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1.
Small ; 20(33): e2309651, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38530065

RESUMO

The scientific community is pursuing significant efforts worldwide to develop environmentally viable film materials from biomass, particularly transparent, high-performance regenerated cellulose (RC) films, to replace traditional plastics. However, the inferior mechanical performance and hydrophilic nature of RC films are generally not suitable for use as a substitute for plastics in practical applications. Herein, lignin homogenization is used to synthesize high-performance composite films. The esterified lignin nanoparticles (ELNPs) with dispersible and binding advantages are prepared through esterification and nanometrization. In the presence of ELNPs, RC films exhibit a higher tensile strength (110.4 MPa), hydrophobic nature (103.6° water contact angle, 36.6% water absorption at 120 min, and 1.127 × 10-12 g cm cm-2 s-1 Pa-1 water vapor permeability), and exciting optical properties (high visible and low ultraviolet transmittance). The films further display antioxidant activity, oxygen barrier ability, and thermostability. The films completely biodegrade at 12 and 30% soil moisture. Overall, this study offers new insights into lignin valorization and regenerated cellulose composite films as novel bioplastic materials.

2.
Small ; 20(24): e2309459, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38519858

RESUMO

Redox flow batteries (RFBs) are increasingly being considered for a wide range of energy storage applications, and such devices rely on proton exchange membranes (PEMs) to function. PEMs are high-cost, petroleum-derived polymers that often possess limited durability, variable electrochemical performance, and are linked to discharge of perfluorinated compounds. Alternative PEMs that utilize biobased materials, including lignin and sulfonated lignin (SL), low-cost byproducts of the wood pulping process, have struggled to balance electrochemical performance with dimensional stability. Herein, SL nanoparticles are demonstrated for use as a nature-derived, ion-conducting PEM material. SL nanoparticles (NanoSLs) can be synthesized for increased surface area, uniformity, and miscibility compared with macrosized lignin, improving proton conductivity. After addition of polyvinyl alcohol (PVOH) as a structural backbone, membranes with the highest NanoSL concentration demonstrated an ion exchange capacity of 1.26 meq g-1, above that of the commercial PEM Nafion 112 (0.98 meq g-1), along with a conductivity of 80.4 mS cm-1 in situ, above that of many biocomposite PEMs, and a coulombic efficiency (CE), energy efficiency (EE) and voltage efficiency (VE) of 91%, 68% and 78%, respectively at 20 mA cm-2. These nanocomposite PEMs demonstrate the potential for valorization of forest biomass waste streams for high value clean energy applications.

3.
Small ; 19(7): e2205672, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36478382

RESUMO

The design of stimuli-responsive lignin nanoparticles (LNPs) for advanced applications has hitherto been limited to the preparation of lignin-grafted polymers in which usually the lignin content is low (<25 wt.%) and its role is debatable. Here, the preparation of O2 -responsive LNPs exceeding 75 wt.% in lignin content is shown. Softwood Kraft lignin (SKL) is coprecipitated with a modified SKL fluorinated oleic acid ester (SKL-OlF) to form colloidal stable hybrid LNPs (hy-LNPs). The hy-LNPs with a SKL-OlF content ranging from 10 to 50 wt.% demonstrated a reversible swelling behavior upon O2 /N2 bubbling, increasing their size - ≈35% by volume - and changing their morphology from spherical to core-shell. Exposition of hy-LNPs to O2 bubbling promotes a polarity change on lignin-fluorinated oleic chains, and consequently their migration from the inner part to the surface of the particle, which not only increases the particle size but also endows hy-LNPs with enhanced stability under harsh conditions (pH < 2.5) by the hydration barrier effect. Furthermore, it is also demonstrated that these new stimuli-responsive particles as gas tunable nanoreactors for the synthesis of gold nanoparticles. Combining a straightforward preparation with their enhanced stability and responsiveness to O2 gas these new LNPs pave the way for the next generation of smart lignin-based nanomaterials.

