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1.
Biomacromolecules ; 25(2): 700-714, 2024 Feb 12.
Artículo en Inglés | MEDLINE | ID: mdl-38295273

RESUMEN

Every 1.2 s, a diabetic foot ulcer is developed, and every 20 s, one amputation is carried out in diabetic patients. Monitoring and controlling protease activity have been considered as a strategy for more efficient management of diabetic and other chronic wounds. This study aimed to develop a casein-based dressing that, by its disappearance, provides information about the activity of proteases and simultaneously harnesses proteolytic activity. Casein films were fabricated by using an aqueous solution, and heat treatment was successfully deployed as a green and clean approach to confer hydrolytic stability. Our results showed that casein-based films' mechanical characteristics, water absorption, and proteolytic stability could be controlled by the length of the heat treatment, which proved to be a useful tool. An increase in the treatment duration from 30 min to 3 h led to toleration of 2.4 times higher stress, 2 times lower water uptake, and 3.4 times higher proteolytic stability at examined conditions. Selected casein-based structures responded to Bacillus sp. bacteria's protease (BSP) and human neutrophil elastase (HNE) as representatives of bacterial and nonbacterial proteases found in the wounds at 10 and 200 ng mL-1 levels, respectively. The hydrolysis was accompanied by a 36% reduction in proteolytic activity measured by using a casein-based universal protease activity assay. The released casein fragments could scavenge 90% of the examined radicals. In-vitro cell culture studies showed that the hydrolysates were not cytotoxic, and the casein-based film had a favorable interaction with fibroblast cells, indicating its potential as a scaffold in the case that proteolytic activity would not be to the extent that causes its rapid disintegration. In general, these findings hold promise for applying the developed casein-based structure for detecting proteolytic activity without the need for any equipment, kits, or expertise and, more importantly, in a highly economical manner. In the case that the proteolytic activity would not be severe, it could also serve as a substrate for cell adhesion and growth; this would aid in the healing process.


Asunto(s)
Caseínas , Pie Diabético , Humanos , Péptido Hidrolasas/metabolismo , Vendajes , Pie Diabético/terapia , Pie Diabético/diagnóstico , Agua
2.
Molecules ; 25(7)2020 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-32272769

RESUMEN

Biopolymer aerogels of appropriate open-porous morphology, nanotopology, surface chemistry, and mechanical properties can be promising cell scaffolding materials. Here, we report a facile approach towards the preparation of cellulose phosphate aerogels from two types of cellulosic source materials. Since high degrees of phosphorylation would afford water-soluble products inappropriate for cell scaffolding, products of low DSP (ca. 0.2) were prepared by a heterogeneous approach. Aiming at both i) full preservation of chemical integrity of cellulose during dissolution and ii) utilization of specific phase separation mechanisms upon coagulation of cellulose, TBAF·H2O/DMSO was employed as a non-derivatizing solvent. Sequential dissolution of cellulose phosphates, casting, coagulation, solvent exchange, and scCO2 drying afforded lightweight, nano-porous aerogels. Compared to their non-derivatized counterparts, cellulose phosphate aerogels are less sensitive towards shrinking during solvent exchange. This is presumably due to electrostatic repulsion and translates into faster scCO2 drying. The low DSP values have no negative impact on pore size distribution, specific surface (SBET ≤ 310 m2 g-1), porosity (Π 95.5-97 vol.%), or stiffness (Eρ ≤ 211 MPa cm3 g-1). Considering the sterilization capabilities of scCO2, existing templating opportunities to afford dual-porous scaffolds and the good hemocompatibility of phosphorylated cellulose, TBAF·H2O/DMSO can be regarded a promising solvent system for the manufacture of cell scaffolding materials.


