Photoinitiator-free photopolymerization of acrylate-bismaleimide mixtures and their application for inkjet printing

There is growing interest in using photoinitiator-free systems in coating applications such as inkjet-printing, because residual photoinitiator can alter the properties of the resulting polymer. Bismaleimides (BMI) offer the opportunity to polymerize acrylates without the addition of photoinitiators, as this class of molecules can serve both as polymerizable monomer and as photoinitiator together with electron donor systems, like vinyl ether monomers or acrylates. The UV-induced copolymerization of a low-molecular-weight BMI with various acrylate monomers and oligomers without any photoinitiator was characterized. The BMI-acrylate systems show comparable polymerization speeds to widely used acrylic systems with photoinitiator. Superior thermal stability as well as thermomechanical properties are achieved by enhancing acrylics with BMI. Such photoinitiator-free systems lend themselves to be used for low-migration coatings as well as for high-temperature applications. Here, a characterization of selected BMI-acrylate mixtures regarding their photocuring kinetics and their application as inks for inkjet printing is shown. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47789.     

Temperature stimuli-responsive nanoparticles from chitosan-graft-poly(N-vinylcaprolactam) as a drug delivery system

This work describes the preparation of thermosensitive chitosan-graft-poly(N-vinylcaprolactam) nanoparticles by ionic gelation and their potential use as a controlled drug delivery system, using doxorubicin as a model drug. A systematic study of the effect of the main processing parameters on both the size and thermoresponsive behavior of nanoparticles was investigated. The size of the particles is strongly dependent on the length of the poly(N-vinylcaprolactam) grafted chains and the concentration of the copolymer and crosslinking agent solutions. The molecular structure of the copolymer plays an essential role in the phase transition temperature of the particles, which decreases with the length of PVCL grafted chain. The system displayed proper drug-association parameters, and the drug-loaded nanoparticles exhibited dose-dependent cytotoxicity. A significant increase in the doxorubicin delivery rate was observed above the phase transition temperature (40 °C). These features indicate that these nanoparticles are suitable for the development of a new thermally controlled anti-cancer drug delivery system. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47831.     

Alteration of the Route to Menaquinone towards Isochorismate-Derived Metabolites

Chorismate and isochorismate constitute branch-point intermediates in the biosynthesis of many aromatic metabolites in microorganisms and plants. To obtain unnatural compounds, we modified the route to menaquinone in Escherichia coli. We propose a model for the binding of isochorismate to the active site of MenD ((1R,2S, 5S,6S)-2-succinyl-5-enolpyruvyl-6-hydroxycyclohex-3-ene-1-carboxylate (SEPHCHC) synthase) that explains the outcome of the native reaction with α-ketoglutarate. We have rationally designed variants of MenD for the conversion of several isochorismate analogues. The double-variant Asn117Arg–Leu478Thr preferentially converts (5S,6S)-5,6-dihydroxycyclohexa-1,3-diene-1-carboxylate (2,3-trans-CHD), the hydrolysis product of isochorismate, with a >70-fold higher ratio than that for the wild type. The single-variant Arg107Ile uses (5S,6S)-6-amino-5-hydroxycyclohexa-1,3-diene-1-carboxylate (2,3-trans-CHA) as substrate with >6-fold conversion compared to wild-type MenD. The novel compounds have been made accessible in vivo (up to 5.3 g L⁻¹). Unexpectedly, as the identified residues such as Arg107 are highly conserved (>94 %), some of the designed variations can be found in wild-type SEPHCHC synthases from other bacteria (Arg107Lys, 0.3 %). This raises the question for the possible natural occurrence of as yet unexplored branches of the shikimate pathway.     

Improvement of Aglycone π-Stacking Yields Nanomolar to Sub-nanomolar FimH Antagonists

Antimicrobial resistance has become a serious concern for the treatment of urinary tract infections. In this context, an anti-adhesive approach targeting FimH, a bacterial lectin enabling the attachment of E. coli to host cells, has attracted considerable interest. FimH can adopt a low/medium-affinity state in the absence and a high-affinity state in the presence of shear forces. Until recently, mostly the high-affinity state has been investigated, despite the fact that a therapeutic antagonist should bind predominantly to the low-affinity state. In this communication, we demonstrate that fluorination of biphenyl α-d -mannosides leads to compounds with perfect π–π stacking interactions with the tyrosine gate of FimH, yielding low nanomolar to sub-nanomolar K_D values for the low- and high-affinity states, respectively. The face-to-face alignment of the perfluorinated biphenyl group of FimH ligands and Tyr48 was confirmed by crystal structures as well as ¹H,¹⁵N-HSQC NMR analysis. Finally, fluorination improves pharmacokinetic parameters predictive for oral availability.     

