Synthesis of a Liquid Lignin-Based Methacrylate Resin and Its Application in 3D Printing without Any Reactive Diluents.

3D printing of bio-based and renewable polymers such as lignin has gained research attention during the last few decades. We report on the synthesis and characterization of a liquid lignin-based photopolymer and its application in additive manufacturing (AM). Wheat straw soda lignin is liquified in an oxyalkylation reaction with propylene oxide under alkaline conditions and modified with methacryloyl chloride to obtain a lignin-based methacrylate resin. Ninety percent of the functional hydroxyl groups are grafted during the synthesis. The photopolymerization efficiency was evaluated by real-time-NIR-photorheology experiments with two different photoinitiators, leading to double bond conversions (DBC) of ≥80%. 3D-printing experiments of the methacrylated lignin were performed with the hot lithography technology. For the first time, a light-curable lignin derivative with a lignin content of over 30% was successfully 3D printed via vat photopolymerization without any reactive diluents, which is a significant improvement over current state-of-the-art solutions. This outstanding result is a motivating proof of concept and a promising starting point for the in-depth evaluation of bio-based precursors as an alternative to nonrenewable derivatives for 3D printing.

DMTMM-mediated methylamidation for MALDI mass spectrometry analysis of N-glycans with structurally conserved sialic acid residues in biological fluids "via direttissima".

Characterization of serum glycoprotein N-glycans with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) in positive-ion mode needs a derivatization step to stabilize and neutralize the negative charge on sialic acids. The acidic sugars are attached to the end of glycoproteins, glycolipids or gangliosides. Here, we present a method for sialic acid stabilization via modification based on derivatization of carboxylic acid group activated with 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) with methylamine. DMTMM substitutes in many processes N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide (EDC/NHS) as activation reagent due to its better performance and higher stability in water. Glycosylated proteins are used as solid phase support for glycan derivatization and purification from excess of derivatization reagents. We evaluated our glycan analysis method in murine sera and intestinal lavages. The stabilization of sialic acid enables a complete conservation of the glycan structures, in contrast to other methods where sialic acids are partially lost. In BALB/c mouse sera, we detected predominantly mono- and di-sialylated N-glycans with mostly N-Glycolylneuraminic acid (Neu5Gc) and only trace amounts of N-Acetyl neuraminic acid (Neu5Ac). BALB/c mouse intestinal lavages glycoproteins contained asialo N-glycans. DMTMM-mediated methylamidation of N-glycans for MALDI mass spectrometry analysis is a fast and cheap method for structurally conserved glycan derivatization.

Improving Rheological and Mechanical Properties of Various Virgin and Recycled Polypropylenes by Blending with Long-Chain Branched Polypropylene.

Blends of two long-chain branched polypropylenes (LCB-PP) and five linear polypropylenes (L-PP) were prepared in a single screw extruder at 240 °C. The two LCB-PPs were self-created via reactive extrusion at 180 °C by using dimyristyl peroxydicarbonate (PODIC C126) and dilauroyl peroxide (LP) as peroxides. For blending two virgin and three recycled PPs like coffee caps, yoghurt cups and buckets with different melt flow rate (MFR) values were used. The influence of using blends was assessed by investigating the rheological (dynamic and extensional rheology) and mechanical properties (tensile test and impact tensile test). The dynamic rheology indicated that the molecular weight as well as the molecular weight distribution could be increased or broadened. Also the melt strength behavior could be improved by using the two peroxide modified LCB-PP blends on the basis of PODIC C126 or PEROXAN LP (dilauroyl peroxide). In addition, the mechanical properties were consistently enhanced or at least kept constant compared to the original material. In particular, the impact tensile strength but also the elongation at break could be increased considerably. This study showed that the blending of LCB-PP can increase the investigated properties and represents a promising option, especially when using recycled PP, which demonstrates a real "up-cycling" process.

