1. |
- Jiang, Xuehe, et al.
(author)
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Multifunctional Cellulose Nanofibrils-GdF3 Nanoparticles Hybrid Gel and Its Potential Uses for Drug Delivery and Magnetic Resonance Imaging
- 2023
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In: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 6:22, s. 21182-21193
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Journal article (peer-reviewed)abstract
- A multifunctional hybrid gel based on cellulose nanofibrils (CNFs) was developed by grafting on its surface stearyl acrylate (PSA) and gadolinium(III) fluoride nanoparticles (GdF3 NPs) via Cu0-mediated surface-initiated radical polymerization (SET-LRP) while encapsulating antimicrobial peptides in it. GdF3 NPs were first surface-modified with 11-phosphonoundecyl acrylate (PDA) to participate in the SET-LRP and cross-linked the grafted polymer-modified CNF. Several characterizations of the hybrid material (GdF3-PSA-CNF) were carried out, such as Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), rheology, and microscopic analyses. The grafted PSA and cross-linked GdF3 NPs created sophisticated networks in the CNF-based gel, presenting outstanding rheological properties and promising three-dimensional (3D) printability of this hybrid material (GdF3-PSA-CNF). The nanostructures of GdF3 NPs and their incorporated CNF species were characterized via small-angle X-ray scattering (SAXS). In addition, due to the unique intrinsic property of the GdF3 nanoparticles, properties for magnetic resonance imaging (MRI) of GdF3-PSA-CNF were investigated, showing the potential application as a contrast agent. Finally, the encapsulation of the antimicrobial peptides added another function to the hybrid material, evaluated by an antimicrobial test against methicillin-resistant Staphylococcus aureus (MRSA) in vitro.
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2. |
- Betker, Marie, et al.
(author)
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Sprayed Hybrid Cellulose Nanofibril-Silver Nanowire Transparent Electrodes for Organic Electronic Applications
- 2023
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In: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 6:14, s. 13677-13688
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Journal article (peer-reviewed)abstract
- In times of climate change and resource scarcity, researchers are aiming to find sustainable alternatives to synthetic polymers for the fabrication of biodegradable, eco-friendly, and, at the same time, high-performance materials. Nanocomposites have the ability to combine several favorable properties of different materials in a single device. Here, we evaluate the suitability of two kinds of inks containing silver nanowires for the fast, facile, and industrial-relevant fabrication of two different types of cellulose-based silver nanowire electrodes via layer-by-layer spray deposition only. The Type I electrode has a layered structure, which is composed of a network of silver nanowires sprayed on top of a cellulose nanofibrils layer, while the Type II electrode consists of a homogeneous mixture of silver nanowires and cellulose nanofibrils. A correlation between the surface structure, conductivity, and transparency of both types of electrodes is established. We use the Haacke figure of merit for transparent electrode materials to demonstrate the favorable influence of cellulose nanofibrils in the spray ink by identifying Type II as the electrode with the lowest sheet resistance (minimum 5 ± 0.04 Ω/sq), while at the same time having a lower surface roughness and shorter fabrication time than Type I. Finally, we prove the mechanical stability of the Type II electrode by bending tests and its long-time stability under ambient conditions. The results demonstrate that the mixed spray ink of silver nanowires and cellulose nanofibrils is perfectly suitable for the fast fabrication of highly conductive organic nanoelectronics on an industrial scale.
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3. |
- Bulut, Yusuf, et al.
(author)
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Diblock copolymer pattern protection by silver cluster reinforcement
- 2023
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In: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 15:38, s. 15768-15774
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Journal article (peer-reviewed)abstract
- Pattern fabrication by self-assembly of diblock copolymers is of significant interest due to the simplicity in fabricating complex structures. In particular, polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP) is a fascinating base material as it forms an ordered micellar structure on silicon surfaces. In this work, silver (Ag) is applied using direct current magnetron sputter deposition and high-power impulse magnetron sputter deposition on an ordered micellar PS-b-P4VP layer. The fabricated hybrid materials are structurally analyzed by field emission scanning electron microscopy, atomic force microscopy, and grazing incidence small angle X-ray scattering. When applying simple aqueous posttreatment, the pattern is stable and reinforced by Ag clusters, making micellar PS-b-P4VP ordered layers ideal candidates for lithography. The pristine micellar pattern of the diblock copolymer PS-b-P4VP degrades upon drying of a water droplet, which can be stabilized and inhibited upon deposition of silver clusters.
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4. |
- Harder, Constantin, et al.
