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The complexity of plant cell walls on different hierarchical levels still impedes the detailed understanding of biosynthetic pathways, interferes with processing in industry and finally limits applicability of cellulose materials. While there exist many challenges to readily accessing these hierarchies at (sub-) angström resolution, the development of advanced computational methods has the potential to unravel important questions in this field. Here, we summarize the contributions of molecular dynamics simulations in advancing the understanding of the physico-chemical properties of natural fibres. We aim to present a comprehensive view of the advancements and insights gained from molecular dynamics simulations in the field of carbohydrate polymers research. The review holds immense value as a vital reference for researchers seeking to undertake atomistic simulations of plant cell wall constituents. Its significance extends beyond the realm of molecular modeling and chemistry, as it offers a pathway to develop a more profound comprehension of plant cell wall chemistry, interactions, and behavior. By delving into these fundamental aspects, the review provides invaluable insights into future perspectives for exploration. Researchers within the molecular modeling and carbohydrates community can greatly benefit from this resource, enabling them to make significant strides in unraveling the intricacies of plant cell wall dynamics.
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Pared Celular , Celulosa , Simulación de Dinámica Molecular , Polisacáridos , Pared Celular/química , Pared Celular/metabolismo , Celulosa/química , Polisacáridos/química , Plantas/química , Plantas/metabolismo , Células Vegetales/química , Células Vegetales/metabolismoRESUMEN
Adhesion between solid materials is caused by intermolecular forces that only take place if the adhering surfaces are at nanoscale contact (NSC) (i.e., 0.1-0.4 nm. To study adhesion, NSC can be evaluated with Förster Resonance Energy Transfer (FRET). FRET uses the interaction of compatible fluorescence molecules to measure the nanometer distance between bonded surfaces. For this, each surface is labeled with one fluorescence dye, named the Donor or Acceptor. If these molecules are in NSC, a nonradiative Donor-Acceptor energy transfer will occur and can be detected using FRET spectroscopy. Here, for the first time, we introduce an innovative concept of a FRET-based NSC measurement employing dye-nanolayer films prepared by a physical vapor deposition (PVD). The dye nanolayers were prepared by PVD from the vaporization of the Donor and Acceptor molecules separately. The selected molecules, 7-Amino-4-methyl-cumarin (C120) and 5(6)-Carboxy-2',7'-dichlor-fluorescein (CDCF), present high quantum yields (QY, QYD = 0.91 and QYA = 0.64) and a low FRET distance range of 0.6-2.2 nm, adequate for the study of NSC. The produced dye-nanolayer films exhibit a uniform dye distribution (verified by atomic force microscopy) and suitable fluorescence intensities. To validate the NSC measurements, FRET spectroscopy experiments were performed with bonded dye-nanolayer films prepared under different loads (from 1.5 to 140 bar), thus creating different degrees of NSC. The results show an increase in FRET intensity (R 2 = 0.95) with the respective adhesion energy between the films, which is directly related to the degree of NSC. Hence, this work establishes FRET as an experimental technique for the measurement of NSC, and its relation to surface adhesion. Additionally, thanks to the FRET dye-nanolayer approach, the method can be employed on arbitrary surfaces. Essentially, any sufficiently transparent substrate can be functionalized with FRET compatible dyes to evaluate NSC, which represents a breakthrough in contact mechanics investigations of soft and hard solid materials.
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The research conducted on kraft cooking of for different chip sizes is often not representative for the industrial process since the chip size fractions were made of high-quality wood without impurities. We evaluated the effects and the potential of cooking non ideal spruce chip fractions after industrial chipping and screening. The chips were classified according to SCAN 40:01, and the respective fractions were cooked under the identical conditions to mimic the effect of a joint cooking in the industrial digester. For the undersized chips we found higher bark content, a lower screened yield, a higher Kappa number, lower fiber length and lower tensile strength. For the oversized chips, the fiber length and tensile index were also considerably lower. A lower wood quality due to high knot content in the larger fractions was found to be the reason for that. Based on the data obtained from the experiments and literature, different process options for increased yield and reduced chemical consumption are discussed, e.g., separate cooking of different chip fractions. Improved chip screening seems to be the process improvement with lowest costs and highest impact.
