Lignins from Agroindustrial by-Products as Natural Ingredients for Cosmetics: Chemical Structure and In Vitro Sunscreen and Cytotoxic Activities.

The growing concern about the environmental impact and human health risk related to the excessive use of synthetic ingredients in cosmetics and topical formulations calls for the exploration of safe and sustainable natural alternatives. Lignin-rich lignocellulosic industrial wastes such as hazelnut and walnut shells were used as a lignin polymer source. Agro-derived lignins were evaluated as a potential natural active ingredient for health care products. Aside from the structural characteristics of isolated lignins, which were identified by GPC, Py-GC-MS, and 2D HSQC NMR techniques, functional properties such as antioxidant power and UV absorption ability were investigated. The SPF values found for creams containing 5% of hazelnut and walnut lignin content were 6.9 and 4.5, respectively. Additionally, both lignin types presented appropriate protection against UVA radiation, highly interesting property to block the full ultraviolet spectrum. The biological activity of isolated lignins assessed at different concentrations (0.01-1 mg/mL) and different times (24, 48, and 72 h) on murine fibroblast cell line 3T3 suggested their suitability for cosmetic applications.

Potential of lignin multifunctionality for a sustainable skincare: Impact of emulsification process parameters and oil-phase on the characteristics of O/W Pickering emulsions.

Colloidal lignin particles (CLPs) from softwood kraft lignin were evaluated as a multifunctional ingredient to prepare bio-based oil-in-water (O/W) Pickering emulsions. After a preliminary screening, three Pickering emulsions systems were formulated using orange, coconut, and paraffin oils, at varying concentration of CLPs, oil/water ratio, and by applying two-step homogenisation processes (rotor-stator homogenisation followed by ultrasonication). Ultrasonication as a second homogenisation step considerably enhanced the emulsification efficiency, generating emulsions with smaller droplet size and less polydisperse distribution. Furthermore, the effect of ultrasonication on the characteristics of emulsions and the stability of the systems was evaluated over time. The oil content and type, the concentration of CLPs, and the homogenisation methods significantly influenced the characteristics of the emulsions and drop size. Higher concentrations of oil and CLPs favoured the formation of the emulsion and contributed to higher physical stability after 120 days of monitoring. The in vitro Sun Protection Factor (SPF) results demonstrated that the incorporation of natural oils containing phenolic compounds in Pickering formulations improves the SPF value of emulsions, showing an interesting synergic effect between lignin particles and vegetable oils, which was not observed in the case of paraffin oil. Furthermore, the broad-spectrum sun blocker of Pickering emulsions was confirmed by the values of UVA/UVB between 0.74 and 0.90 and Cλ > 380.

Simultaneous Improvement of Surface Wettability and UV Resistance of Wood with Lignin-Based Treatments.

Recent advancements in wood modification aim to enhance the inherent qualities of this versatile biological material, which includes renewability, ease of processing, and thermal insulation. This study focuses on evaluating the effectiveness of lignin as a protective agent for less durable wood species, namely, Pinus nigra and Fagus sylvatica L. The impregnation of wood with three various forms of lignin, such as kraft lignin, acetylated kraft lignin, and lignin nanoparticles, was carried out using the vacuum technique at room conditions. The results showed that the treatments significantly improve the hydrophobicity of wood surfaces, particularly in pine wood, and provide protection against UV ageing. Additionally, the treatments contributed to the stabilisation of moisture content at different humidity levels. Although slight colour variations were observed, their impact on the visual appearance was minimal, and the thermal analysis confirmed enhanced thermal properties. Additionally, plasma treatment further enhanced hydrophobicity after treatments, offering potential benefits in terms of moisture resistance and durability. The findings of this study highlight the promising effects of lignin-based treatments on wood properties, providing sustainable solutions for wood protection in various sectors. However, further optimisation is needed to fully explore the potential of lignin and lignin nanoparticles.

One-Step Lignin Refining Process: The Influence of the Solvent Nature on the Properties and Quality of Fractions.

Heterogeneity of kraft lignin is one of the main limitations for the development of high-performance applications. Therefore, refining lignin using organic solvents is a promising strategy to obtain homogenous fractions with controlled quality in terms of structure and properties. In this work, one-step refining processes for hardwood kraft lignin using nine organic solvents of different chemical nature and polarity were carried out with the aim of investigating and understanding the effect of the type of organic solvent on the quality of resulting fractions. Structural features of both soluble and insoluble lignin fractions were assessed by GPC, Py-GC-MS, and FTIR linked to PCA analysis. Moreover, functional properties such as physical appearance, hygroscopicity, antioxidant capacity, and thermal properties were evaluated. The results evidenced the relationship between the nature and polarity of the solvents and the properties of the obtained soluble and insoluble fractions.

Surface chemistry and bioactivity of colloidal particles from industrial kraft lignins.

