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Hepcidin-25 was identified as themain iron regulator in the human body, and it by binds to the sole iron-exporter ferroportin. Studies showed that the N-terminus of hepcidin is responsible for this interaction, the same N-terminus that encompasses a small copper(II) binding site known as the ATCUN (amino-terminal Cu(II)- and Ni(II)-binding) motif. Interestingly, this copper-binding property is largely ignored in most papers dealing with hepcidin-25. In this context, detailed investigations of the complex formed between hepcidin-25 and copper could reveal insight into its biological role. The present work focuses on metal-bound hepcidin-25 that can be considered the biologically active form. The first part is devoted to the reversed-phase chromatographic separation of copper-bound and copper-free hepcidin-25 achieved by applying basic mobile phases containing 0.1% ammonia. Further, mass spectrometry (tandemmass spectrometry (MS/MS), high-resolutionmass spectrometry (HRMS)) and nuclear magnetic resonance (NMR) spectroscopy were employed to characterize the copper-peptide. Lastly, a three-dimensional (3D)model of hepcidin-25with bound copper(II) is presented. The identification of metal complexes and potential isoforms and isomers, from which the latter usually are left undetected by mass spectrometry, led to the conclusion that complementary analytical methods are needed to characterize a peptide calibrant or referencematerial comprehensively. Quantitative nuclear magnetic resonance (qNMR), inductively-coupled plasma mass spectrometry (ICP-MS), ion-mobility spectrometry (IMS) and chiral amino acid analysis (AAA) should be considered among others.
The title compound was prepared by the reaction of 1,4,10,13-tetraoxa-7,16-diazacyclo-octadecane with 4-chloro-2-methyl-phenoxyacetic acid in a ratio of 1:2. The structure has been proved by the data of elemental analysis, IR spectroscopy, NMR ( 1 H, 13 C) technique and by X-ray diffraction analysis. Intermolecular hydrogen bonds between the azonium protons and oxygen atoms of the carboxylate groups were found. Immunoactive properties of the title compound have been screened. The compound has the ability to suppress spontaneous and Con A-stimulated cell proliferation in vitro and therefore can be considered as immunodepressant.
This opinion article describes recent approaches to use the "biorefinery" concept to lower the carbon footprint of typical mass polymers, by replacing parts of the fossil monomers with similar or even the same monomer made from regrowing dendritic biomass. Herein, the new and green catalytic synthetic routes are for lactic acid (LA), isosorbide (IS), 2,5-furandicarboxylic acid (FDCA), and p-xylene (pXL). Furthermore, the synthesis of two unconventional lignocellulosic biomass derivable monomers, i.e., alpha-methylene-gamma-valerolactone (MeGVL) and levoglucosenol (LG), are presented. All those have the potential to enter in a cost-effective way, also the mass market and thereby recover lost areas for polymer materials. The differences of catalytic unit operations of the biorefinery are also discussed and the challenges that must be addressed along the synthesis path of each monomers.
Monolayers of rod-shaped and disc-shaped liquid crystalline compounds at the air-water interface
(1986)
Calamitic (rod-shaped) and discotic (disc-shaped) thermotropic liquid crystalline (LC) compounds were spread at the air-water interface, and their ability to form monolayers was studied. The calamitic LCs investigated were found to form monolayers which behave analogously to conventional amphiphiles such as fatty acids. The spreading of the discotic LCs produced monolayers as well, but with a behaviour different from classical amphiphiles. The areas occupied per molecule are too small to allow the contact of all hydrophilic groups with the water surface and the packing of all hydrophobic chains. Various molecular arrangements of the discotics at the water surface to fit the spreading data are discussed.
Several types of insect cuticle contain enzymes catalyzing the formation ofof adducts between N-acetyldopamine (NADA) and N-acetylhistidine (NAH). Two such adducts, NAH-NADA-I and NAH NADA-II, have been isolated and their structures determined. In one of the adducts the link connecting the two residues occurs between the I-position (ß-position) in the NADA side chain and the 1-N atom (τ-N) in the imidazole ring of histidine. Diphenoloxidase activity alone is not sufficient for formation of this adduct, whereas extracts containing both diphenoloxidase and o-quinone-p-quinone methide isomerase activities catalyze the coupling reaction. The adduct consists of a mixture of two diastereomers and they are presumably formed by spontaneous reaction between enzymatically produced NADA-p-quinone methide and N-acetylhistidine. The other adduct has been identified as a ring addition product of N-acetylhistidine and NADA. In contrast to the former adduct it can be formed by incubation of the two substrates with mushroom tyrosinase alone. An adduct between N-acetylhistidine and the benzodioxan-type NADA-dimer is produced in vitro, when the N-acetylhistidine-NADA adduct is incubated with NADA and locust cuticle containing a 1,2-dehydro-NADA generating enzyme system. Trimeric NADA-polymerization products of the substituted benzodioxan-type have been obtained from in vivo sclerotized locust cuticle, confirming the ability of cuticle to produce NADA-oligomers. The results indicate that some insect cuticles contain enzymes promoting linkage of oxidized NADA to histidine residues. It is suggested that histidine residues in the cuticular proteins can serve as acceptors for oxidized NADA and that further addition of NADA-residues to the phenolic groups of bound NADA can occur, resulting in formation of protein-linked NADA-oligomers. The coupling reactions identified may be an important step in natural cuticular sclerotization.
This article describes recent achievements in the field of micellar polymers, or polysoaps. Taking advantage of zwitterionic model polymers, systematic variations of the molecular architecture have provided an improved understanding of the relationship between the molecular structure of the polymers and their key properties such as surface activity and solubilization capacity. Useful rules are established, which take into account much of the previous data in the literature.
Several zwitterionic polymers were prepared by radical homopolymerization of surfactant monomers which bear diallyl, diene or vinylcyclopropane moieties. These polymer systems were complemented by alternating copolymers of appropriate zwitterionic vinyl compounds. Thus, polymers with reduced (as compared with simple vinylic homopolymers, or statistical copolymers) and well defined density of surfactant side groups are obtained. The solubilities found for these polymers are dominated by polymer geometry rather than by the balance of hydrophilic and hydrophobic fragments, thus corroborating a main-chain spacer model proposed recently. All water-soluble polymers exhibit characteristic features of classical polysoaps, as shown by surface tension measurements and by solubilization of hydrophobic dyes. In contrast, the water-insoluble copolymers are capable to form stable monolayers at the air-water interface.
Solubilization by polysoaps
(1994)
The aqueous solubilization power of several series of micellar homopolymers and copolymers (polysoaps) is investigated. Using five insoluble or poorly water-soluble dyes, comparisons of the capacities are made with respect ot the influence of structural variables such as the polymer backbone, the polymer geometry, the comonomer content, and the charge of the hydrophilic group. Some guidelines for polysoap structures suited for efficient solubilization are established. Noteworthy is that the solubilization capacities of the polysoaps are neither linked to the ability to reduce the surface tension of water, nor to the polarity of the solubilization sites deduced from spectroscopic probes.
Reversible changes in the self-organization of polysoaps may be induced by controlling their charge numbers via covalently bound redox moieties. This is illustrated with two viologen polysoaps, which in response to an electrochemical stimulus, change their solubility and aggregation in water, leading from homogeneously dissolved and aggregated molecules to collapsed ones and vice verse. Using the electrochemical quartz crystal microbalance (EQCM), it could be shown that the reversibility of this process is better than 95% in 16 cycles.