Direct Functionalization of Polysaccharide-Based Xylan Phenyl Carbonate Nanoparticles with Tumor Cell Specific Antibodies.

An efficient and easy-to-use approach is presented for obtaining biocompatible polysaccharide-based nanoparticles (NP) that can act as tumor-specific drug delivery agents. Two antibodies are directly immobilized onto reactive xylan phenyl carbonate (XPC) NP; namely Cetuximab (CTX) that binds to human epidermal growth factor receptor (EGFR) and Atezolizumab (ATZ) that binds to programmed death-ligand 1 (PD-L1). High coupling efficiency (up to 100 %) are achieved without any pre-activation and no aggregation occurs during antibody immobilization. By quartz crystal microbalance experiments with dissipation monitoring (QCM-D), flow cytometry assays, and confocal laser scanning microscopy imaging it is demonstrated that the functionalized XPC-NP specifically bind to cells carrying the corresponding antigens. Moreover, the NP retain the antibody specific bioactivities (growth inhibition for CTX and induction of T-cell cytotoxicity for ATZ).

Efficient heterogeneous synthesis of nucleophilic carboxymethyl hydrazides of polysaccharides.

Nucleophilic moieties in polysaccharides (PS) with distinct higher reactivity compared with the hydroxy group are interesting for sustainable applications in chemistry, medicine, and pharmacy. An efficient heterogeneous method for the formation of such nucleophilic PS is described. Employing alcohols as slurry medium, protonated carboxymethyl (CM) PS and hydrazine hydrate are allowed to react at elevated temperatures. The CM derivatives of starch and pullulan can be transformed almost quantitatively to the corresponding hydrazides. The reaction is less efficient for CM dextrans and CM xylans. As slurry media, 2-propanol and ethanol were probed, and the results are compared with a homogeneous procedure performed in water. Overall, the heterogeneous procedure is superior compared with the homogeneous route. 2-Propanol is the best slurry medium investigated yielding PS hydrazides with the highest nitrogen content.

[Innovation Crisis in Public Theatre? A Longitudinal Study of Theaters in North Rhine-Westphalia, 1995-2018]. / Innovationskrise im staatlichen Theatersektor? Eine Längsschnitt-Analyse für Theater in Nordrhein-Westfalen, 1995­2018.

This paper examines cultural innovations in German public theaters, using North Rhine-Westphalia (NRW) as the most populated region as an example. While existing analyses, including social structure-centered audience research, have focused on the demand side, diagnosing in particular the steady decline and aging of the cultural audience, our analysis addresses the supply side, especially the number of premieres and new productions as well as their adoption into the repertoire. The paper shows that recent efforts by public theaters on the municipal or regional level to increase both the number of venues and the number of plays have not been sufficient to stabilize the declining audience. Too few new plays are scheduled, of which even fewer make it into the long-term repertoire. Our results suggest that theaters can retain their capability for renewal only by staging significantly more new plays, thus attracting new audiences. With regard to such renewal, decentralized competition as a characteristic of the NRW theater landscape seems a favorable institutional context.

Green Fabrication of Highly Conductive Paper Electrodes via Interface Engineering with Aminocellulose.

Herein, a novel, facile, and versatile approach to fabricate highly flexible and conductive paper is proposed by electroless deposition (ELD) with the assistance of aminocellulose as the interface layer. The obtained Cu nanoparticles (NPs)-coated cellulose paper is highly conductive with a significant low resistance of 0.38 Ω sq-1 after only 10 min of ELD treatment. This conductive cellulose paper shows excellent stability when it suffers from bending, folding, and tape adhesion cycles. With the same method, the Cu NPs can also be successfully deposited on the polypropylene (PP)-filled hybrid paper. The conductive paper exhibits very smooth and hydrophobic surface with high reflection, which can be used for special electronic devices. In a word, the fabrication of aminocellulose interface permits a controlled ELD of metal nanoparticles on paper substrate, and this mild and low-cost method opens up new opportunities for large-scale production of flexible and wearable electronics.

Starch Formates: Synthesis and Modification.