4.
Small ; 19(24): e2207085, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36919307

RESUMO

Fabricating bio-latex colloids with core-shell nanostructure is an effective method for obtaining films with enhanced mechanical characteristics. Nano-sized lignin is rising as a class of sustainable nanomaterials that can be incorporated into latex colloids. Fundamental knowledge of the correlation between surface chemistry of lignin nanoparticles (LNPs) and integration efficiency in latex colloids and from it thermally processed latex films are scarce. Here, an approach to integrate self-assembled nanospheres of allylated lignin as the surface-activated cores in a seeded free-radical emulsion copolymerization of butyl acrylate and methyl methacrylate is proposed. The interfacial-modulating function on allylated LNPs regulates the emulsion polymerization and it successfully produces a multi-energy dissipative latex film structure containing a lignin-dominated core (16% dry weight basis). At an optimized allyl-terminated surface functionality of 1.04 mmol g-1 , the LNPs-integrated latex film exhibits extremely high toughness value above 57.7 MJ m-3 . With multiple morphological and microstructural characterizations, the well-ordered packing of latex colloids under the nanoconfinement of LNPs in the latex films is revealed. It is concluded that the surface chemistry metrics of colloidal cores in terms of the abundance of polymerization-modulating anchors and their accessibility have a delicate control over the structural evolution of core-shell latex colloids.

5.
Biotechnol Bioeng ; 120(6): 1557-1568, 2023 06.
Artigo em Inglês | MEDLINE | ID: mdl-36892176

RESUMO

Lignin separation from natural lignocellulose for the preparation of lignin nanoparticles (LNPs) is often challenging owing to the recalcitrant and complex structure of lignocellulose. This paper reports a strategy for the rapid synthesis of LNPs via microwave-assisted lignocellulose fractionation using ternary deep eutectic solvents (DESs). A novel ternary DES with strong hydrogen bonding was prepared using choline chloride, oxalic acid, and lactic acid in a 1:0.5:1 ratio. Efficient fractionation of rice straw (0.5 × 2.0 cm) (RS) was realized by the ternary DES under microwave irradiation (680 W) within only 4 min, and 63.4% of lignin could be separated from the RS to prepare LNPs with a high lignin purity (86.8%), an average particle size of 48-95 nm, and a narrow size distribution. The mechanism of lignin conversion was also investigated, which revealed that dissolved lignin aggregated into LNPs via π-π stacking interactions.


Assuntos
Lignina , Oryza , Lignina/química , Solventes Eutéticos Profundos , Micro-Ondas , Solventes/química , Biomassa , Hidrólise
6.
Cellulose (Lond) ; 30(14): 8955-8971, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37736116

RESUMO

Nanocellulose is very hydrophilic, preventing interactions with the oil phase in Pickering emulsions. This limitation is herein addressed by incorporating lignin nanoparticles (LNPs) as co-stabilizers of nanocellulose-based Pickering emulsions. LNP addition decreases the oil droplet size and slows creaming at pH 5 and 8 and with increasing LNP content. Emulsification at pH 3 and LNP cationization lead to droplet flocculation and rapid creaming. LNP application for emulsification, prior or simultaneously with nanocellulose, favors stability given the improved interactions with the oil phase. The Pickering emulsions can be freeze-dried, enabling the recovery of a solid macroporous foam that can act as adsorbent for pharmaceutical pollutants. Overall, the properties of nanocellulose-based Pickering emulsions and foams can be tailored by LNP addition. This strategy offers a unique, green approach to stabilize biphasic systems using bio-based nanomaterials without tedious and costly modification procedures. Supplementary Information: The online version contains supplementary material available at 10.1007/s10570-023-05399-y.

7.
Int J Mol Sci ; 24(10)2023 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-37240391

RESUMO

A dual-target strategy was designed for the application of lignin nanoparticles in the lipase mediated biosynthesis of novel 3-O-ethyl-L-ascorbyl-6-ferulate and 3-O-ethyl-L-ascorbyl-6-palmitate and in their successive solvent-shift encapsulation in order to improve stability and antioxidant activity against temperature and pH-dependent degradation. The loaded lignin nanoparticles were fully characterized in terms of kinetic release, radical scavenging activity and stability under pH 3 and thermal stress (60 °C), showing improved antioxidant activity and high efficacy in the protection of ascorbic acid esters from degradation.


