Untersuchungen zur Cyanhydrinsynthese in ionischen Flüssigkeiten

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A General Aqueous Silanization Protocol to Introduce Vinyl, Mercapto or Azido Functionalities onto Cellulose Fibers and Nanocelluloses

The effective and straight-forward modification of nanostructured celluloses under aqueous conditions or as “never-dried” materials is challenging. We report a silanization protocol in water using catalytic amounts of hydrogen chloride and then sodium hydroxide in a two-step protocol. The acidic step hydrolyzes the alkoxysilane to obtain water-soluble silanols and the subsequent addition of catalytic amounts of NaOH induces a covalent reaction between cellulose surficial hydroxyl groups and the respective silanols. The developed protocol enables the incorporation of vinyl, thiol, and azido groups onto cellulose fibers and cellulose nanofibrils. In contrast to conventional methods, no curing or solvent-exchange is necessary, thereby the functionalized celluloses remain never-dried, and no agglomeration or hornification occurs in the process. The successful modification was proven by solid state NMR, ATR-IR, and EDX spectroscopy. In addition, the covalent nature of this bonding was shown by gel permeation chromatography of polyethylene glycol grafted nanofibrils. By varying the amount of silane agents or the reaction time, the silane loading could be tuned up to an amount of 1.2 mmol/g. Multifunctional materials were obtained either by prior carboxymethylation and subsequent silanization; or by simultaneously incorporating both vinyl and azido groups. The protocol reported here is an easy, general, and straight-forward avenue for introduction of anchor groups onto the surface of never-dried celluloses, ready for click chemistry post-modification, to obtain multifunctional cellulose substrates for high-value applications

Porous lyocell powders as sound absorbers

International audienc

Self-Assembly of Soft Cellulose Nanospheres into Colloidal Gel Layers with Enhanced Protein Adsorption Capability for Next-Generation Immunoassays

| openaire: EC/H2020/760876/EU//INNPAPER | openaire: EC/H2020/788489/EU//BioELCellSoft cationic core/shell cellulose nanospheres can deform and interpenetrate allowing their self-assembly into densely packed colloidal nanogel layers. Taking advantage of their water-swelling capacity and molecular accessibility, the nanogels are proposed as a new and promising type of coating material to immobilize bioactive molecules on thin films and paper. The specific and nonspecific interactions between the cellulosic nanogel and human immunoglobulin G as well as bovine serum albumin (BSA) are investigated. Confocal microscopy, electroacoustic microgravimetry, and surface plasmon resonance are used to access information about the adsorption behavior and viscoelastic properties of self-assembled nanogels. A significant BSA adsorption capacity on nanogel layers (17 mg m−2) is measured, 300% higher compared to typical polymer coatings. This high protein affinity further confirms the promise of the introduced colloidal gel layer, in increasing sensitivity and advancing a new generation of substrates for a variety of applications, including immunoassays, as demonstrated in this work.Peer reviewe

Soft cellulose II nanospheres

| openaire: EC/H2020/788489/EU//BioELCellHigh axial aspect crystalline nanomaterials have emerged as polymeric building blocks for the construction of supermaterials. In contrast to this form, amorphous nanospheres have remained largely untapped. This is especially peculiar in the context of material assembly, due to the wide range of opportunities they offer by virtue of their soft particle characteristics, high volume ratio at low solid content and their highly swollen and accessible structure. In the context of cellulose, these colloids represent a new field in the family of nanocelluloses. We report an organic solvent-free, heterogeneous and simple synthesis of spherical carboxylated nanoparticles bearing a distinctive, amorphous outer shell structure. The particle shape is evaluated by atomic force microscopy, cryo-transmission electron microscopy, dynamic light scattering and small-angle X-ray scattering. The soft shell structure of the particles and their responsiveness to ionic strength and pH are quantified by the combination of quartz-crystal microgravimetry and atomic force microscopy. Aqueous dispersions of the nanocolloids feature distinctive sol/gel behaviour: At solid content <2 wt% they behave as a low viscous liquid (sol state), whereas at higher concentrations the shells dominate the interparticle interactions, causing an exponential increase in viscosity, typical of a gel state (hydrogel). Gelation is reversible and can be triggered alternatively by protonation of the carboxylate groups under acidic conditions. Supercritical drying of the hydrogels yields a highly porous, isotropic aerogel composed of aggregated nanoparticles. In contrast, ambient drying results in an anisotropic, fully transparent film. These colloids will allow the study of the interaction between soft cellulose and rigid matter, and have high potential as toughening additives in composites. Furthermore, the amorphous nature of this new class of cellulose nanocolloids makes them attractive as support materials for catalysts and enzymes.Peer reviewe