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Cationic polyelectrolytes (PEs) are commonly used additives in manufacturing of cellulose based products such as regenerated fibers and paper to tailor their product properties. Here we are studying the adsorption of poly(diallyldimethylammonium chloride), PD, on cellulose, using in situ surface plasmon resonance spectroscopy (SPR) measurements. We employ model surfaces from regenerated cellulose xanthate (CX) and trimethylsilyl cellulose (TMSC), mimicking industrially relevant regenerated cellulose substrates. The effects of the PDs molecular weight were strongly depending on the ionic strength and type of electrolyte (NaCl vs CaCl2). Without electrolytes, the adsorption was monolayer-type, i.e. independent of molecular weight. At moderate ionic strength, adsorption increased due to more pronounced PE coiling, while at high ionic strength electrostatic shielding strongly reduced adsorption of PDs. Results exhibited pronounced differences for the chosen substrates (cellulose regenerated from xanthate (CXreg) vs. regenerated from trimethylsilyl cellulose, TMSCreg). Consistently higher adsorbed amounts of the PD were determined on CXreg surfaces compared TMSC. This can be attributed to a more negative zeta potential, a higher AFM roughness and a higher degree of swelling (investigated by QCM-D) of the CXreg substrates.
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Celulosa , Electrólitos , Adsorción , Peso Molecular , Propiedades de Superficie , Celulosa/química , Electrólitos/químicaRESUMEN
HYPOTHESIS: The widely used Lucas-Washburn (LW) equation depends on the contact angle as the driving force for liquid penetration. However, the contact angle depends on both, the liquid and the substrate. It would be desirable to predict the penetration into porous materials, without the requirement to measure the solid-liquid interaction. Here, we propose a novel modeling approach for liquid penetration from mutually independent substrate- and liquid properties. For this purpose, the contact angle in the LW-equation is replaced by polar and dispersive surface energies, utilizing the theories of Owens-Wendt-Rabel-Kaelble (OWRK), Wu, or van Oss, Good, Chaudhury (vOGC). EXPERIMENTS: The proposed modelling approach is validated exhaustively by measuring penetration speed for 96 substrate-liquid pairings and comparing the results to model predictions based on literature- and measured data. FINDINGS: Liquid absorption is predicted very well (R2 = 0.8-0.9) with all three approaches, spanning a wide range of penetration speed, substrate- and liquid surface energy, viscosity, and pore size. The models for liquid penetration without measurement of solid-liquid interaction (contact angle) performed well. Modeling calculations are entirely relying on physical data of the solid and the liquid phase (surface energies, viscosity and pore size), which can be measured or retrieved from databases.
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The longitudinal stiffness of cellulosic fibres plays an important role in the mechanical performance of many products these fibres are used for. Especially, the fibres' viscoelastic properties are having an influence on the product performance. In this work, tensile testing at different strain rates was performed on single fibres to investigate the rate dependence of their moduli. Four different fibre types were tested: chemi-thermomechanical softwood pulp (CTMP), bleached chemical softwood pulp (CP), unbleached softwood kraft pulp (UKP), and viscose (VIS). For each fibre sample, ten strain rates ranging from 0.113% s-1 to 800% s-1 were applied. The rate-dependent modulus E r of each fibre at each strain rate was calculated by linearly fitting the stress-strain curves. By obtaining the values of the normalized modulus, a slope value per decade was calculated to quantify the rate dependence. To exclude possible plastic and relaxation effects, two additional experiments were used: a force-controlled loading-unloading experiment and a reverse rate protocol. All cellulosic fibres tested exhibited rate-dependent behaviour with a log-linear relationship between loading rate and modulus. For each tenfold increase in loading rate we found an increase in modulus up to nearly 20%-depending on the fibre type. Viscose fibres exhibit the highest rate dependence, whereas chemical softwood pulp fibres exhibit the lowest. Supplementary Information: The online version contains supplementary material available at 10.1007/s10853-022-07722-7.
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Cellulose nanocrystals (CNCs) offer excellent mechanical properties. However, measuring the strength by performing reliable experiments at the nanoscale is challenging. In this paper, we model Iß crystalline cellulose using reactive molecular dynamics simulations. Taking the fibril twist into account, structural changes and hydrogen-bonding characteristics of CNCs during the tensile test are inspected and the failure mechanism of CNCs is analyzed down to the scale of individual bonds. The C4-O4 glycosidic bond is found to be responsible for the failure of CNCs. Finally, the effect of strain rate on ultimate properties is analyzed and a nonlinear model is used to predict the ultimate strength of 9.2 GPa and ultimate strain of 8.5% at a 1 s-1 strain rate. This study sheds light on the applications of cellulose in nanocomposites and further modeling of cellulose nanofibres.