Development of Biarylalkyl Carboxylic Acid Amides with Improved Anti-schistosomal Activity

The parasitic disease schistosomiasis is the cause of more than 200 000 human deaths per year. Although the disease is treatable, there is one major shortcoming: praziquantel has been the only drug used to combat these parasites since 1977. The risk of the emergence of resistant schistosomes is known to be increasing, as a reduced sensitivity of these parasites toward praziquantel has been observed. We developed a new class of substances, which are derived from inhibitors of human aldose reductase, and which showed promising activity against Schistosoma mansoni couples in vitro. Further optimisation of the compounds led to an increase in anti-schistosomal activity with observed phenotypes such as reduced egg production, vitality, and motility as well as tegumental damage and gut dilatation. Here, we performed structure–activity relationship studies on the carboxylic acid moiety of biarylalkyl carboxylic acids. Out of 82 carboxylic acid amides, we identified 10 compounds that are active against S. mansoni at 25 μm . The best five compounds showed an anti-schistosomal activity up to 10 μm and induced severe phenotypes. Cytotoxicity tests in human cell lines showed that two derivatives had no cytotoxicity at 50 or 100 μm . These compounds are promising candidates for further optimisation toward the new anti-schistosomal agents.     

NMR study on reaction processes from aluminum chloride hydroxides to alpha alumina powders

Starting from gelatinous aluminum chloride hydroxide, the transformation process toward α-Al₂O₃ was examined using ²⁷Al NMR, both in the liquid and solid states, as a main analytical tool. By increasing the hydrolysis ratio (h, defined as [OH⁻]/[Al³⁺]) of the starting aqueous precursor up to h = 2.5, the transition temperature to the final product, α-Al₂O₃, decreased to as low as 500°C. In this case, the structural change from amorphous alumina to α-Al₂O₃ took place without intermediate transition Al₂O₃ phases. Examining the process of networking during the transition from aqueous sol–through the state of xerogel–to final anhydrous oxide by nuclear magnetic resonance (NMR) revealed the presence of highly polymeric species mainly ascribed to δ-[Al₂O₈Al₂₈(OH)₅₆(H₂O)₂₄]¹⁸⁺ (δ-Al₃₀). δ-Al₃₀ species were found in the solution phase and became predominant after drying. We conclude that the lower temperature synthesis of α-Al₂O₃ became possible due to preformation of polymerized AlO₆ construction units in the precursor, reducing the energy barrier for the nucleation of the final α-Al₂O₃ phase.     

The effect of gelation on statically and dynamically freeze-cast structures

Freeze-casting is a technique used to produce structures with anisotropic porosity in the form of well-defined microchannels throughout a sample. Here, this technique is used on the magnetocaloric ceramic La_0.66Ca_0.26Sr_0.07 Mn_1.05O₃. We show that a dynamic freezing profile, where the temperature is decreased continuously at −10 K/min, results in homogeneous, lamellar channels with widths of ∼15 µm, while static freezing, where the temperature is kept constant at 177 K, results in channels of increasing size away from the initial ice crystal nucleation site. The effect of gelation before freeze-casting is also investigated. Gelation inhibits ice crystal growth, which significantly changes the morphology by making channel cross sections less elongated, while additionally introducing more dendrites and ceramic bridges in the structure. The latter significantly dominates the flow path through the gelated structures, affecting the calculated tortuosity, which increases to τ ≈ 4 when compared to non-gelated samples where calculated tortuosities are in the range of ∼1.3 to ∼3. Finally, we present a systematic and automatic approach for evaluating channel and wall sizes and calculating tortuosities. This is based on analysis of images obtained by scanning electron microscopy using a continuous particle size distribution method and the TauFactor application in MATLAB^®.     

Polymer derived ceramic materials from Si,B and MoSiB filler-loaded perhydropolysilazane precursor for oxidation protection

Silica-based coating systems were developed using polymer derived ceramics (PDCs) technology. Ceramic composites on the base of a SiO₂ and SiNO matrix and homogeneously distributed Mo₅SiB₂, SiB₆, Si and B fillers were manufactured. The coating systems have low porosity and provide a high oxidation resistance up to 100 h at 800 °C and 1100 °C in air. The influence of temperature and atmosphere of pyrolysis on the polymer precursor, the volume fraction of filler materials on the chemical composition of compacts as well as their high-temperature oxidation protection was investigated.