Starch can be efficiently converted into the corresponding formates homogeneously using N-formyl imidazole obtained by the reaction of 1,1'-carbonyldiimidazole and formic acid in dimethyl sulfoxide as a solvent. Starch formates are soluble in polar aprotic solvents, not susceptible against hydrolysis, and not meltable. Thermoplastics could be generated by conversion of starch formates with long-chain fatty acids exemplified by the conversion with lauroyl chloride in N,N-dimethylacetamide, leading to mixed starch laurate formates. The mixed esters show melting temperatures mainly dependent on the amount of laurate ester moieties.

Reactive Nanoparticles Derived from Polysaccharide Phenyl Carbonates.

Polysaccharide (PS) based nanoparticles (NP) are of great interest for biomedical applications. A key challenge in this regard is the functionalization of these nanomaterials. The aim of the present work was the development of reactive PS-NP that can be coupled with an amino group containing compounds under mild aqueous conditions. A series of cellulose phenyl carbonates (CPC) and xylan phenyl carbonates (XPC) with variable degrees of substitution (DS) was obtained by homogeneous synthesis. The preparation of PS-NP by self-assembling of these hydrophobic derivatives was studied comprehensively. While CPC mostly formed macroscopic aggregates, XPC formed well-defined spherical NP with diameters around 100 to 200 nm that showed a pronounced long-term stability in water against both particle aggregation as well as cleavage of phenyl carbonate moieties. Using an amino group functionalized dye it was demonstrated that the novel XPC-NP are reactive towards amines. A simple coupling procedure was established that enables direct functionalization of the reactive NP in an aqueous dispersion. Finally, it was demonstrated that dye functionalized XPC-NP are non-cytotoxic and can be employed in advanced biomedical applications.

Aminoethyl substitution enhances the self-assembly properties of an aminocellulose as a potential archaeological wood consolidant.

The 6-deoxy-6-aminocelluloses-or "aminocelluloses"-are a class of synthetic natural cellulose derivatives which are mostly aqueous soluble and have excellent film-forming properties. Recent studies have connected these properties at the molecular level with protein-like self-associative behaviour for a range of aminocelluloses including a 6-deoxy-6-(ω-aminoethyl) aminocellulose AEA-1 with the association being a two-stage process-a reversible oligomerisation followed by further (semi-reversible) aggregation into larger structures. Here, we synthesise and compare a new 6-deoxy-6-(ω-aminoethyl) aminocellulose AEA-1' with different degree of substitution with one with further alkyl derivatisation, namely 6-deoxy-6-(ω-hydroxyethyl) aminocellulose HEA-1'. As with AEA-1, sedimentation velocity and sedimentation equilibrium in the analytical ultracentrifuge still show a two-stage process for both AEA-1' and HEA-1', with the latter giving higher molar masses. The consequences of these properties for use as consolidants for archaeological wood are considered.

Comparative Studies on Regioselectivity of α- and ß-Linked Glucan Tosylation.

Alpha- and beta-linked 1,3-glucans have been subjected to conversion with p-toluenesulfonic acid (tosyl) chloride and triethylamine under homogeneous reaction conditions in N,N-dimethyl acetamide/LiCl. Samples with a degree of substitution of tosyl groups (DSTs) of up to 1.91 were prepared by applying 5 mol reagent per mole repeating unit. Hence, the reactivity of α-1,3-glucan is comparable with cellulose and starch, while the ß-1,3-linked glucan curdlan is less reactive. The samples dissolve in aprotic dipolar media independent of the DSTs and possess a solubility in less polar solvents that depends on the DSTs. NMR studies on the tosyl glucans and of the peracylated derivatives showed a preferred tosylation of position 2 of the repeating unit. However, the selectivity is less pronounced compared with starch. It could be concluded that the α-configurated glycosidic bond directs tosyl groups towards position 2.

Non-Cytotoxic Agarose/Hydroxyapatite Composite Scaffolds for Drug Release.

Healing of large bone defects requires implants or scaffolds that provide structural guidance for cell growth, differentiation, and vascularization. In the present work, an agarose-hydroxyapatite composite scaffold was developed that acts not only as a 3D matrix, but also as a release system. Hydroxyapatite (HA) was incorporated into the agarose gels in situ in various ratios by a simple procedure consisting of precipitation, cooling, washing, and drying. The resulting gels were characterized regarding composition, porosity, mechanical properties, and biocompatibility. A pure phase of carbonated HA was identified in the scaffolds, which had pore sizes of up to several hundred micrometers. Mechanical testing revealed elastic moduli of up to 2.8 MPa for lyophilized composites. MTT testing on Lw35human mesenchymal stem cells (hMSCs) and osteosarcoma MG-63 cells proved the biocompatibility of the scaffolds. Furthermore, scaffolds were loaded with model drug compounds for guided hMSC differentiation. Different release kinetic models were evaluated for adenosine 5'-triphosphate (ATP) and suramin, and data showed a sustained release behavior over four days.