Assuntos
Antioxidantes , Ácido Ascórbico , Ácido Ascórbico/química , Lignina , Ésteres , Lipase/metabolismo
8.
J Environ Manage ; 330: 117210, 2023 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-36608603

RESUMO

Adsorption is a relatively simple wastewater treatment method that has the potential to mitigate the impacts of pharmaceutical pollution. This requires the development of reusable adsorbents that can simultaneously remove pharmaceuticals of varying chemical structure and properties. Here, the adsorption potential of nanostructured wood-based adsorbents towards different pharmaceuticals in a multi-component system was investigated. The adsorbents in the form of macroporous cryogels were prepared by anchoring lignin nanoparticles (LNPs) to the nanocellulose network via electrostatic attraction. The naturally anionic LNPs were anchored to cationic cellulose nanofibrils (cCNF) and the cationic LNPs (cLNPs) were combined with anionic TEMPO-oxidized CNF (TCNF), producing two sets of nanocellulose-based cryogels that also differed in their overall surface charge density. The cryogels, prepared by freeze-drying, showed layered cellulosic sheets randomly decorated with spherical lignin on the surface. They exhibited varying selectivity and efficiency in removing pharmaceuticals with differing aromaticity, polarity and ionic characters. Their adsorption potential was also affected by the type (unmodified or cationic), amount and morphology of the lignin nanomaterials, as well as the pH of the pharmaceutical solution. Overall, the findings revealed that LNPs or cLNPs can act as functionalizing and crosslinking agents to nanocellulose-based cryogels. Despite the decrease in the overall positive surface charge, the addition of LNPs to the cCNF-based cryogels showed enhanced adsorption, not only towards the anionic aromatic pharmaceutical diclofenac but also towards the aromatic cationic metoprolol (MPL) and tramadol (TRA) and neutral aromatic carbamazepine. The addition of cLNPs to TCNF-based cryogels improved the adsorption of MPL and TRA despite the decrease in the net negative surface charge. The improved adsorption was attributed to modes of removal other than electrostatic attraction, and they could be π-π aromatic ring or hydrophobic interactions brought by the addition of LNPs or cLNPs. However, significant improvement was only found if the ratio of LNPs or cLNPs to nanocellulose was 0.6:1 or higher and with spherical lignin nanomaterials. As crosslinking agents, the LNPs or cLNPs affected the rheological behavior of the gels, and increased the firmness and decreased the water holding capacity of the corresponding cryogels. The resistance of the cryogels towards disintegration with exposure to water also improved with crosslinking, which eventually enabled the cryogels, especially the TCNF-based one, to be regenerated and reused for five cycles of adsorption-desorption experiment for the model pharmaceutical MPL. Thus, this study opened new opportunities to utilize LNPs in providing nanocellulose-based adsorbents with additional functional groups, which were otherwise often achieved by rigorous chemical modifications, at the same time, crosslinking the nanocellulose network.


Assuntos
Poluentes Ambientais , Nanopartículas , Poluentes Químicos da Água , Lignina/química , Criogéis/química , Celulose , Água , Adsorção , Poluentes Químicos da Água/química
9.
Bioprocess Biosyst Eng ; 45(6): 1011-1018, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35312864

RESUMO

This study proposed a recyclable p-toluenesulfonic acid (p-TsOH) fractionation process for co-producing lignin nanoparticles (LNPs) and fermentable sugars from lignocellulosic biorefinery biowaste (enzymatic hydrolysis residue (EHR)). The prepared LNPs were used to detoxify the inhibitors in the xylose-rich prehydrolyzate for improving ethanol production. Results showed that the EHR was fractionated into a cellulose-rich water-insoluble solid (WIS) fraction and a lignin-rich spent liquor (SL) fraction. Cellulase hydrolysis of WIS produced 97.7% of glucose yield, while the LNPs of an average particle size of 98.0 nm with 76.3 % yield (based on the untreated EHR) were obtained from the diluted SL. LNPs demonstrated higher detoxification ability than EHR at the same dosage. Moreover, the fermentability of the detoxified xylose-rich prehydrolyzate was significantly improved. The sugar utilization ratio was 94.8%, and the ethanol yield reached its peak value of 85.4% after 36 h of fermenting the detoxified xylose-rich prehydrolyzate.