Asunto(s)
Celulosa/análogos & derivados , Celulosa/química , Dimetilsulfóxido/química , Geles/química , Compuestos de Amonio Cuaternario/química , Agua/química , Biopolímeros/química , Nanoestructuras/química , Fosfatos/química , Porosidad , Solventes/química
3.
Soft Matter ; 15(41): 8372-8380, 2019 Oct 23.
Artículo en Inglés | MEDLINE | ID: mdl-31588953

RESUMEN

Cellulose II aerogels are a highly porous class of biobased ultra-light-weight materials. They consist of interlinked networks of loosely aggregated cellulose fibrils. The latter typically have random orientation due to spontaneous phase separation triggered by addition of antisolvent to moleculardisperse cellulose solutions. Deceleration of phase separation has been recently proposed as a novel approach towards aerogels featuring preferred cellulose orientation. Here, we investigate the mechanical response of such oriented cellulose aerogels towards load up to 80% compression. Stress-strain curves were recorded and in situ small angle X-ray scattering (SAXS) was performed during compression test to obtain information about the structural alterations of the aerogel fibril networks on the nano-scale related to deformation. Using SAXS in addition, structural changes can be followed in much more detail than by recording stress-strain curves alone. Buckling and coalescence of fibers and a change in fibril orientation can be related to certain regimes in the stress-strain curve. If the loading axis is oriented parallel to the network orientation the aerogels show higher resilience towards the compression.


Asunto(s)
Celulosa/química , Geles/química , Nanoestructuras/química , Anisotropía , Cristalización , Guanidinas/química , Conformación Molecular , Transición de Fase , Porosidad , Presión , Solventes/química , Relación Estructura-Actividad
4.
Molecules ; 24(9)2019 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-31083427

RESUMEN

Aerogels are a special class of nanostructured materials with very high porosity and tunable physicochemical properties. Although a few types of aerogels have already reached the market in construction materials, textiles and aerospace engineering, the full potential of aerogels is still to be assessed for other technology sectors. Based on current efforts to address the material supply chain by a circular economy approach and longevity as well as quality of life with biotechnological methods, environmental and life science applications are two emerging market opportunities where the use of aerogels needs to be further explored and evaluated in a multidisciplinary approach. In this opinion paper, the relevance of the topic is put into context and the corresponding current research efforts on aerogel technology are outlined. Furthermore, key challenges to be solved in order to create materials by design, reproducible process technology and society-centered solutions specifically for the two abovementioned technology sectors are analyzed. Overall, advances in aerogel technology can yield innovative and integrated solutions for environmental and life sciences which in turn can help improve both the welfare of population and to move towards cleaner and smarter supply chain solutions.


Asunto(s)
Geles/química , Nanoestructuras/química , Porosidad
5.
Biomacromolecules ; 19(11): 4411-4422, 2018 11 12.
Artículo en Inglés | MEDLINE | ID: mdl-30252450

RESUMEN

Assembly of (bio)polymers into long-range anisotropic nanostructured gels and aerogels is of great interest in advanced material engineering since it enables directional tuning of properties, such as diffusivity, light, heat, and sound propagation, cell proliferation, and mechanical properties. Here we present an approach toward anisotropic cellulose II gels and aerogels that employs specific diffusion and phase separation phenomena occurring during decelerated infusion of an antisolvent into isotropic supercooled solutions of cellulose in an ionic liquid to effectuate supramolecular assembly of cellulose in anisotropic colloidal network structures. At the example of the distillable ionic liquid 1,1,3,3-tetramethylguanidinium acetate, the antisolvent ethanol, and spherocylindrical porous molds, we demonstrate that the proposed facile, environmental-benign and versatile route affords gels and aerogels whose specific anisotropic nanomorphology and properties reflect the preferred supramolecular cellulose orientation during phase separation, which is perpendicular to the direction of antisolvent diffusion. Comprehensive X-ray scattering experiments revealed that the (aero)gels are composed of an interconnected, fibrous, highly crystalline (CrI ≈ 72%), cellulose II with a cross-sectional Guinier radius of the struts of about 2.5 nm, and an order parameter gradient from about 0.1 to 0.2. The obtained gels and aerogels feature high specific surface areas (350-630 m2 g-1) and excellent mechanical properties like high toughness (up to 471 kJ m-3 for a 60% compression, ρB = 80 mg cm-3) and resilience (up to 13.4 kJ m-3, ρB = 65 mg cm-3).