Bottom-up Layer-by-Layer Assembling of Antibacterial Freestanding Nanobiocomposite Films.

In this study, freestanding nanobiocomposite films were obtained by the sequential deposition of biopolymer-capped silver nanoparticles (AgNPs) and hyaluronic acid (HA). At first, dispersions of AgNPs decorated with chitosan (CS) or aminocellulose (AC) were synthesized by applying high intensity ultrasound. These polycationic nanoentities were layer-by-layer assembled with the HA polyanion to generate stable 3D supramolecular constructs, where the biopolymer-capped AgNPs play the dual role of active agent and structural element. SEM images of the assemblies revealed gradual increase of thickness with the number of deposited bilayers. The composites of ≥50 bilayers were safe to human cells and demonstrated 100% antibacterial activity against Staphylococcus aureus and Escherichia coli. Moreover, the films containing CSAgNPs brought about the total prevention of biofilm formation reducing the cells surface adherence by up to 6 logs. Such nanobiocomposites could serve as an effective barrier to control bacterial growth on injured skin, burns, and chronic wounds.

Synthesis of Biopolymer-Based Precursors for the Formation of Organic-Inorganic Hybrid Materials.

Cellulose acetates can be homogeneously transferred with (3-isocyanatopropyl) triethoxysilane, yielding the corresponding carbamates containing reactive ethoxysilane moieties. The products obtained under different conditions are characterized by liquid and solid-state NMR spectroscopy. A slight hydrolysis in products of high Si-content occurs, which strongly affects the solubility of the polymers. The soluble products can be shaped and crosslinked, forming siloxane and silanol polymer network. By incorporating tetraethoxysilane as inorganic precursor, novel silanized film can be prepared and are studied by scanning electron microscopy.

Recent Advances in Solvents for the Dissolution, Shaping and Derivatization of Cellulose: Quaternary Ammonium Electrolytes and their Solutions in Water and Molecular Solvents.

There is a sustained interest in developing solvents for physically dissolving cellulose, i.e., without covalent bond formation. The use of ionic liquids, ILs, has generated much interest because of their structural versatility that results in efficiency as cellulose solvents. Despite some limitations, imidazole-based ILs have received most of the scientific community's attention. The objective of the present review is to show the advantages of using quaternary ammonium electrolytes, QAEs, including salts of super bases, as solvents for cellulose dissolution, shaping, and derivatization, and as a result, increase the interest in further investigation of these important solvents. QAEs share with ILs structural versatility; many are liquids at room temperature or are soluble in water and molecular solvents (MSs), in particular dimethyl sulfoxide. In this review we first give a historical background on the use of QAEs in cellulose chemistry, and then discuss the common, relatively simple strategies for their synthesis. We discuss the mechanism of cellulose dissolution by QAEs, neat or as solutions in MSs and water, with emphasis on the relevance to cellulose dissolution efficiency of the charge and structure of the cation and. We then discuss the use of cellulose solutions in these solvents for its derivatization under homogeneous and heterogeneous conditions. The products of interest are cellulose esters and ethers; our emphasis is on the role of solvent and possible side reactions. The final part is concerned with the use of cellulose dopes in these solvents for its shaping as fibers, a field with potential commercial application.

Determination of Percent Crystallinity of Side-Chain Crystallized Alkylated-Dextran Derivatives with Raman Spectroscopy and Multivariate Curve Resolution.

We demonstrate a methodology to estimate the percent crystallinity of polymers directly with Raman spectroscopy and multivariate curve resolution (MCR) by alternating least-squares (ALS). In this methodology, the Raman spectrum of semicrystalline polymer is separated into two constituent components (crystalline and molten) and their corresponding concentrations. The percent crystallinity can be estimated as the change in area intensity of the molten spectral-component when polymer cools from a temperature above melting point to room temperature. The number of carbons in the crystalline lattice has also been estimated from the position of longitudinal acoustic (LA) Raman bands with the correlation established by Mizushima and Simanouti [ Mizushima, S.; Simanouti, T. J. Am. Chem. Soc. 1949 , 71 , 1320 ]. The new method allows direct Raman estimation of absolute percent crystallinity of polymers. Until now, Raman spectroscopic estimation of percent crystallinity was possible only in conjunction with other techniques or by using internal standards.