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Nanocompuestos , Nanopartículas , Celulosa/química , Simulación de Dinámica Molecular , Nanocompuestos/química , Nanopartículas/química , Resistencia a la TracciónRESUMEN
We present how harmful different wood extractives carried over to paper mill with unbleached softwood Kraft pulp are for the strength of packaging papers and boards. The investigations were done by simulating industrial papermaking conditions in laboratory-scale trials for handsheet production. It was found that fatty acids are the most relevant compounds in the carryover pitch extractives (CPEs), as they readily interfere in fiber-fiber bonding strength, control the properties of CPE micelles, and are furthermore the most abundant compounds. Addition of cationic starch improved strength and evened out the strength differences of handsheets with different CPE compounds. Oleic acid (unsaturated fatty acid) was an exception, as it was above average harmful for paper strength without cationic starch and also heavily impaired the functioning of cationic starch. As a whole, these findings demonstrate that fatty acids, especially unsaturated ones, are the most relevant CPE compounds contributing to the reduced efficiency of cationic starch and decreased strength of unbleached softwood Kraft paper. This makes the cleaning of process waters by precipitating CPEs on the pulp fibers harmful for paper strength.
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Cellulose fibers are a major industrial input, but due to their irregular shape and anisotropic material response, accurate material characterization is difficult. Single fiber tensile testing is the most popular way to estimate the material properties of individual fibers. However, such tests can only be performed along the axis of the fiber and are associated with problems of enforcing restraints. Alternative indirect approaches, such as micro-mechanical modeling, can help but yield results that are not fully decoupled from the model assumptions. Here, we compare these methods with nanoindentation as a method to extract elastic material constants of the individual fibers. We show that both the longitudinal and the transverse elastic modulus can be determined, additionally enabling the measurement of fiber properties in-situ inside a sheet of paper such that the entire industrial process history is captured. The obtained longitudinal modulus is comparable to traditional methods for larger indents but with a strongly increased scatter as the size of the indentation is decreased further.
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In this work, we study interactions of five different hemicellulose models, i.e. Galactoglucomannan, O-Acetyl-Galactoglucomannan, Fuco-Galacto-Xyloglucan, 4-O-Methylglucuronoxylan, and 4-O-Methylglucuronoarabinoxylan, and their respective binding strength to cellulose nanocrystals by molecular dynamics simulations. Glucuronoarabinoxylan showed the highest free energy of binding, whereas Xyloglucan had the lowest interaction energies amongst the five models. We further performed simulated shear tests and concluded that failure mostly happens at the inter-molecular interaction level within the hemicellulose fraction, rather than at the interface with cellulose. The presence of water molecules seems to have a weakening effect on the interactions of hemicellulose and cellulose, taking up the available hydroxyl groups on the surface of the cellulose for hydrogen bonding. We believe that these studies can shed light on better understanding of plant cell walls, as well as providing evidence on variability of the structures of different plant sources for extractions, purification, and operation of biorefineries.
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Celulosa/química , Nanopartículas/química , Polisacáridos/química , Adsorción , Pared Celular/química , Glucanos/química , Enlace de Hidrógeno , Espectroscopía de Resonancia Magnética/métodos , Mananos/química , Simulación de Dinámica Molecular , Resistencia al Corte , Agua/química , Xilanos/químicaRESUMEN
Adhesion is caused by molecular interactions that only take place if the surfaces are in nanoscale contact (NSC); i.e., the distance between the surfaces is in the range of 0.1-0.4 nm. However, there are several difficulties measuring the NSC between surfaces, mainly because regions that appear to be in full contact at low magnification may show no NSC when observed at higher magnifications. Thus, the measurement area of NSC is very small with imaging techniques, and an experimental technique to evaluate NSC for large contact areas has not been available thus far. Here, we are proposing Förster resonance energy transfer (FRET) spectroscopy/microscopy for this purpose. We demonstrate that NSC in a distance range of 1-10 nm can be evaluated. Our experiments reveal that, for thin films pressed under different loads, NSC increases with the applied pressure, resulting in a higher FRET signal and a corresponding increase in adhesion force/energy when separating the films. Furthermore, we show that local variations in molecular contact can be visualized with FRET microscopy. Thus, we are introducing a spectroscopic technique for quantification (FRET spectroscopy) and imaging (FRET microscopy) of NSC between surfaces, demonstrated here for the application of surface adhesion. This could be of interest for all fields where adhesion or nanoscale surface contact are playing a role, for example, soft matter, biological materials, and polymers, but also engineering applications, like tribology, adhesives, and sealants.
