Wood and other cellulosic materials are highly sensitive to changes in moisture content, which affects their use in most applications. We investigated the effects of moisture changes on the nanoscale ...structure of wood using X-ray and neutron scattering, complemented by dynamic vapor sorption. The studied set of samples included tension wood and normal hardwood as well as representatives of two softwood species. Their nanostructure was characterized in wet state before and after the first drying as well as at relative humidities between 15 and 90%. Small-angle neutron scattering revealed changes on the microfibril level during the first drying of wood samples, and the structure was not fully recovered by immersing the samples back in liquid water. Small and wide-angle X-ray scattering measurements from wood samples at various humidity conditions showed moisture-dependent changes in the packing distance and the inner structure of the microfibrils, which were correlated with the actual moisture content of the samples at each condition. In particular, the results implied that the degree of crystalline order in the cellulose microfibrils was higher in the presence of water than in the absence of it. The moisture-related changes observed in the wood nanostructure depended on the type of wood and were discussed in relation to the current knowledge on the plant cell wall structure.
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The development of a new sample environment enabling X‐ray scattering measurements at small and large angles under mechanical compression and hydraulic flow is presented. The cell, which is adapted ...for moderate pressures, includes beryllium windows, and allows applying simultaneously a compressive pressure up to 2.5 kbar in the perpendicular direction to the flow and either a hydrostatic pressure up to 300 bar or a pressure gradient of the same amplitude. The development of high‐pressure devices for synchrotron experiments is relevant for many scientific fields in order to unveil details of a material's structure under relevant conditions of stresses. In particular, mechanical constraints coupled to hydrostatic pressure or flow, leading to complex stress tensor and mechanical response, and therefore unexpected deformations (swelling and pore deformation), are poorly addressed. Here, first the design of the environment is described, and then its performance with measurements carried out on a regenerated cellulose membrane is demonstrated.
The innovative pressure cell described, suitable for X‐ray measurements combining both hydraulic and compressive pressures, is well adapted for studying poromechanical coupling in soft environments.
An emerging target to overcome cancer resistance to treatments is copper, which is upregulated in a wide variety of tumors and may be associated with cancer progression and metastases. The aim of ...this study was to develop a multimodal ultrasmall nanoparticle, CuPRiX, based on the clinical AGuIX nanoparticle made of the polysiloxane matrix on which gadolinium chelates are grafted. Such hybrid nanoparticles allow: (i) a localized depletion of copper in tumors to prevent tumor cell dissemination and metastasis formation and (ii) an increased sensitivity of the tumor to radiotherapy (RT) due to the presence of high Z gadolinium (Gd) atoms. CuPRiX nanoparticles are obtained by controlled acidification of AGuIX nanoparticles. They were evaluated in vitro on two cancer cell lines (lung and head and neck) using the scratch-wound assay and clonogenic cell survival assay. They were able to reduce cell migration and invasion and displayed radiosensitizing properties.
Anomalous small-angle X-ray scattering (ASAXS) is a technique developed in the 1980s giving access to chemical information of nano-objects besides characteristic features like size and volume ...fraction given by classical SAXS. ASAXS is an element-selective technique based on the anomalous variation of the scattering factor near the absorption edge of one chosen element. A simple approach is proposed to extract chemical information from anomalous SAXS data. To illustrate the procedure, data treatment is applied to discriminate between different possible phases that may form nano-oxides in oxide-dispersion-strengthened (ODS) steels.
•Anomalous small-angle X-ray scattering (ASAXS) is a non-destructive technique.•ASAXS gives access to chemical information of nano-objects.•A straightforward procedure is proposed for ASAXS data treatment.•The procedure is applied to nano-oxides in ODS steels.