Asunto(s)
Celulosa/química , Congelación , Geles/química , Líquidos Iónicos/química , Nanofibras/química , Polímeros/química , Solventes/química , Anisotropía , Transición de Fase , Porosidad , Conductividad Térmica
6.
Biomacromolecules ; 19(7): 2969-2978, 2018 07 09.
Artículo en Inglés | MEDLINE | ID: mdl-29757619

RESUMEN

2,3-Dialdehyde cellulose (DAC) of a high degree of oxidation (92% relative to AGU units) prepared by oxidation of microcrystalline cellulose with sodium periodate (48 °C, 19 h) is soluble in hot water. Solution casting, slow air drying, hot pressing, and reinforcement by cellulose nanocrystals afforded films (∼100 µm thickness) that feature intriguing properties: they have very smooth surfaces (SEM), are highly flexible, and have good light transmittance for both the visible and near-infrared range (89-91%), high tensile strength (81-122 MPa), and modulus of elasticity (3.4-4.0 GPa) depending on hydration state and respective water content. The extraordinarily low oxygen permeation of <0.005 cm3 µm m-2 day-1 kPa-1 (50% RH) and <0.03 cm3 µm m-2 day-1 kPa-1 (80% RH) can be regarded as a particularly interesting feature of DAC films. The unusually high initial contact angle of about 67° revealed a rather low hydrophilicity compared to other oxidatively modified or unmodified cellulosic materials which is most likely the result of inter- and intramolecular hemiacetal and hemialdal formation during drying and pressing.


Asunto(s)
Celulosa/análogos & derivados , Membranas Artificiales , Celulosa/química , Celulosa/efectos de la radiación , Elasticidad , Calor , Luz , Nanopartículas/química , Oxígeno/química
7.
Sensors (Basel) ; 18(7)2018 Jul 18.
Artículo en Inglés | MEDLINE | ID: mdl-30021995

RESUMEN

The growing incidence of chronic wounds in the world population has prompted increased interest in chronic wound dressings with protease-modulating activity and protease point of care sensors to treat and enable monitoring of elevated protease-based wound pathology. However, the overall design features needed for the combination of a chronic wound dressing that lowers protease activity along with protease detection capability as a single platform for semi-occlusive dressings has scarcely been addressed. The interface of dressing and sensor specific properties (porosity, permeability, moisture uptake properties, specific surface area, surface charge, and detection) relative to sensor bioactivity and protease sequestrant performance is explored here. Measurement of the material's zeta potential demonstrated a correlation between negative charge and the ability of materials to bind positively charged Human Neutrophil Elastase. Peptide-cellulose conjugates as protease substrates prepared on a nanocellulosic aerogel were assessed for their compatibility with chronic wound dressing design. The porosity, wettability and absorption capacity of the nanocellulosic aerogel were consistent with values observed for semi-occlusive chronic wound dressing designs. The relationship of properties that effect dressing functionality and performance as well as impact sensor sensitivity are discussed in the context of the enzyme kinetics. The sensor sensitivity of the aerogel-based sensor is contrasted with current clinical studies on elastase. Taken together, comparative analysis of the influence of molecular features on the physical properties of three forms of cellulosic transducer surfaces provides a meaningful assessment of the interface compatibility of cellulose-based sensors and corresponding protease sequestrant materials for potential use in chronic wound sensor/dressing design platforms.


Asunto(s)
Vendajes , Celulosa/metabolismo , Fibra de Algodón , Elastasa de Leucocito/aislamiento & purificación , Elastasa de Leucocito/metabolismo , Péptidos/metabolismo , Absorción Fisicoquímica , Humanos , Permeabilidad , Porosidad , Humectabilidad
8.
Int J Mol Sci ; 19(3)2018 Mar 13.
Artículo en Inglés | MEDLINE | ID: mdl-29534033