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Scientific publications and newsfeeds recently focused on flushable wet wipes and their role in sewage system blockages. It is stated that although products are marked as flushable, they do not disintegrate after being disposed of via the toilet. In this work it is shown that wetlaid hydroentangled wet wipes lose their initially good dispersive properties during their storage in wet condition. As a consequence, we are suggesting to add tests after defined times of wet storage when assessing the flushability of wet wipes. Loss of dispersibility is found for both, wet wipes from industrial production and wipes produced on pilot facilities. We found it quite surprising that the wet wipes' dispersibility is deteriorating after storage in exactly the same liquid they are dispersed in, i.e. water. This is probably why the effect of wet storage has not been investigated earlier. It is demonstrated that the deteriorating dispersibility of these wipes is linked to the used type of short cellulosic fibres - only wipes containing unbleached softwood pulp as short fibre component were preserving good dispersibility during wet storage. Possible mechanisms that might be responsible are discussed, e.g. long term fiber swelling causing a tightening of the fiber network, or surface interdiffusion.
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Hydrophobization of cellulosic materials and particularly paper products is a commonly used procedure to render papers more resistant to water and moisture. Here, we explore the hydrophobization of unsized paper sheets via the gas phase. We employed three different compounds, namely palmitoyl chloride (PCl), trifluoroacetic anhydride/acetic anhydride (TFAA/Ac2O)) and hexamethyldisilazane (HMDS) which were vaporized and allowed to react with the paper sheets via the gas phase. All routes yielded hydrophobic papers with static water contact angles far above 90° and indicated the formation of covalent bonds. The PCl and TFAA approach negatively impacted the mechanical and optical properties of the paper leading to a decrease in tensile strength and yellowing of the sheets. The HMDS modified papers did not exhibit any differences regarding relevant paper technological parameters (mechanical properties, optical properties, porosity) compared to the non-modified sheets. XPS studies revealed that the HMDS modified samples have a rather low silicon content, pointing at the formation of submonolayers of trimethylsilyl groups on the fiber surfaces in the paper network. This was further investigated by penetration dynamic analysis using ultrasonication, which revealed that the whole fiber network has been homogeneously modified with the silyl groups and not only the very outer surface as for the PCl and the TFAA modified papers. This procedure yields a possibility to study the influence of hydrophobicity on paper sheets and their network properties without changing structural and mechanical paper parameters.
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Celulosa/química , Papel , Agua/química , Humectabilidad , Anhídridos Acéticos/química , Fluoroacetatos/química , Compuestos de Organosilicio/química , Palmitatos/química , Espectroscopía de Fotoelectrones , Porosidad , Espectrofotometría Infrarroja , Resistencia a la Tracción , Ondas Ultrasónicas , VolatilizaciónRESUMEN
Optical brightening agents (OBAs) are commonly used in textile and paper industry to adjust product brightness and color appearence. Continuous production processes lead to short residence time of the dyes in the fiber suspension, making it necessary to understand the kinetics of adsorption. The interaction mechanisms of OBAs with cellulose are challenging to establish as the fibrous nature of cellulosic substrates complicates acquisition of real-time data. Here, we explore the real-time adsorption of different OBAs (di, tetra- and hexasulfonated compounds) onto different cellulose surfaces using surface plasmon resonance spectroscopy. Ionic strength, surface topography and polarity were varied and yielded 0.76-11.35â¯mgâ¯m-2 OBA on cellulose. We identified four independent mechanisms governing OBA-cellulose interactions. These involve the polarity of the cellulose surface, the solubility of the OBA, the ionic strength during adsorption and presence of bivalent cations such as Ca2+. These results can be exploited for process optimization in related industries as they allow for a simple adjustment and experimental testing procedures including performance assessment of novel OBAs.
