solutions acidified with formic acid. The major produced fraction was cellulose pulp obtained with the yield of 44–67% (bagasse based) and the cellulose content of 60–92%. Lignins dissolved during the treatments were isolated from the spent solutions by dilution with water and filtration. The yields of the lignins were 11.8–14.7% (bagasse based) and their purity ranged from 88 to 94%. Generally, the purity of both fractions and the yield of lignin were higher at more severe process conditions. However, the more severe conditions resulted in lower average molar masses of the lignins and lower intrinsic viscosity values of the cellulose fractions. The composition of the spent solutions also varied with the treatment conditions, and, besides the lignins, they contained different amounts of dissolved hemicelluloses, sugar monomers, furfural and acetic and formic acids. The results of the present study showed that the hydrotropic process could be successfully applied for the valorization of sugarcane bagasse by its fractionation into lignin, cellulose and other products.status: publishe

Bark Extractives and Suberin Monomers from Arbutus andrachne and Platanus orientalis

Arbutus andrachne and Platanus orientalis grow naturally in Turkey. They do not occur in stands but can be seen as solitary trees. A. andrachne is seen in coastal parts of Anatolia, whereas P. orientalis can be found from west to the east of Turkey, mostly in river banks. Lipophilic extractives, hydrophilic extractives, and suberin monomers from Arbutus andrachne and Platanus orientalis bark was analyzed by chromatography. The total amount of lipophilic extractives was higher in P. orientalis (8.55 mg/g). However, the total amount of hydrophilic extractives had a bigger proportion, 100.86 mg/g, in A. andrachne bark. Dioic and hydroxy acids were the dominant group in the suberin monomers of both species of bark. Acid 1,18-dioic-18:0 and acid 18-hydroxy-18:1 were determined as the main compounds of suberin monomers in both samples. In addition, total amount of suberin monomers was determined to be 11.36 mg/g in A. andrachne and 15.95 mg/g in P. orientalis bark