The morphology control of lignin through particle size reduction to nanoscale seems to be a suitable conversion technology to overcome the intrinsic limitations of its native form to develop a wide range of biomaterials with high performance. Colloidal lignin particles (CLPs) in the range of 150-200 nm were synthesised from hardwood and softwood kraft lignins by the solvent shifting method. The initial molecular features of kraft lignins were evaluated in terms of purity, molecular weight distribution, and chemical functionalities. The impact of the lignin source and structure on the morphology, size distribution, and surface chemistry of CLPs was evaluated by particle size analyser, SEM, TEM and 1H NMR. The results evidenced the influence of the botanical origin on the morphology and surface chemistry of particles. Furthermore, the antioxidant properties and cytotoxicity of lignins and corresponding CLPs, towards lung fibroblast cells were compared. CLPs from hardwood kraft lignins exhibited higher antioxidant power against DPPH free radical and a higher cytotoxic effect (IC30 = 67-70 µg/mL) against lung fibroblast when compared to CLPs from softwood kraft lignin (IC30 = ~91 µg/mL). However, the cytotoxicity of these biomaterials was dose-dependent, suggesting their potential application as active ingredients in cosmetic and pharmaceutic products at low concentrations.

Fractionation of lignin using organic solvents: A combined experimental and theoretical study.

Refining of industrial lignin to produce homogeneous fractions is essential for high-value applications. However, the understanding of key interactions between a variety of solvents with lignin polymer is still uncertain. In this work, single-step fractionation of industrial hardwood kraft lignin (HKL) using organic solvents of different polarities - ethanol, acetone, diethyl ether and hexane - was investigated by combining an experimental and theoretical approach. Experimental results revealed that higher polarity solvents (ethanol and acetone) exhibited higher solubility yield compared to moderate and low polarity solvents. The chemical differences between lignin fractions were proven by pyrolysis gas chromatography mass spectrometry and near infrared spectroscopy. Density functional theory (DFT) results indicated that ethanol presented higher interaction energy followed by acetone, diethyl ether and hexane, which was consistent with experimental findings. Hydrogen bond and non-covalent interaction results from DFT demonstrated that the predominant interaction was found for high polarity of ethanol over other solvents and γ-OH in the lignin model is the key site.

Enhancement of UV absorbance and mechanical properties of chitosan films by the incorporation of solvolytically fractionated lignins.

In this work, an effective sequential organic solvent extraction of kraft and organosolv lignins was carried out to separate lignin into more homogeneous fractions with specific properties. The selected solvents were ethyl acetate, ethanol, methanol, and acetone in that order. Fractions were analysed in terms of their yield, molecular weight, S/G ratio, and phenolic hydroxyl groups content. The incorporation of lignin fractions into the chitosan was aimed to increase the UV absorbance and the mechanical resistance of the chitosan films, which would provide good properties for applications in the packaging field. Films were analysed in terms of UV-vis absorption spectra, tensile strength, as well as colour changes. Results showed a significant increase in the absorbance of UV-A and UV-B with the addition of lignin fractions, mechanical properties showed an increase in the ultimate tensile strength in case of kraft fractions, while organosolv fractions do not affect tensile strength significantly.

Organic acids as a greener alternative for the precipitation of hardwood kraft lignins from the industrial black liquor.

The use of three organic acids such as acetic, lactic and citric acid has been investigated as green precipitation agents for kraft lignin isolation from the industrial hardwood black liquor. Chemical composition, molecular structure characteristics in addition to thermal and antioxidant properties were evaluated and compared to kraft lignin precipitated with sulfuric acid. A clear influence of the organic acids was observed in the chemical composition and molecular properties. Organic acids generated lignins with high purity and low ash and carbohydrate contents. FT-IR and Py-GC-MS analyses revealed the ability of organic acids to produce lignins with greater content of methoxylated structures and carbonyl groups than sulfuric acid. Moreover, all evaluated kraft lignins exhibited a suitable radical scavenging activity, and higher than found for commercial antioxidant used as control. TG analysis showed that the employment of organic acids with higher ionic strength lead less thermally stable kraft lignin. In addition, the proximate analysis confirmed the high potential of kraft lignins as an energy source (21-24 MJ/Kg).

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.

In vitro cytotoxicity studies of industrial Eucalyptus kraft lignins on mouse hepatoma, melanoma and Chinese hamster ovary cells.

Kraft lignin is a polyphenolic compound generated as a by-product from the kraft pulping process in large quantities annually worldwide. In addition to its commercial availability, its structural features make it worth to be considered in the pharmaceutical area. The present study was carried out to evaluate in vitro antioxidant and cytotoxic properties of kraft lignin on mouse hepatoma MH-22A, melanoma B16 (tumor cells) and Chinese hamster ovary (CHO, non-cancerous) cells. Moreover, several analytical techniques were used in order to elucidate the chemical structure of isolated industrial lignins (FT-IR, GPC, Py-GC-MS, 2D HSQC NMR). Results revealed high phenolic content in their composition, high-condensed structure and high phenolic hydroxyls group content. DPPH and ABTS⁎+ radical scavenging assays demonstrated their strong antioxidant activity, which was higher than found for commercial antioxidant (BHT). Kraft lignins act cytotoxically inducing apoptosis- and necrosis-like processes on both on tumor and normal cells. However, the results evidenced that MH-22A cells showed greater sensitive behavior than B16 and non-cancerous CHO cells, which were more tolerant of kraft lignin.