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Herein, colloidal dispersions of alkaline nanoparticles (NPs: CaCO3 and Mg(OH)2) are stabilized by trimethylsilyl cellulose (TMSC) in hexamethyldisiloxane and employed to treat historical wood pulp paper by an effortless dip-coating technique. Both alkaline NPs exhibit high stability and no size and shape changes upon stabilization with the polymer, as shown by UV-vis spectroscopy and transmission electron microscopy. The long-term effect of NP/TMSC coatings is investigated in detail using accelerated aging. The results from the pH-test and back-titration of coated papers show a complete acid neutralization (pH â¼ 7.4) and introduction of adequate alkaline reserve even after prolonged accelerated aging. Scanning electron microscopy-energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and infrared and water contact angle measurements showed the introduction of a thin and smooth hydrophobic NP/TMSC coating on the paper fibers. Acid-catalyzed desilylation of TMSC was observed by declining C-Si infrared absorbance peaks upon aging. The CaCO3 coatings are superior to Mg(OH)2 with respect to a reduced yellowing and lower cellulose degradation upon aging as shown by colorimetric measurements and degree of polymerization analysis. The tensile strength and folding endurance of coated and aged papers are improved to 200-300 and 50-70% as illustrated by tensile strength and double folding endurance measurements.
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Ultrasonic liquid penetration (ULP) measurements of porous sheets have been applied for a variety of purposes ranging from determining liquid absorption dynamics to surface characterization of substrates. Interpretation of ULP results, however, is complex as the ultrasound signal can be affected by several mechanisms: (1) air being replaced by the liquid in the substrate pores, (2) air bubbles forming during penetration, and (3) structural changes of the substrate due to swelling of the substrate material. Analyzing tailored liquids and substrates in combination with contact angle measurements we are demonstrating that the characteristic shape of the ULP measurement curves can be interpreted in terms of the regime of liquid uptake. A fast and direct decline of the curve corresponds to capillary penetration, the slope of the curve indicates the penetration speed. A slow decline after a previous maximum in the signal can be related to diffusive liquid transport and swelling of the substrate material.
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Atomistic modelling of cellulose has widely been investigated for years using molecular dynamics simulations. In this paper, we model Iß crystalline cellulose as well as develop a model including dislocations in between the crystal regions. The model including dislocations shows a tensile modulus of 109â¯GPa, 25% lower than that of the fully crystalline model (146â¯GPa). The change in dihedral angle preferences is analysed, and its effect on hydrogen bonding pattern is assessed. How presence of hydrogen bonds contributes to elastic properties of cellulose nano-fibrils is shown. Effect of water on the elastic modulus of fibrils is also investigated. Moreover, an illustration is given of how the tensile behaviour of fibrils is controlled by a synergy between the geometry changes occurring at the glycosidic linkage, reflected by specific torsional and glycosidic angles. These findings can be useful in further modelling of cellulosic fibrils at the atomistic and coarse-grained scales.
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This review focuses on cationic starches with a low degree of substitution (<0.06) which are mainly used for production of paper-based products. After a brief introduction on starch in general, cationization pathways and importance of cationic starches in paper production, this review emphasizes on the analytical challenges from different perspectives. These include the different length scales of starches when in solution: the macromolecular level, their assembly into nm aggregates and finally hydrocolloids with hundreds of nanometers of diameter. We give an overview on the current state of the art on the analysis of such challenging samples and aim at providing a guideline for obtaining and presenting reliable analytical data.
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Papel , Almidón/análisis , Cationes/análisis , Estructura Molecular , Tamaño de la Partícula , Propiedades de SuperficieRESUMEN
Two molecules, 7-(diethylamino)coumarin-3-carbohydrazide (DCCH) and fluorescein-5-thiosemicarbazide (FTSC) were investigated in different solvents, under varying pH conditions regarding their spectroscopic properties for the usage as a Förster Resonance Energy Transfer (FRET) pair to study the molecular interaction between cellulosic surfaces. All the relevant spectroscopic properties to determine the Förster distance were measured and the performance as a FRET system was checked. From the results, it is clear that the environmental conditions need to be accurately controlled as both, but especially the FTSC dyes are sensitive to changes. For high enough concentrations positive FRET systems were observed in DMF, DMSO, H2O, THF and alkaline DMF. However due to the low quantum yield of the unmodified DCCH throughout the investigated parameter range and the strong environmental dependency of FTSC, both dyes are not preferable for being used in a FRET system for studying interaction between cellulosic surfaces.