In this work, we propose the formation of stretchable hydrogels at neutral pH from the physical crosslinking of chitosan (CS) and hyaluronic acid (HA) by polyelectrolyte complexation. A mixture of CS ...(Mw ≈ 600 kg/mol, degree of acetylation ≈ 50 %) solution and HA (Mw ≈ 77 kg/mol) solution was prepared with an excess of salts screening the electrostatic interactions CS/HA. In a controlled manner, the polyelectrolyte complexation was induced through the progressive dialysis of the salted polymer mixture against a sodium acetate solution (AcONa, 0.01 M) for 7 days. Depending on HA, various materials were obtained: viscous solutions at HA = 0.75 % (w/v); hydrogels at HA = 1.50–2.24 % (w/v) with Young modulus of 14 kPa and stretchable to 200 %. The small angle X-ray scattering characterization of the hydrogels revealed a multiscale organization related to the conformation of the polymers induced by the physical interactions. The dialysis process with AcONa was optimized by adding a dialysis step against a zinc acetate solution containing Zn2+. The combination of polyelectrolyte complexation between CS/HA and metal complexation between Zn2+ and the polymers led to an enhancement of the hydrogel stretchability up to 400 %.
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The use of two techniques, differential interferometry and quasi-elastic light scattering (QELS), allowed us to study solutions of chitosan varying in degree of acetylation (DA), degree of ...dissociation (alpha), and concentration (C(p)). With the first technique, we demonstrated the modification of the electric polarizability of the polymer chains, through a law of behavior of the variation of the refractive index increment dn/dC with DA and alpha. This brought us information on the various kinds of interactions (H-bonds, electrostatic, and hydrophobic) involved in the evolution of the solution properties. QELS experiments performed in dilute regime showed the presence of supramolecular structures depending on DA and alpha. The topology and the nature of these objects are discussed. The typical presence of aggregates and their evolution with concentration was also demonstrated in semidilute regime.
Hydrothermal treatment between 150 °C and 230 °C is widely used in wood processing, from the steam treatment of timber for better dimensional stability and durability to the pretreatment for ...enzymatic saccharification and chemical pulping. Understanding the ultrastructural changes of wood cell walls through hydrothermal treatments is crucial for controlling and optimizing these hydrothermal treatment-based processes. Here, we studied the ultrastructure of wood cell walls of 24 hardwood species using simultaneous small- and wide-angle X-ray scattering measurements before and after the hydrothermal treatment at 200 °C. Most hardwoods show similar equatorial scattering features, representing the structure in the cross-section of the cell walls. In a water-saturated native state, there is a prominent correlation peak between 0.1 and 0.2 Å
−1
and a second peak between 0.2 and 0.4 Å
−1
. The hydrothermal treatment above 160 ˚C drastically altered the structure at this nanometric scale: the two native correlation peaks disappeared, coincident with a buildup of a correlation peak in the 0.03–0.04 Å
−1
range. The hydrothermal treatment likely removed the cell wall matrix component between the microfibrils through autohydrolysis and phase separation, leading to the collapse of microfibrils with each other in the normal wood. In cellulose-rich cell walls, such as the G-layer in tension wood, cellulose microfibrils are already collated in the native state.
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Supramolecular polymer bottlebrushes (SPBs) consist in the 1D self-assembly of building blocks composed of a self-assembling core with pendant polymer arms. Kinetic hurdles often ...hinder their stimuli-responsiveness in solution. Changing the nature of the solvent should alleviate these hurdles by modulating the self-association strength, leading to stimuli-responsive SPBs.
The SPBs were formed, in various solvents, by hydrogen bond-driven self-assembly of an azobenzene-bisurea decorated with poly(ethylene oxide) polymer arms. The photo-isomerization of the azobenzene unit was studied by UV/visible spectroscopy and proton NMR spectroscopy, whereas the consequences on supramolecular self-assembly were studied by small angle neutron and X-ray scattering.
In water, the assembly was previously shown to be driven by both hydrogen-bonds and strong hydrophobic effects, the latter rendering the system kinetically frozen and the disassembly irreversible. Here we show that in organic solvents such as toluene or chloroform, reversible light-responsive dissociation is achieved. Solvophobic effects in these solvents are expected to be much weaker than in water, which probably allows reversibility of the light-response in the former solvents. The key role of the solvent on the reversibility of the process opens up new perspectives for the design of stimuli-responsive SPBs and their applications in various fields.
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