RESUMEN

Nanocellulose has high specific surface area, hydration properties, and ease of derivatization to prepare protease sensors. A Human Neutrophil Elastase sensor designed with a nanocellulose aerogel transducer surface derived from cotton is compared with cotton filter paper, and nanocrystalline cellulose versions of the sensor. X-ray crystallography was employed along with Michaelis-Menten enzyme kinetics, and circular dichroism to contrast the structure/function relations of the peptide-cellulose conjugate conformation to enzyme/substrate binding and turnover rates. The nanocellulosic aerogel was found to have a cellulose II structure. The spatiotemporal relation of crystallite surface to peptide-cellulose conformation is discussed in light of observed enzyme kinetics. A higher substrate binding affinity (Km) of elastase was observed with the nanocellulose aerogel and nanocrystalline peptide-cellulose conjugates than with the solution-based elastase substrate. An increased Km observed for the nanocellulosic aerogel sensor yields a higher enzyme efficiency (kcat/Km), attributable to binding of the serine protease to the negatively charged cellulose surface. The effect of crystallite size and ß-turn peptide conformation are related to the peptide-cellulose kinetics. Models demonstrating the orientation of cellulose to peptide O6-hydroxymethyl rotamers of the conjugates at the surface of the cellulose crystal suggest the relative accessibility of the peptide-cellulose conjugates for enzyme active site binding.


Asunto(s)
Técnicas Biosensibles/métodos , Celulosa/análogos & derivados , Elastasa de Leucocito/química , Nanopartículas/química , Biocatálisis , Geles/química , Gossypium/química , Humanos , Elastasa de Leucocito/metabolismo , Péptidos/química , Unión Proteica , Relación Estructura-Actividad
9.
Biomacromolecules ; 18(7): 2045-2055, 2017 Jul 10.
Artículo en Inglés | MEDLINE | ID: mdl-28530806

RESUMEN

We present an approach to construct biocompatible and photoluminescent hybrid materials comprised of carbon quantum dots (CQDs) and TEMPO-oxidized cellulose nanocrystals (TO-CNCs). First, the amino-functionalized carbon quantum dots (NH2-CQDs) were synthesized using a simple microwave method, and the TO-CNCs were prepared by hydrochloric acid (HCl) hydrolysis followed by TEMPO-mediated oxidation. The conjugation of NH2-CQDs and TO-CNCs was conducted via carbodiimide-assisted coupling chemistry. The synthesized TO-CNC@CQD hybrid nanomaterials were characterized using X-ray photoelectron spectroscopy, cryo-transmittance electron microscopy, confocal microscopy, and fluorescence spectroscopy. Finally, the interactions of TO-CNC@CQD hybrids with HeLa and RAW 264.7 macrophage cells were investigated in vitro. Cell viability tests suggest the surface conjugation with NH2-CQDs not only improved the cytocompatibility of TO-CNCs, but also enhanced their cellular association and internalization on both HeLa and RAW 264.7 cells after 4 and 24 h incubation.


Asunto(s)
Celulosa , Colorantes Fluorescentes , Ensayo de Materiales , Nanopartículas/química , Puntos Cuánticos/química , Animales , Celulosa/química , Celulosa/farmacología , Colorantes Fluorescentes/química , Colorantes Fluorescentes/farmacología , Células HeLa , Humanos , Ratones , Microscopía Fluorescente/métodos , Células RAW 264.7
10.
Cellulose (Lond) ; 23: 1949-1966, 2016.
Artículo en Inglés | MEDLINE | ID: mdl-27340346