Assuntos
Lignina , Nanopartículas , Etanol , Fermentação , Hidrólise , Lignina/química , Xilose
10.
Int J Mol Sci ; 23(23)2022 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-36499190

RESUMO

The exploration of functional films using sustainable cellulose-based materials to replace plastics has been of much interest. In this work, two kinds of lignin nanoparticles (LNPs) were mixed with cellulose nanofibrils (CNFs) for the fabrication of composite films with biodegradable, flexible and ultraviolet blocking performances. LNPs isolated from p-toluenesulfonic acid hydrolysis was easily recondensed and deposited on the surface of composite film, resulting in a more uneven surface; however, the composite film consisting of CNFs and LNPs isolated from maleic acid hydrolysis exhibited a homogeneous surface. Compared to pure CNF film, the composite CNF/LNP films exhibited higher physical properties (tensile strength of 164 MPa and Young's modulus of 8.0 GPa), a higher maximal weight loss temperature of 310 °C, and a perfect UVB blocking performance of 95.2%. Meanwhile, the composite film had a lower environmental impact as it could be rapidly biodegraded in soil and manmade seawater. Overall, our results open new avenues for the utilization of lignin nanoparticles in biopolymer composites to produce functional and biodegradable film as a promising alternative to petrochemical plastics.


Assuntos
Nanofibras , Nanopartículas , Lignina/química , Nanofibras/química , Celulose/química , Nanopartículas/química , Resistência à Tração
11.
Int J Mol Sci ; 23(2)2022 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-35055101

RESUMO

We report here the synthesis of novel thymine biomimetic photo-adducts bearing an alkane spacer between nucleobases and characterized by antimelanoma activity against two mutated cancer cell lines overexpressing human Topoisomerase 1 (TOP1), namely SKMEL28 and RPMI7951. Among them, Dewar Valence photo-adducts showed a selectivity index higher than the corresponding pyrimidine-(6-4)-pyrimidone and cyclobutane counterpart and were characterized by the highest affinity towards TOP1/DNA complex as evaluated by molecular docking analysis. The antimelanoma activity of novel photo-adducts was retained after loading into UV photo-protective lignin nanoparticles as stabilizing agent and efficient drug delivery system. Overall, these results support a combined antimelanoma and UV sunscreen strategy involving the use of photo-protective lignin nanoparticles for the controlled release of thymine dimers on the skin followed by their sacrificial transformation into photo-adducts and successive inhibition of melanoma and alert of cellular UV machinery repair pathways.


Assuntos
Antineoplásicos/química , Antineoplásicos/farmacologia , Mimetismo Biológico , Portadores de Fármacos/química , Lignina , Nanopartículas , Timina/química , Biomimética , Linhagem Celular Tumoral , Dano ao DNA/efeitos dos fármacos , Sistemas de Liberação de Medicamentos , Humanos , Lignina/química , Modelos Moleculares , Conformação Molecular , Estrutura Molecular , Nanopartículas/química , Nanopartículas/ultraestrutura , Fotoquímica , Dímeros de Pirimidina/química , Solventes , Análise Espectral , Relação Estrutura-Atividade , Raios Ultravioleta
12.
Int J Mol Sci ; 23(19)2022 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-36232983

RESUMO

Providing clean drinking water is a great challenge worldwide, especially for low-income countries where the access to safe water is limited. During the last decade, new biotechnological approaches have been explored to improve water management. Among them, the use of antimicrobial nanoparticles for designing innovative centralized and decentralized (point-of-use) water treatment systems for microbial decontamination has received considerable attention. Herein, antimicrobial lignin capped silver nanoparticles (AgLNP) were embedded on residual cork pieces using high-intensity ultrasound coupled with laccase-mediated grafting to obtain biofunctionalized nanomaterial. The developed AgLNP-coated cork proved to be highly efficient to drastically reduce the number of viable Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus in liquid medium. Additionally, the coated-cork was characterized using FTIR-ATR spectroscopy and SEM imaging, and further used as a filter bed in a point-of-use device for water disinfection. The constructed water filtering system significantly reduced the amount of viable E. coli and resistant Bacillus cereus spores from filtered water operating at increasing residence times of 1, 4, 6, 16, 24, and 48 h. Therefore, the presented results prove that the obtained cork-based antimicrobial nanocomposite material could be used as a filtering medium for the development of water filtration system to control pathogen dissemination.