Advanced Cellulose Fibers for Efficient Immobilization of Enzymes.

Biocatalytic pulp fibers were prepared using surface functionalization of bleached kraft pulp with amino groups (F) and further immobilization of a cross-linked glucose oxidase (G*) from Aspergillus niger. The cross-linked enzymes (G*) were characterized using X-ray spectroscopy, Fourier transform infrared spectroscopy, dynamic scanning calorimetry, and dynamic light scattering. According to standard assays, the G* content on the resulting fibers (FG*) was of 11 mg/g of fiber, and enzyme activity was of 215 U/g. The results from confocal- and stimulated emission depletion microscopy techniques demonstrated that glucose oxidase do not penetrate the interlayers of fibers. The benefit of pulp fiber functionalization was evident in the present case, as the introduction of amino groups allowed the immobilization of larger amount of enzymes and rendered more efficient systems. Using the approach described on this paper, several advanced materials from wood pulp fibers and new bioprocesses might be developed by selecting the correct enzyme for the target applications.

Development and validation of a capillary electrophoresis method for the characterization of sulfoethyl cellulose.

To characterize sulfoethyl cellulose el samples, a capillary electrophoresis method was developed and validated sulfoethyl cellulose el was hydrolyzed, and the resulting d-glucose derivatives were analyzed after reductive amination with 4-aminobenzoic acid using 150 mM boric acid, pH 9.5, as background electrolyte at 20°C and a voltage of 28 kV. Peak identification was derived from capillary electrophoresis with mass spectrometry using 25 mM ammonia adjusted to pH 6.2 by acetic acid as electrolyte. Besides mono-, di-, and trisulfoethyl d-glucose small amounts of disaccharides could be identified resulting from incomplete hydrolysis. The linearity of the borate buffer-based capillary electrophoresis method was evaluated using d-glucose in the concentration range of 3.9-97.5 µg/mL, while limits of detection and quantification derived from the signal-to-noise ratio of 3 and 10 were 0.4 ± 0.1 and 1.2 ± 0.3 µg/mL, respectively. Reproducibility and intermediate precision were determined using a hydrolyzed sulfoethyl cellulose el sample and ranged between 0.2 and 8.8% for migration times and between 0.3 and 10.4% for peak area. The method was applied to the analysis of the degree of substitution of synthetic sulfoethyl cellulose el samples obtained by variation of the synthetic process and compared to data obtained by elemental analysis.

Magnetic Biocomposites for Remote Melting.

A new approach toward the fabrication of biocompatible composites suitable for remote melting is presented. It is shown that magnetite nanoparticles (MNP) can be embedded into a matrix of biocompatible thermoplastic dextran esters. For that purpose, fatty acid esters of dextran with adjustable melting points in the range of 30-140 °C were synthesized. Esterification of the polysaccharide by activation of the acid as iminium chlorides guaranteed mild reaction conditions leading to high quality products as confirmed by FTIR- and NMR spectroscopy as well as by gel permeation chromatography (GPC). A method for the preparation of magnetically responsive bionanocomposites was developed consisting of combined dissolution/suspension of the dextran ester and hydrophobized MNPs in an organic solvent followed by homogenization with ultrasonication, casting of the solution, drying and melting of the composite for a defined shaping. This process leads to a uniform distribution of MNPs in nanocomposite as revealed by scanning electron microscope. Samples of different geometries were exposed to high frequency alternating magnetic field. It could be shown that defined remote melting of such biocompatible nanocomposites is possible for the first time. This may lead to a new class of magnetic remote control systems, which are suitable for controlled release applications or self-healing materials.

Designing Hydrophobically Modified Polysaccharide Derivatives for Highly Efficient Enzyme Immobilization.