(author)
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Optical Properties of Slot‐Die Coated Hybrid Colloid/Cellulose‐Nanofibril Thin Films
- 2023
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In: Advanced Optical Materials. - : Wiley. - 2162-7568 .- 2195-1071. ; 11:13
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Journal article (peer-reviewed)abstract
- Correlating nanostructure and optical properties of thin hybrid films is the crucial ingredient for designing sustainable applications ranging from structural colors in anticounterfeiting to sensors. Here, the tailoring of the refractive index of hybrid cellulose nanofibril/water-dispersed colloidal ink thin films is presented. The authors apply scalable, layer-by-layer slot-die coating for preparing the cellulose nanofibril and hybrid thin films. Making use of the mobility of the polymer chains in the colloids upon annealing, the influence of the different colloid sizes and their glass transition temperature on the refractive index of the hybrid material is shown. The complex refractive indices of the thin films are characterized by spectroscopic ellipsometry and correlated to the different nanostructures of the thin films. The authors find that post-deposition annealing changes the colloidal nanostructure from particulate to agglomerates. Depending on the size of the colloids, imbibition of the colloids into the cellulose nanofibril template is observed. This scalable approach offers new avenues in structural color functional biomaterial hybrid layers.
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5. |
- Harder, Constantin, et al.
(author)
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Poly(sobrerol methacrylate) Colloidal Inks Sprayed onto Cellulose Nanofibril Thin Films for Anticounterfeiting Applications
- 2024
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In: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 7:9, s. 10840-10851
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Journal article (peer-reviewed)abstract
- The colloidal layer formation on porous materials is a crucial step for printing and applying functional coatings, which can be used to fabricate anticounterfeiting paper. The deposition of colloidal layers and subsequent thermal treatment allows for modifying the hydrophilicity of the surface of a material. In the present work, wood-based colloidal inks are applied by spray deposition on spray-deposited porous cellulose nanofibrils (CNF) films. The surface modification by thermal annealing of the fabricated colloid-cellulose hybrid thin films is investigated in terms of layering and hydrophobicity. The polymer colloids in the inks are core-shell nanoparticles with different sizes and glass transition temperatures (T-g), thus enabling different and low thermal treatment temperatures. The ratio between the core polymers, poly(sobrerol methacrylate) (PSobMA), and poly(-butyl methacrylate) (PBMA) determines the T-g and hence allows for tailoring of the T-g. The layer formation of the colloidal inks on the porous CNF layer depends on the imbibition properties of the CNF layer which is determined by their morphology. The water adhesion of the CNF layer decreases due to the deposition of the colloids and thermal treatment except for the colloids with a size smaller than the void size of the porous CNF film. In this case, the colloids are imbibed into the CNF layer when T-g of the colloids is reached and the polymer chains transit in a mobile phase. Tailored aggregate and nanoscale-embedded hybrid structures are achieved depending on the colloid properties. The imbibition of these colloids into the porous CNF films is verified with grazing incidence small-angle X-ray scattering. This study shows a route for tuning the nanoscale structure and macroscopic physicochemical properties useful for anticounterfeiting paper.
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6. |
- Kohantorabi, Mona, et al.
(author)
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Light-Induced Transformation of Virus-Like Particles on TiO2
- 2024
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In: ACS Applied Materials and Interfaces. - : American Chemical Society. - 1944-8244 .- 1944-8252. ; 16:28, s. 37275-37287
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Journal article (peer-reviewed)abstract
- Titanium dioxide (TiO2) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO2 surface. The in situ GISAXS measurements under an N2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.
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7. |
- Liu, Sirui, et al.
(author)
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Design of Hygroscopic Bioplastic Products Stable in Varying Humidities
- 2023
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In: Macromolecular materials and engineering. - : Wiley. - 1438-7492 .- 1439-2054. ; 308:2
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Journal article (peer-reviewed)abstract
- Hygroscopic biopolymers like proteins and polysaccharides suffer from humidity-dependent mechanical properties. Because humidity can vary significantly over the year, or even within a day, these polymers will not generally have stable properties during their lifetimes. On wheat gluten, a model highly hygroscopic biopolymer material, it is observed that larger/thicker samples can be significantly more mechanically stable than thinner samples. It is shown here that this is due to slow water diffusion, which, in turn, is due to the rigid polymer structure caused by the double-bond character of the peptide bond, the many bulky peptide side groups, and the hydrogen bond network. More than a year is required to reach complete moisture saturation (≈10 wt.%) in a 1 cm thick plate of glycerol-plasticized wheat gluten, whereas this process takes only one day for a 0.5 mm thick plate. The overall moisture uptake is also retarded by swelling-induced mechanical effects. Hence, hygroscopic biopolymers are better suited for larger/thicker products, where the moisture-induced changes in mechanical properties are smeared out over time, to the extent that the product remains sufficiently tough over climate changes, for example, throughout the course of a year.
