A pair of FRET dyes designed to measure nano-scale contact and the associated adhesion force

Interfacial adhesion is caused by intermolecular forces that only occur between surfaces at nano-scale contact (NSC) i.e., 0.1-0.4nm. To evaluate NSC and its influence on adhesion, F\"orster resonance energy transfer (FRET) spectroscopy has been used. FRET is a technique capable to measure nanometric distances between surfaces by taking advantage of the interaction amid some specific fluorescence molecules, named donor and acceptor. The F\"orster radius (R0) of the FRET pair indicates the distance detection range (0.5R0-2R0) of the system and, must be selected considering the final purpose of each study. Here, we propose a new FRET pair: 7-Amino-4-methyl-cumarin (C120) and 5(6)-Carboxy-2',7'-dichlor-fluorescein (CDCF) with high quantum yield (QY, QYC120=0.91 and QYCDCF=0.64) and a distance range of 0.6-2.2nm (0.1 mM) specifically developed to measure NSC between soft surfaces. For this, polymeric thin films were bonded using different loads, from 1.5 to 150 bar, to create different degrees of NSC, analyzed by FRET spectroscopy, and later pulled apart to measure their interfacial separation energy (adhesion force). Our experiments showed that NSC increases with the applied pressure in the bonded thin films, leading to higher FRET intensity and adhesion force/separation energy. Thus, we have validated a new FRET pair, suitable to measure the degree of NSC between surfaces and establish a linear relationship between FRET and adhesion force; which can be of interest for any type of study with soft materials interfaces that include NSC and its influence on adhesion, as sealants, adhesives or sensors

Multilayer Density Analysis of Cellulose Thin Films

An approach for the multilayer density analysis of polysaccharide thin films at the example of cellulose is presented. In detail, a model was developed for the evaluation of the density in different layers across the thickness direction of the film. The cellulose thin film was split into a so called “roughness layer” present at the surface and a “bulk layer” attached to the substrate surface. For this approach, a combination of multi-parameter surface plasmon resonance spectroscopy (SPR) and atomic force microscopy (AFM) was employed to detect changes in the properties, such as cellulose content and density, thickness and refractive index, of the surface near layer and the bulk layer. The surface region of the films featured a much lower density than the bulk. Further, these results correlate to X-ray reflectivity studies, indicating a similar layered structure with reduced density at the surface near regions. The proposed method provides an approach to analyse density variations in thin films which can be used to study material properties and swelling behavior in different layers of the films. Limitations and challenges of the multilayer model evaluation method of cellulose thin films were discussed. This particularly involves the selection of the starting values for iteration of the layer thickness of the top layer, which was overcome by incorporation of AFM data in this study

Estimation of the in-situ elastic constants of wood pulp fibers in freely dried paper via AFM experiments

Atomic force microscopy-based nanoindentation (AFM-NI) enables characterization of the basic mechanical properties of wood pulp fibers in conditions representative of the state inside a paper sheet. Determination of the mechanical properties under different loads is critical for the success of increasingly advanced computational models to understand, predict and improve the behavior of paper and paperboard. Here, AFM-NI was used to indent fibers transverse to and along the longitudinal axis of the fiber. Indentation moduli and hardness were obtained for relative humidity from 25 % to 75 %. The hardness and the indentation modulus exhibit moisture dependency, decreasing by 75 % and 50 %, respectively, over the range tested. The determined indentation moduli were combined with previous work to estimate the longitudinal and transverse elastic modulus of the fiber wall. Due to the relatively low indentation moduli, the elastic constants are also low compared to values obtained via single fiber testing

Role of intrinsic and extrinsic xylan in softwood kraft pulp fiber networks

Xylan is primarily found in the secondary cell wall of plants providing strength and integrity. To take advantage of the reinforcing effect of xylan in papermaking, it is crucial to understand its role in pulp fibers, as it undergoes substantial changes during pulping. However, the contributions of xylan that is added afterwards (extrinsic) and xylan present after pulping (intrinsic) remain largely unexplored. Here, we partially degraded xylan from refined bleached softwood kraft pulp (BSKP) and adsorbed xylan onto BSKP. Enzymatic degradation of 1 % xylan resulted in an open hand sheet structure, while adsorption of 3 % xylan created a denser fiber network. The mechanical properties improved with adsorbed xylan, but decreased more significantly after enzymatic treatment. We propose that the enhancement in mechanical properties by adsorbed extrinsic xylan is due to increased fiber-fiber bonds and sheet density, while the deterioration in mechanical properties of the enzyme treated pulp is caused by the opposite effect. These findings suggest that xylan is decisive for fiber network strength. However, intrinsic xylan is more critical, and the same properties cannot be achieved by readsorbing xylan onto the fibers. Therefore, pulping parameters should be selected to preserve intrinsic xylan within the fibers to maintain paper strength