Assuntos
Anti-Infecciosos , Água Potável , Nanopartículas Metálicas , Purificação da Água , Antibacterianos/química , Antibacterianos/farmacologia , Desinfecção/métodos , Escherichia coli , Lacase , Lignina , Nanopartículas Metálicas/química , Prata/química , Prata/farmacologia , Purificação da Água/métodos
13.
Molecules ; 26(3)2021 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-33525445

RESUMO

Due to their biocompatibility, biodegradability, and non-toxicity, lignocellulosic-derived nanoparticles are very potential materials for drug carriers in drug delivery applications. There are three main lignocellulosic-derived nanoparticles discussed in this review. First, lignin nanoparticles (LNPs) are an amphiphilic nanoparticle which has versatile interactions toward hydrophilic or hydrophobic drugs. The synthesis methods of LNPs play an important role in this amphiphilic characteristic. Second, xylan nanoparticles (XNPs) are a hemicellulose-derived nanoparticle, where additional pretreatment is needed to obtain a high purity xylan before the synthesis of XNPs. This process is quite long and challenging, but XNPs have a lot of potential as a drug carrier due to their stronger interactions with various drugs. Third, cellulose nanocrystals (CNCs) are a widely exploited nanoparticle, especially in drug delivery applications. CNCs have low cytotoxicity, therefore they are suitable for use as a drug carrier. The research possibilities for these three nanoparticles are still wide and there is potential in drug delivery applications, especially for enhancing their characteristics with further surface modifications adjusted to the drugs.


Assuntos
Celulose/química , Lignina/química , Nanopartículas/química , Preparações Farmacêuticas/química , Xilanos/química , Animais , Sistemas de Liberação de Medicamentos/métodos , Humanos
14.
Int J Mol Sci ; 22(1)2020 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-33374628

RESUMO

Lignin, the term commonly used in literature, represents a group of heterogeneous aromatic compounds of plant origin. Protolignin or lignin in the cell wall is entirely different from the commercially available technical lignin due to changes during the delignification process. In this paper, we assess the status of lignin valorization in terms of commercial products. We start with existing knowledge of the lignin/protolignin structure in its native form and move to the technical lignin from various sources. Special attention is given to the patents and lignin-based commercial products. We observed that the technical lignin-based commercial products utilize coarse properties of the technical lignin in marketed formulations. Additionally, the general principles of polymers chemistry and self-assembly are difficult to apply in lignin-based nanotechnology, and lignin-centric investigations must be carried out. The alternate upcoming approach is to develop lignin-centric or lignin first bio-refineries for high-value applications; however, that brings its own technological challenges. The assessment of the gap between lab-scale applications and lignin-based commercial products delineates the challenges lignin nanoparticles-based technologies must meet to be a commercially viable alternative.


Assuntos
Biotecnologia , Economia , Lignina/química , Algoritmos , Biotecnologia/economia , Biotecnologia/métodos , Biotecnologia/tendências , Economia/tendências , Hidrólise , Lignina/análogos & derivados , Lignina/classificação , Lignina/isolamento & purificação , Modelos Teóricos , Plantas/química
15.
Molecules ; 26(1)2020 Dec 29.
Artigo em Inglês | MEDLINE | ID: mdl-33383931

RESUMO

Polylactic acid (PLA) films containing 1 wt % and 3 wt % of lignin nanoparticles (pristine (LNP), chemically modified with citric acid (caLNP) and acetylated (aLNP)) were prepared by extrusion and characterized in terms of their overall performance as food packaging materials. Morphological, mechanical, thermal, UV-Vis barrier, antioxidant and antibacterial properties were assayed; appropriate migration values in food simulants and disintegration in simulated composting conditions were also verified. The results obtained indicated that all lignin nanoparticles succeeded in conferring UV-blocking, antioxidant and antibacterial properties to the PLA films, especially at the higher filler loadings assayed. Chemical modification of the fillers partially reduced the UV protection and the antioxidant properties of the resulting composites, but it induced better nanoparticles dispersion, reduced aggregates size, enhanced ductility and improved aesthetic quality of the films through reduction of the characteristic dark color of lignin. Migration tests and disintegration assays of the nanocomposites in simulated composting conditions indicated that, irrespectively of their formulation, the multifunctional nanocomposite films prepared behaved similarly to neat PLA.