RESUMEN

The impact of selected cellulose solvent systems based on the principal constituents tetrabutylammonium fluoride (TBAF), 1-ethyl-3-methyl-1H-imidazolium-acetate, N-methylmorpholine-N-oxide, or calcium thiocyanate octahydrate (CTO) on the properties of cellulose II aerogels prepared from these solvent systems has been investigated as a means towards tailoring cellulose aerogel properties with respect to specific applications. Cotton linters were used as representative plant cellulose. Cellulose was coagulated from solutions with comparable cellulose content, and dried with supercritical carbon dioxide after solvent exchange. The resulting bulk aerogels were comprehensively morphologically and mechanically tested to relate structure and mechanical properties. Different solvent systems caused considerable differences in the properties of the bulk samples, such as internal surface area (nitrogen sorption), morphology, porosity (He pycnometry, thermoporosimetry), and mechanical stability (compression testing). The results of SAXS, WAXS, and solid-state 13C NMR spectroscopy suggest that this is due to different mechanisms of cellulose self-assembling on the supramolecular and nanostructural level, respectively, as reflected by the broad ranges of cellulose crystallinity, fibril diameter, fractal dimension and skeletal density. Both solid state NMR and WAXS experiments confirmed the sole existence of the cellulose II allomorph for all aerogels, with crystallinity reaching a maximum of 46-50 % for CTO-derived aerogels. Generally, higher fibril diameter, degree of crystallinity, hence increased skeletal density were associated with good preservation of shape and dimension throughout conversion of lyogels to aerogels, and enhanced mechanical stability, but somewhat reduced specific surface area. Amorphous, yet highly rigid aerogels derived from TBAF/DMSO mixtures deviated from this trend, most likely due to their particular homogeneous and nanostructured morphology.

11.
Sensors (Basel) ; 16(11)2016 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-27792201

RESUMEN

Nanocellulosic aerogels (NA) provide a lightweight biocompatible material with structural properties, like interconnected high porosity and specific surface area, suitable for biosensor design. We report here the preparation, characterization and activity of peptide-nanocellulose aerogels (PepNA) made from unprocessed cotton and designed with protease detection activity. Low-density cellulosic aerogels were prepared from greige cotton by employing calcium thiocyanate octahydrate/lithium chloride as a direct cellulose dissolving medium. Subsequent casting, coagulation, solvent exchange and supercritical carbon dioxide drying afforded homogeneous cellulose II aerogels of fibrous morphology. The cotton-based aerogel had a porosity of 99% largely dominated by mesopores (2-50 nm) and an internal surface of 163 m²·g-1. A fluorescent tripeptide-substrate (succinyl-alanine-proline-alanine-4-amino-7-methyl-coumarin) was tethered to NA by (1) esterification of cellulose C6 surface hydroxyl groups with glycidyl-fluorenylmethyloxycarbonyl (FMOC), (2) deprotection and (3) coupling of the immobilized glycine with the tripeptide. Characterization of the NA and PepNA included techniques, such as elemental analysis, mass spectral analysis, attenuated total reflectance infrared imaging, nitrogen adsorption, scanning electron microscopy and bioactivity studies. The degree of substitution of the peptide analog attached to the anhydroglucose units of PepNA was 0.015. The findings from mass spectral analysis and attenuated total reflectance infrared imaging indicated that the peptide substrate was immobilized on to the surface of the NA. Nitrogen adsorption revealed a high specific surface area and a highly porous system, which supports the open porous structure observed from scanning electron microscopy images. Bioactivity studies of PepNA revealed a detection sensitivity of 0.13 units/milliliter for human neutrophil elastase, a diagnostic biomarker for inflammatory diseases. The physical properties of the aerogel are suitable for interfacing with an intelligent protease sequestrant wound dressing.


Asunto(s)
Técnicas Biosensibles/métodos , Celulosa/química , Geles/química , Gossypium/química , Elastasa de Leucocito/análisis , Oligopéptidos/química , Adsorción , Fibra de Algodón , Geles/síntesis química , Gossypium/metabolismo , Humanos , Microscopía Electrónica de Rastreo , Nanoestructuras/química , Nitrógeno/química , Pectinas/análisis , Porosidad , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción , Espectrofotometría Infrarroja
12.
Cellulose (Lond) ; 20(6): 3007-3024, 2013.
Artículo en Inglés | MEDLINE | ID: mdl-26412950