Size and surface charge of gold nanoparticles determine absorption across intestinal barriers and accumulation in secondary target organs after oral administration

It is of urgent need to identify the exact physico-chemical characteristics which allow maximum uptake and accumulation in secondary target organs of nanoparticulate drug delivery systems after oral ingestion. We administered radiolabelled gold nanoparticles in different sizes (1.4-200 nm) with negative surface charge and 2.8 nm nanoparticles with opposite surface charges by intra-oesophageal instillation into healthy adult female rats. The quantitative amount of the particles in organs, tissues and excrements was measured after 24 h by gamma-spectroscopy. The highest accumulation in secondary organs was mostly found for 1.4 nm particles; the negatively charged particles were accumulated mostly more than positively charged particles. Importantly, 18 nm particles show a higher accumulation in brain and heart compared to other sized particles. No general rule accumulation can be made so far. Therefore, specialized drug delivery systems via the oral route have to be individually designed, depending on the respective target organ

A comparison of five optical surface topography measurement methods

The results of optical surface topography measurement techniques have been questioned in the past because of possible measurement artifacts due to light penetration into the paper. We compared the topography measurement results from five optical techniques: laser profilometry, shape-from-focus, stripe projection, chromatic sensing, and photometric stereo. These techniques were tested on coated and uncoated papers with a PPS roughness range from 0.7 μm to 7.7 μm. We made the measurement results directly comparable by measuring exactly the same regions on the paper samples and registering the resulting topography maps. We then calculated the point-wise Pearson correlation between the maps at different wavelength bands to obtain quantitative values for the similarity of the measurement results at different structure sizes. The correspondences between the measured topography maps were also examined through multivariate linear regression and roughness indices evaluated at two different structure sizes. For rougher grades like office paper or sack paper, the topography measurements from the five measurement techniques showed corresponding results. For a moderately smooth lightweight coated (LWC) paper, the measured topographies agreed to some degree, and for smooth supercalendered (SC) and woodfree coated (WFC) papers, the agreement was poor. From the available data, it is impossible to tell which of the measurement techniques delivers the true surface topography of smooth papers.acceptedVersionPeer reviewe

Long term curl of printing paper due to ink solvent migration

The dimensional stability of paper during printing is crucial for ensuring production quality and runnability. However, inkjet printing faces inherent challenges due to the hygroscopic nature of paper and the use of water-based inks. Despite freshly printed sheets are flat, a considerable development of paper curl is often observed during storage. In this study, we establish the link between the migration of ink co-solvents and the long-term curl development of printed paper. A4 paper sheets were sprayed with a water-glycerol model ink and changes in the sheet's curvature were monitored using a 2D-laser sensor. We also investigated glycerol migration by splitting the sheets into layers and determining the glycerol distribution using high-performance liquid chromatography. Our results demonstrate the development of curl during storage as well as glycerol migration in thickness direction of the sheet, both on a comparable timescale. We thus propose that long term curl in inkjet printing can be caused by z-directional migration of the co-solvent (glycerol) over time. This study enhances understanding of the physical mechanisms that drive the long-term curl phenomenon in inkjet-printed sheets. The results can be used to optimize printing processes, allowing for the production of higher quality printed products with greater dimensional stability

How the Test Setup Can Affect Single Fiber Tensile Testing

ABSTRACTTensile testing is the most common method to investigate natural fibers. The fibers’ mechanical behavior can be considered non-linear and is influenced by viscoelasticity, plasticity, and environmental conditions. Very often such fibers are tested by gluing them with an adhesive onto a sample holder. Such a system consisting of a polymeric sample holder, adhesive, and natural fiber is complex and there is a risk that the mechanical response measured is a mix of the different contributions of those components. In this work, the key components for tensile testing of natural fibers ‒ sample holder and adhesive ‒ are investigated, to determine their influence on the measurement results. In order to isolate the influence of the measurement setup, the natural fiber is replaced with a platinum wire, which is purely linear-elastic. Hence all non-linear contributions from sample holder or adhesive can be identified. The main influence factor on the results was the glue used for fixating the fiber on the sample holder. Epoxy resin was found to be best suited. Taking these findings into account, a series of tensile tests was performed on cellulose-based natural fibers for demonstration but is applicable to any natural fiber