Assuntos
Plásticos Biodegradáveis/química , Embalagem de Alimentos , Lignina/química , Nanocompostos/química , Poliésteres/química , Antibacterianos/química , Antibacterianos/farmacologia , Antioxidantes/química , Antioxidantes/farmacologia , Plásticos Biodegradáveis/farmacologia , Compostos de Bifenilo/química , Compostos de Bifenilo/farmacologia , Carbamatos/química , Carbamatos/farmacologia , Ácido Cítrico/química , Ácido Cítrico/farmacologia , Fulerenos/química , Fulerenos/farmacologia , Lignina/farmacologia , Nanocompostos/ultraestrutura , Nanopartículas/química , Nanopartículas/ultraestrutura , Niacinamida/análogos & derivados , Niacinamida/química , Niacinamida/farmacologia , Poliésteres/farmacologia , Pirazóis/química , Pirazóis/farmacologia , Protetores Solares/química , Protetores Solares/farmacologia
16.
Small ; 15(24): e1901427, 2019 06.
Artigo em Inglês | MEDLINE | ID: mdl-31062448

RESUMO

The surface modification of nanoparticles (NPs) using different ligands is a common strategy to increase NP-cell interactions. Here, dentin phosphophoryn-derived peptide (DSS) lignin nanoparticles (LNPs) are prepared and characterized, the cellular internalization of the DSS-functionalized LNPs (LNPs-DSS) into three different cancer cell lines is evaluated, and their efficacy with the widely used iRGD peptide is compared. It is shown that controlled extent of carboxylation of lignin improves the stability at physiological conditions of LNPs formed upon solvent exchange. Functionalization with DSS and iRGD peptides maintains the spherical morphology and moderate polydispersity of LNPs. The LNPs exhibit good cytocompatibility when cultured with PC3-MM2, MDA-MB-231, and A549 in the conventional 2D model and in the 3D cell spheroid morphology. Importantly, the 3D cell models reveal augmented internalization of peptide-functionalized LNPs and improve antiproliferative effects when the LNPs are loaded with a cytotoxic compound. Overall, LNPs-DSS show equal or even superior cellular internalization than the LNPs-iRGD, suggesting that DSS can also be used to enhance the cellular uptake of NPs into different types of cells, and release different cargos intracellularly.


Assuntos
Antineoplásicos/administração & dosagem , Portadores de Fármacos/síntese química , Portadores de Fármacos/farmacocinética , Proteínas da Matriz Extracelular/química , Lignina/química , Nanopartículas/química , Fosfoproteínas/química , Sialoglicoproteínas/química , Células A549 , Antineoplásicos/farmacocinética , Transporte Biológico/efeitos dos fármacos , Proliferação de Células/efeitos dos fármacos , Portadores de Fármacos/química , Liberação Controlada de Fármacos , Humanos , Teste de Materiais , Células PC-3 , Peptídeos/química , Esferoides Celulares/efeitos dos fármacos , Esferoides Celulares/metabolismo , Células Tumorais Cultivadas
17.
Mikrochim Acta ; 186(11): 727, 2019 10 27.
Artigo em Inglês | MEDLINE | ID: mdl-31655902

RESUMO

Lignin nanoparticles (LNPs) were employed as the reducing and stabilizing agent in the preparation of silver nanoparticles (Ag NPs) from silver nitrate under solar light. The Ag NPs were characterized by spectrophotometry, TEM, HRTEM, element mapping, XRD and XPS. The formation of Ag NPs and the structural changes of lignin during the reaction was monitored by analysis via 31P NMR, 1H NMR and 13C NMR. The Ag NPs have uniform shape and an average size of ~14 nm. They were loaded onto the surface of LNPs and entangled in lignin. The resulting Ag NP-LNP suspension displays an ultrasensitive and selective optical response to Hg (II) in giving a color change from yellow to colorless. The assay was performed by spectrophotometry at 450 nm. The analytically useful range extends from 5 nM to 100 nM of Hg (II), and the limit of detection is 1.4 nM in deionized water and 1.8 nM in spiked tap water. This is lower than the threshold level (10 nM) in drinking water specified by the US Environmental Protection Agency. Graphical abstract Schematic representation of the solar light induced synthesis of sliver nanoparticles (Ag NPs) by lignin nanoparticles (LNPs) and their application to colorimetric determination of Hg2+.