Potential use of kraft and organosolv lignins as a natural additive for healthcare products.

The growing interest in substituting synthetic products coming from non-renewable sources with products from biomass has focused attention on the lignin biopolymer. Its high availability, low price and properties make the development of new and valuable uses for lignin interesting, thus improving the economic and environmental aspects of the biomass conversion. To achieve this objective, the potential use of industrial kraft and organosolv lignins as antioxidants, antimicrobials and sunscreen products has been evaluated. The results of a detailed antibacterial and antifungal study demonstrated the high potential of kraft lignins against a variety of foodborne and human pathogenic microorganisms. Moreover, both organosolv and kraft lignins presented an effective protection factor (SPF values from 10-20), demonstrating their effectiveness as natural additives for the sun lotion market. In addition, lignin samples presented high antioxidant capacity compared to butylated hydroxytoluene (BHT), one common commercial antioxidant industrially used. Therefore, the development of innovative applications of lignins as a commodity for the chemical, pharmaceutical or cosmetic industries could expand their possible uses in the market giving new added values to lignin.

Production of cellulose nanoparticles from blue agave waste treated with environmentally friendly processes.

Tequila elaboration leaves two main byproducts that are undervalued (bagasse and leaves). Organosolv pulping and Total Chlorine Free bleaching were integrated to obtain cellulose fibers from agricultural waste which consisted of blue agave bagasse and leaf fibers; together they represent a green process which valorizes biomass waste. The obtained celluloses were characterized by FT-IR, colorimetry, and SEM and their extraction yields were evaluated. These celluloses were used to produce cellulose nanocrystals and cellulose nanofibers. First, an acid hydrolysis was performed in a sonication bath to induce cavitation during the reaction to produce cellulose nanocrystals. Then a high-pressure homogenization was selected to produce cellulose nanofibers. These nanocelluloses were characterized by powder XRD, Nanosizer, zeta potential, NMR, and electronic microscopy. Results showed that cellulose from organosolv pulps bleached with TCF bleaching is suitable for nanocellulose production. Moreover, the use of a new step to separate cellulose nanocrystals resulted in yields almost doubling traditional yields, while the rest of the properties remained within the expected.

Dataset on cellulose nanoparticles from blue agave bagasse and blue agave leaves.

These data and analyses support the research article "Production of cellulose nanoparticles from blue agave waste treated with environmentally friendly processes" Robles et al. [1]. The data and analyses presented here include fitted curves for selected carbons of the 13C CP-MAS NMR analysis; SEM images of the raw and bleached fibers, graphics with chemical composition and visual images of the fibers throughout the process.

Assessment of suitability of vine shoots for hemicellulosic oligosaccharides production through aqueous processing.

Vine shoots were subjected to non-isothermal aqueous processing. A range of severities (S0) from 3.20 to 4.65 was assayed and their effects in terms of solubilization, composition, molar mass distribution, structural characterization and thermal stability of the liquors were studied using HPLC, HPSEC, TGA and FTIR. The spent solids were characterized by HPLC and FTIR. When autohydrolysis was carried out at S0=4.01, the substrate solubilization achieved a 38.7% of the raw material and 83.1% of the initial xylan was converted into xylooligosaccharides (XOS). The amount of TOS (total oligosaccharides) in the hydrolysates was 28.4g/L while the other non volatile compounds (ONVC) were 0.08g/g NVC. The spent solid from the treatment at S0=4.01 was composed about 90% of cellulose and lignin. Therefore, it can be concluded that autohydrolysis is a suitable pretreatment of vine shoots such as a first stage of a biomass refinery.

Xylan-cellulose films: improvement of hydrophobicity, thermal and mechanical properties.

Xylan-rich hemicellulose from corn cob has been used for new material elaboration. Commercial cellulose was used as reinforcement in different percentages to improve properties of the films. Two types of composites were elaborated by solvent casting. Hydrophilic films, composed by bleached hemicellulose (BH), unmodified cellulose and glycerol as plasticizer, and hydrophobic films formed by acetylated bleached hemicellulose (BAH) and acetylated cellulose. The degree of substitution of BAH was 1.8 and acetylated cellulose presented a degree of substitution of 0.54. Thermal and mechanical properties of films were analyzed. A significant improvement was observed in the thermal behavior of hydrophobic films (Tmax ∼ 368 °C) respect to hydrophilic films (Tmax ∼ 300 °C). Although the addition of cellulose clearly increase the properties of both type of films, hydrophobic films (Young's modulus ∼ 2300 MPa, strength ∼ 44.1MPa, strain at break ∼ 5.7%) showed better mechanical properties than hydrophilic films (Young's modulus ∼ 3 MPa, strength ∼ 3.3 MPa, strain at break ∼ 5.3%).