RESUMEN

Photoluminiscent (PL) cellulose aerogels of variable shape containing homogeneously dispersed and surface-immobilized alloyed (ZnS)x(CuInS2)1-x/ZnS (core/shell) quantum dots (QD) have been obtained by (1) dissolution of hardwood prehydrolysis kraft pulp in the ionic liquid 1-hexyl-3-methyl-1H-imidazolium chloride, (2) addition of a homogenous dispersion of quantum dots in the same solvent, (3) molding, (4) coagulation of cellulose using ethanol as antisolvent, and (5) scCO2 drying of the resulting composite aerogels. Both compatibilization with the cellulose solvent and covalent attachment of the quantum dots onto the cellulose surface was achieved through replacement of 1-mercaptododecyl ligands typically used in synthesis of (ZnS)x(CuInS2)1-x/ZnS (core-shell) QDs by 1-mercapto-3-(trimethoxysilyl)-propyl ligands. The obtained cellulose-quantum dot hybrid aerogels have apparent densities of 37.9-57.2 mg cm-3. Their BET surface areas range from 296 to 686 m2 g-1 comparable with non-luminiscent cellulose aerogels obtained via the NMMO, TBAF/DMSO or Ca(SCN)2 route. Depending mainly on the ratio of QD core constituents and to a minor extent on the cellulose/QD ratio, the emission wavelength of the novel aerogels can be controlled within a wide range of the visible light spectrum. Whereas higher QD contents lead to bathochromic PL shifts, hypsochromism is observed when increasing the amount of cellulose at constant QD content. Reinforcement of the cellulose aerogels and hence significantly reduced shrinkage during scCO2 drying is a beneficial side effect when using α-mercapto-ω-(trialkoxysilyl) alkyl ligands for QD capping and covalent QD immobilization onto the cellulose surface.

13.
ACS Appl Bio Mater ; 6(2): 543-551, 2023 02 20.
Artículo en Inglés | MEDLINE | ID: mdl-36745634

RESUMEN

Mesenchymal stem cells (MSCs) are the most prominent type of adult stem cells for clinical applications. Three-dimensional (3D) cultivation of MSCs in biomimetic hydrogels provides a more physiologically relevant cultivation microenvironment for in vitro testing and modeling, thus overcoming the limitations of traditional planar cultivation methods. Cellulose nanofibers are an excellent candidate biomaterial for synthesis of hydrogels for this application, due to their biocompatibility, tunable properties, availability, and low cost. Herein, we demonstrate the capacity of hydrogels prepared from 2,2,6,6-tetramethylpiperidine-1-oxyl -oxidized and subsequently individualized cellulose-nanofibrils to support physiologically relevant 3D in vitro cultivation of human MSCs at low solid contents (0.2-0.5 wt %). Our results show that MSCs can spread, proliferate, and migrate inside the cellulose hydrogels, while the metabolic activity and proliferative capacity of the cells as well as their morphological characteristics benefit more in the lower bulk cellulose concentration hydrogels.


Asunto(s)
Celulosa Oxidada , Células Madre Mesenquimatosas , Humanos , Hidrogeles , Materiales Biocompatibles , Celulosa
14.
Front Bioeng Biotechnol ; 11: 1152577, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37152648

RESUMEN

Cellulose is an appealing material for tissue engineering. In an attempt to overcome some obstacles with cellulose II cell scaffolding materials related to insufficient biomineralization, lack of micron-size porosity, and deficiency in surface charge, respective solutions have been proposed. These included covalent phosphorylation of different cellulose materials targeting relatively low degrees of substitution (DS 0.18-0.23) and processing these cellulose derivatives into scaffolding materials by a dissolution/coagulation approach employing the hitherto rarely used TBAF/DMSO/H2O system for cellulose dissolution. Here, we report bioactivity and preliminary hemocompatibility testing of dual-porous cellulose phosphate aerogels (contrasted with the phosphate-free reference) obtained via coagulation (water/ethanol), solvent exchange and scCO2 drying. Deposition of hydroxyapatite from simulated body fluid (7 days of immersion) revealed good bioactivity (1.5-2.2 mg Ca2+ per mg scaffold). Incubation of the scCO2-dried and rehydrated scaffolding materials in heparin anticoagulated human whole blood was conducted to study selected parameters of hemostasis (prothrombin F1+2 fragment, PF4, count of thrombocyte-leukocyte conjugates) and inflammatory response (C5a fragment, leukocyte activation marker CD11b). Adhesion of leukocytes on the surface of the incubated substrates was assessed by scanning electron and fluorescence microscopy (DAPI staining). The results suggest that phosphorylation at low DS does not increase platelet activation. However, a significant increase in platelet activation and thrombin formation was observed after a certain fraction of the negative surface charges had been compensated by Ca2+ ions. The combination of both phosphorylation and calcification turned out to be a potent means for controlling the inflammatory response, which was close to baseline level for some of the studied samples.