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8. |
- Reck, Kristian A., et al.
(author)
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Early-stage silver growth during sputter deposition on SiO2 and polystyrene - Comparison of biased DC magnetron sputtering, high-power impulse magnetron sputtering (HiPIMS) and bipolar HiPIMS
- 2024
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In: Applied Surface Science. - : Elsevier BV. - 0169-4332 .- 1873-5584. ; 666
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Journal article (peer-reviewed)abstract
- The integration of silver thin films into optoelectronic devices has gained much interest due to their exceptional properties in terms of conductivity and compatibility with flexible substrates. For this type of application, ultrathin layers are desirable, because of their optical transparency. Standard direct current magnetron sputtering (DCMS) is known to lead to undesirable formation of islands at low effective film thicknesses on typical substrates like SiO2 or polystyrene (PS). Therefore, in this study, we explore high-power impulse magnetron sputtering (HiPIMS) with optional further acceleration of metal ions by biasing the substrate or an additional positive pulse (bipolar HiPIMS) for the fabrication of ultra-thin silver layers. The morphology and electrical properties of ultra-thin silver layers with selected effective thicknesses are characterized on SiO2 and PS substrates. The growth evolution of characteristic parameters is further investigated by in-situ grazing-incidence small-angle Xray scattering (GISAXS). The results show that HiPIMS deposition yields films with a higher density of clusters than DCMS leading to a percolation threshold at lower effective film thicknesses. This effect is amplified by further ion acceleration. Thus, we suggest HiPIMS as a promising technique for fabricating ultra-thin, conductive layers on organic and oxide substrates.
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9. |
- Ribca, Iuliana, 1993-, et al.
(author)
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Effect of Molecular Organization on the Properties of Fractionated Lignin-Based Thiol-Ene Thermoset Materials
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Other publication (other academic/artistic)abstract
- In this study, the combination of sequential solvent fractionation of technical Kraft lignin were followed by allylation of most OH functionalities to give highly functional thermoset resins. All lignin fractions were highly functionalized on the phenolic (≥95%) and carboxylic acid OH (≥85%), and to a significant extent on the aliphatic OH moieties (between 43 and 75%). The resins were subsequently cross-linked using thiol-ene chemistry. The high amount of allyl functionalities resulted in a high cross-link density. DMA measurements showed that thioether content dominates the performance of these thermosets with a glass transition temperature (Tg) between 73 and 99 °C and with a storage modulus between 1.9 and 3.8 GPa for all thermosets. The lignin fractions and lignin-based thermosets morphology, at nanoscale, was studied by wide angle X-ray scattering measurements (WAXS). Two π-π stacking interactions were observed: sandwich (≈4.1–4.7 Å) and T-shaped (≈5.5–7.2 Å). The introduction of allyl functionalities weakens the T-shaped π-π stacking interactions. A new signal corresponding to a distance of ≈3.5 Å was observed in lignin-based thermosets, which was attributed to a thioether organized structure. At the same time, a lignin superstructure, was observed with a distance/size corresponding to 7.9-17.5 Å in all samples.
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10. |
- Ribca, Iuliana, 1993-, et al.
(author)
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Effect of Molecular Organization on the Properties of Fractionated Lignin-Based Thiol-Ene Thermoset Materials
- 2023
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In: ACS Omega. - : American Chemical Society (ACS). - 2470-1343. ; 8:28, s. 25478-25486
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Journal article (peer-reviewed)abstract
- In this study, the combination of sequential solvent fractionation of technical Kraft lignin was followed by allylation of most OH functionalities to give highly functional thermoset resins. All lignin fractions were highly functionalized on the phenolic (≥95%) and carboxylic acid OH (≥85%) and to a significant extent on the aliphatic OH moieties (between 43 and 75%). The resins were subsequently cross-linked using thiol-ene chemistry. The high amount of allyl functionalities resulted in a high cross-link density. Dynamic mechanical analysis measurements showed that the thioether content, directly related to the allyl content, strongly affects the performance of these thermosets with a glass transition temperature (Tg) between 81 and 95 °C and with a storage modulus between 1.9 and 3.8 GPa for all thermosets. The lignin fractions and lignin-based thermosets’ morphology, at the nanoscale, was studied by wide-angle X-ray scattering measurements. Two π-π stacking interactions were observed: sandwich (≈4.1-4.7 Å) and T-shaped (≈5.5-7.2 Å). The introduction of allyl functionalities weakens the T-shaped π-π stacking interactions. A new signal corresponding to a distance of ≈3.5 Å was observed in lignin-based thermosets, which was attributed to a thioether organized structure. At the same time, a lignin superstructure was observed with a distance/size corresponding to 7.9-17.5 Å in all samples.
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