In this contribution, a hydrophobically modified polysaccharide derivative is synthesized in an eco-friendly solvent water by conjugation of benzylamine with the backbone of the biopolymer. Owing to the presence of aromatic moieties, the resulting water-soluble polysaccharide derivative self-assembles spontaneously and selectively from solution on the surface of nanometric thin films and sheets of polystyrene (PS). The synthetic polymer modified in this way bears a biocompatible nanolayer suitable for the immobilization of horseradish peroxidase (HRP), a heme-containing metalloenzyme often employed in biocatalysis and biosensors. Besides the detailed characterization of the polysaccharide derivative, a quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM) are used to investigate the binding efficiency and interaction of HRP with the tailored polysaccharide interfaces. Subsequent enzyme activity tests reveal details of the interaction of HRP with the solid support. The novel polysaccharide derivative and its use as a material for the selective modification of PS lead to a beneficial, hydrophilic environment for HRP, resulting in high enzymatic activities and a stable immobilization of the enzyme for biocatalytic and analytic purposes.

Sonochemically processed cationic nanocapsules: efficient antimicrobials with membrane disturbing capacity.

Bacterial-mediated diseases are a major healthcare concern worldwide due to the rapid spread of antibiotic-resistant bacteria. One strategy to manage the bacterial infections while avoiding the emergence of resistant strains implies specific targeting and disruption of bacteria membranes. This work evaluates the potential of nanostructured biopolymer derivatives, nanocapsules (NCs), to disrupt the bacteria cell walls and effectively kill planktonic microorganisms. Two biopolymers, chitosan and cellulose, were chemically modified to synthesize derivatives with improved cationic character (thiolated chitosan and aminocellulose) prior to their processing into nanocapsules via a one-step sonochemical process. The interactions of NCs, displaying an average size of around 250 nm, with bacteria membrane were evaluated using two membrane models: Langmuir monolayers and liposome bilayers composed of a l-α-phosphatidylglycerol phospholipid extracted from Escherichia coli. NCs possessed improved membrane disturbing capacity in comparison to the nonprocessed biopolymer derivatives, by drastically increasing the monolayer fluidity and inducing more than 50% leakage of a dye inserted in the bilayered liposomes. In addition, membrane disturbance was directly proportional to the NCs cationic charge. Whereas evidence showed that thiolated chitosan and aminocellulose interacted with the bacteria membrane through a "carpet model", the NCs were found to induce larger surface defects and high local perturbance through a "detergent model". Importantly, the degree of disruption caused by the biopolymer derivatives and NCs correlated well with the antimicrobial capacity against Escherichia coli, selectively killing bacteria cells without imparting toxicity to human fibroblasts.

Triggering protein adsorption on tailored cationic cellulose surfaces.

The equipment of cellulose ultrathin films with BSA (bovine serum albumin) via cationization of the surface by tailor-made cationic celluloses is described. In this way, matrices for controlled protein deposition are created, whereas the extent of protein affinity to these surfaces is controlled by the charge density and solubility of the tailored cationic cellulose derivative. In order to understand the impact of the cationic cellulose derivatives on the protein affinity, their interaction capacity with fluorescently labeled BSA is investigated at different concentrations and pH values. The amount of deposited material is quantified using QCM-D (quartz crystal microbalance with dissipation monitoring, wet mass) and MP-SPR (multi-parameter surface plasmon resonance, dry mass), and the mass of coupled water is evaluated by combination of QCM-D and SPR data. It turns out that adsorption can be tuned over a wide range (0.6-3.9 mg dry mass m(-2)) depending on the used conditions for adsorption and the type of employed cationic cellulose. After evaluation of protein adsorption, patterned cellulose thin films have been prepared and the cationic celluloses were adsorbed in a similar fashion as in the QCM-D and SPR experiments. Onto these cationic surfaces, fluorescently labeled BSA in different concentrations is deposited by an automatized spotting apparatus and a correlation between the amount of the deposited protein and the fluorescence intensity is established.

Acetone-based cellulose solvent.

Acetone containing tetraalkylammonium chloride is found to be an efficient solvent for cellulose. The addition of an amount of 10 mol% (based on acetone) of well-soluble salt triethyloctylammonium chloride (Et3 OctN Cl) adjusts the solvent's properties (increases the polarity) to promote cellulose dissolution. Cellulose solutions in acetone/Et3 OctN Cl have the lowest viscosity reported for comparable aprotic solutions making it a promising system for shaping processes and homogeneous chemical modification of the biopolymer. Recovery of the polymer and recycling of the solvent components can be easily achieved.