15.
Ind Eng Chem Res ; 61(10): 3503-3515, 2022 Mar 16.
Artículo en Inglés | MEDLINE | ID: mdl-35309502

RESUMEN

Current changes toward a more biobased economy have recently created tremendous renewed interest in using lignin as a valuable source for chemicals and materials. Here, we present a facile cationization approach aiming to impart kraft lignin water-solubility, with similar good features as lignosulfonates. Eucalyptus globulus kraft lignin obtained from a paper mill black liquor by applying the LignoBoost process was used as the substrate. Its reaction with 3-chloro-2-hydroxypropyl-trimethylammonium chloride (CHPTAC) in an aqueous alkaline medium was studied to assess the impact of different reaction conditions (temperature, time, educt concentration, molar CHPTAC-to-lignin ratio) on the degree of cationization. It has been shown that at pH 13, 10 wt % lignin content, 70 °C, and 3 h reaction time, a CHPTAC-to-lignin minimum molar ratio of 1.3 is required to obtain fully water-soluble products. Elemental analysis (4.2% N), size-exclusion chromatography (M w 2180 Da), and quantitative 13C NMR spectroscopy of the product obtained at this limit reactant concentration suggest introduction of 1.2 quaternary ammonium groups per C9 unit and substitution of 75% of the initially available phenolic OH groups. The possible contribution of benzylic hydroxyls to the introduction of quaternary ammonium moieties through a quinone methide mechanism has been proposed. Since both molecular characteristics and degree of substitution, and hence solubility or count of surface charge, of colloidal particles can be adjusted within a wide range, cationic kraft lignins are promising materials for a wide range of applications, as exemplarily demonstrated for flocculation of anionic dyes.

16.
Polymers (Basel) ; 14(2)2022 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-35054664

RESUMEN

This study investigates the effect of the enzymatic polymerization of lignosulfonate for the formulation of a lignosulfonate-based adhesive. For this, beech lamellas were glued together and tested according to the EN 302-1 standard. The results showed that the laccase-polymerized lignosulfonate-based wood adhesives (LS-p) had similar mechanical properties as a standard carpenter's glue (PVAc-based D3 class white glue), as no significant difference in tensile shear strength between these two adhesive types was found. However, carpenter's glue showed almost 100% wood failure, while with the lignosulfonate-based wood glue, the samples failed, mainly in the glueline. Pre-polymerization of LS-p is the most critical factor to achieve the required viscosity, which is also connected to the wetting properties and the resulting tensile shear strength. The longer the pre-polymerization, the higher the viscosity of the LS-p adhesive, with the tensile shear strength reaching a plateau. The presented data show the potential of using enzymatically pre-polymerized lignosulfonate as a well-performing wood adhesive. Further development and optimization of the pre-polymerization process is required, which is also important to push towards upscaling and practical applications.

17.
Materials (Basel) ; 15(22)2022 Nov 08.
Artículo en Inglés | MEDLINE | ID: mdl-36431355

RESUMEN

All-lignin coating formulations were prepared while combining water-soluble cationic kraft lignin (quaternized LignoBoost®, CL) and anionic lignosulphonate (LS). The electrostatic attraction between positively charged CL and negatively charged LS led to the formation of insoluble self-organized macromolecule aggregates that align to films. The structures of the formed layers were evaluated by atomic force microscopy (AFM), firstly on glass lamina using dip-coating deposition and then on handsheets and industrial uncoated paper using roll-to-roll coating in a layer-by-layer mode. Coated samples were also characterized by optical microscopy, scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (SEM/EDS), and contact angle measurements. It was suggested that the structure of all-lignin aggregates is the result of the interaction of amphiphilic water-soluble lignin molecules leading to their specifically ordered mutual arrangement depending on the order and the mode of their application on the surface. The all-lignin coating of cellulosic fiber imparts lower air permeability and lower free surface energy to paper, mainly due to a decrease in surface polarity, thus promoting the paper's hydrophobic properties. Moderate loading of lignin coating formulations (5-6 g m-2) did not affect the mechanical strength of the paper.