Influence of Different Types of Peroxides on the Long-Chain Branching of PP via Reactive Extrusion.

Long-chain branching (LCB) is known as a suitable method to increase the melt strength behavior of linear polypropylene (PP), which is a fundamental weakness of this material. This enables the modification of various properties of PP, which can then be used-in the case of PP recyclates-as a practical "upcycling" method. In this study, the effect of five different peroxides and their effectiveness in building LCB as well as the obtained mechanical properties were studied. A single screw extruder at different temperatures (180 and 240 °C) was used, and long-chain branched polypropylene (PP-LCB) was prepared via reactive extrusion by directly mixing the peroxides. The peroxides used were dimyristyl peroxydicarbonate (PODIC C126), tert-butylperoxy isopropylcarbonate (BIC), tert-Butylperoxy 2-ethylhexyl carbonate (BEC), tert-amylperoxy 2-ethylhexylcarbonate (AEC), and dilauroyl peroxide (LP), all with a concentration of 20 mmol/kg. The influence of the temperature on the competitive prevalent reactions of degradation and branching was documented via melt mass-flow rate (MFR), rheology measurements, and gel permeation chromatography (GPC). However, via extensional rheology, strain hardening could be observed in all cases and the mechanical properties could be maintained or even improved. Particularly, PODIC C126 and LP signaled a promising possibility for LCB in this study.

Exact determination of the degree of substitution of high molar mass hyaluronan by controlling the conformation in solution.

The purpose of the present study was the development of an accurate method to determine the degree of substitution (DS) of modified hyaluronic acid (HA) by proton nuclear magnetic resonance (1H NMR) spectroscopy. The influence of the effect of ionic strength and pH on 1H NMR spectra of HA was studied. The results showed a correlation between the conformation of HA in solution and the quality of the 1H NMR spectra. The best spectra with full proton mobility are obtained when HA is dissolved in D2O with 2 M NaCl or D2O with 0.1 M NaOD with a maximum concentration of 5 mg/ml. Under those conditions the size of the polymer coils is reduced below the concentration of chain overlap point, all the protons show the same response and a correct degree of substitution can be determined.

Long chain branching as an innovative up-cycling process of polypropylene post-consumer waste - Possibilities and limitations.

Long chain branching (LCB) was used the first time as an innovative tool for value adding to PP from household post-consumer waste. Due to the highly improved melt properties, the possible application profile is extended and not only a "re-cycling" process, even a real "up-cycling" is presented. The used PP was collected from commingled household polyolefin waste, which contained different types of PP and macromolecular impurities such as 10% of polyethylene with high density (PE-HD). In addition, a single PP waste fraction from cleaned beverage and yoghurt cups was manually sorted. The up-cycled PP from single polymer waste, as well as the post-consumer blend, showed pronounced strain hardening and increased melt strength, which was comparable to LCB-PP prepared from virgin PP. However, the up-cycled post-consumer blend showed weaker mechanical performance especially low elongation at break due to PE-HD.

Influence of the Molar Mass on Long-Chain Branching of Polypropylene.

Long-chain branching (LCB) with peroxydicarbonates (PODIC) is known as a suitable post-reactor process to introduce strain-hardening behaviour and an increase of melt strength to a linear polypropylene (PP). This opens up new possibilities for processing and therefore application. Especially in the case of adding value to PP post-consumer waste, LCB is a promising approach. LCB takes place by a combination of chain scission and recombination after radical activation of the PP macromolecule. However, chemical modification of post-consumer waste is challenging because of the inhomogeneous composition and the manifold number of PP grades. The influence of the molar mass of the linear PP precursor on this reaction was studied with different PP grades ranging from extrusion grade to injection moulding grade. To exclude side effects, all PP grades had similar polydispersity indices. A PP with higher molar mass undergoes significant chain scission during the LCB process compared to a PP with low molar mass for injection moulding. Therefore, the two grades differ significantly in their branching number, which influences their behaviour in elongational flow.