18.
Molecules ; 23(7)2018 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-30041408

RESUMO

Valorization of lignocellulosic biomass into a biorefinery scheme requires the use of all biomass components; in this, the lignin fraction is often underutilized. Conversion of lignin to nanoparticles is an attractive solution. Here, we investigated the effect of different lignin isolation processes and a post-treatment homogenization step on particle formation. Lignin was isolated from birch chips by using two organosolv processes, traditional organosolv (OS) and hybrid organosolv-steam explosion (HOS-SE) at various ethanol contents. For post-treatment, lignin was homogenized at 500 bar using different ethanol:water ratios. Isolation of lignin with OS resulted in unshaped lignin particles, whereas after HOS-SE, lignin micro-particles were formed directly. Addition of an acidic catalyst during HOS-SE had a negative impact on the particle formation, and the optimal ethanol content was 50⁻60% v/v. Homogenization had a positive effect as it transformed initially unshaped lignin into spherical nanoparticles and reduced the size of the micro-particles isolated by HOS-SE. Ethanol content during homogenization affected the size of the particles, with the optimal results obtained at 75% v/v. We demonstrate that organosolv lignin can be used as an excellent starting material for nanoparticle preparation, with a simple method without the need for extensive chemical modification. It was also demonstrated that tuning of the operational parameters results in nanoparticles of smaller size and with better size homogeneity.


Assuntos
Betula/química , Biomassa , Lignina/química , Nanopartículas/química , Solventes/química , Fracionamento Químico , Nanopartículas/ultraestrutura , Espectroscopia de Infravermelho com Transformada de Fourier , Ácidos Sulfúricos , Temperatura
19.
Int J Biol Macromol ; 277(Pt 4): 134464, 2024 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-39098701

RESUMO

In this study, lignin nanoparticles (LN) and octadecylamine-modified LN (LN-ODA) were utilized as coating materials to enhance the hydrophobic, antioxidant, and ultraviolet radiation-shielding (UV-shielding) properties of a TEMPO-oxidized nanocellulose film (TOCNF). The water contact angle (WCA) of the TOCNF was approximately 53° and remained stable for 1 min, while the modified LN-ODA-coated TOCNF reached over 130° and maintained approximately 85° for an hour. Pure TOCNF exhibited low antioxidant properties (4.7 %), which were significantly enhanced in TOCNF-LN (81.6 %) and modified LN-ODA (10.3 % to 27.5 %). Modified LN-ODA-coated TOCNF exhibited antioxidant properties two to six times higher than those of pure TOCNF. Modified LN-ODA exhibited thermal degradation max (Tmax) at 421 °C, while pure LN showed the main degradation temperature at approximately Tmax 330 °C. The thermal stability of TOCNF-LN-ODA-coated materials remained consistent with that of pure TOCNF, while the crystallinity index of the sample showed a slight decrease due to the amorphous nature of the lignin structure. The tensile strength of TOCNF was approximately 114.1 MPa and decreased to 80.1, 51.3, and 30.3 MPa for LN-ODA coating at 5, 10, and 15 g/m2, respectively.

20.
Int J Biol Macromol ; 277(Pt 3): 134474, 2024 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-39102912

RESUMO

Lignin as a natural biopolymer is becoming increasingly in demand due to its eco-friendly properties, while lignin-based electrolyte with high conductivity and reliable durability for applications in supercapacitors is still challenging. Herein, a facile method to prepare lignin nanoparticles (LNPs)-based solid electrolyte thin film (LF) was proposed through chemical cross-linking reaction. The fabricated LF exhibited a distinctive spongy porous structure with the ionic conductivity of 3.26 mS cm-1, demonstrating the exceptional flexibility and favorable mechanical properties. Moreover, the assembly of all-LNPs-based symmetric supercapacitor (SSC) devices was achieved using LF electrolyte and LCA electrodes for the first time, confirming the LF3 electrolyte superior to commercial cellulose separator in capacitive behaviour. This SSC device exhibited a specific capacitance of 122.7 F g-1 at 0.5 A g-1 and the maximum energy density of 17.04 W h kg-1. Furthermore, the incorporation of sodium alginate (SA) significantly enhanced the ionic conductivity of SA/LF3 electrolyte, and the resulting SSC device delivered a higher specific capacitance of 174.5 F g-1 at 0.5 A g-1 and the maximum energy and power densities of 24.24 W h kg-1 and 5023 W kg-1, respectively. This study proposes a promising approach for sustainable utilization of lignin in energy storage applications.

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