18.
Angew Chem Int Ed Engl ; 50(37): A34-9, 2011 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-22022715

RESUMEN

Nitrogen (N) is a major nutrient element controlling the cycling of organic matter in the biosphere. Its availability in soils is closely related to biological productivity. In order to reduce the negative environmental impact, associated with the application of mineral N-fertilizers, the use of ammonoxidised technical lignins is suggested. They can act as potential slow N-release fertilisers which concomitantly may increase C sequestration of soils by its potential to bind CO2. The idea of our study was to combine an improved chemical characterisation of ammonoxidised ligneous matter as well as their CO2-binding potential, with laboratory pot experiments, performed to enable an evaluation of their behaviour and stability during the biochemical reworking occurring in active soils.


Asunto(s)
Amoníaco/metabolismo , Dióxido de Carbono/metabolismo , Lignina/metabolismo , Nitrógeno/metabolismo , Oxígeno/metabolismo , Suelo/química , Aminas/química , Aminas/metabolismo , Amoníaco/química , Dióxido de Carbono/química , Lignina/química , Nitrógeno/química , Oxígeno/química
19.
Polymers (Basel) ; 13(4)2021 Feb 16.
Artículo en Inglés | MEDLINE | ID: mdl-33669181

RESUMEN

The imaging of non-conducting materials by scanning electron microscopy (SEM) is most often performed after depositing few nanometers thick conductive layers on the samples. It is shown in this work, that even a 5 nm thick sputtered gold layer can dramatically alter the morphology and the surface structure of many different types of aerogels. Silica, polyimide, polyamide, calcium-alginate and cellulose aerogels were imaged in their pristine forms and after gold sputtering utilizing low voltage scanning electron microscopy (LVSEM) in order to reduce charging effects. The morphological features seen in the SEM images of the pristine samples are in excellent agreement with the structural parameters of the aerogels measured by nitrogen adsorption-desorption porosimetry. In contrast, the morphologies of the sputter coated samples are significantly distorted and feature nanostructured gold. These findings point out that extra care should be taken in order to ensure that gold sputtering does not cause morphological artifacts. Otherwise, the application of low voltage scanning electron microscopy even yields high resolution images of pristine non-conducting aerogels.

20.
Materials (Basel) ; 14(18)2021 Sep 07.
Artículo en Inglés | MEDLINE | ID: mdl-34576349

RESUMEN

Coating of steel is a frequently applied approach to increase the resistance of moving machine parts towards abrasion, surface oxidation, and corrosion. Here, we show that plating circular saw blades with certain metals can help to reduce the electrical charging of wood dust during cutting, which has significant implications for occupational safety, healthcare, and lifetime of filter systems. With the example of beech wood planks, machine net energy consumption EV (J cm-3) and cumulated field strength E→V (kV m-4) as caused by electrically charged particles were compared for cutting of 10- and 20-mm deep grooves (800 mm length) using saw blades of different toothing (24, 60 teeth) and surface coating (Cu, Ag, and Cr). To ensure uniform feed per tooth (fz = 0.063 mm), saw blades were operated at different rotation speeds (4000 vs. 1600 rpm). The results demonstrate that the extent of electrostatic sawdust charging can be manipulated to a certain extent by the type of saw blade plating. Coating with chromium turned out to be most effective in shifting the electrostatic charge of the wood particles towards neutralization. Lowering of rotation speed using circular saw blades of higher toothing was an additional measure significantly reducing electrostatic charging of wood dust. Hence, cutting with a chrome-coated blade with 60 teeth can be specifically recommended as the reduction of electrical saw dust charging is not associated with higher machine power consumption.

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