Role of Surface Chemistry in the Superhydrophobicity of the Springtail Orchesella cincta (Insecta:Collembola)

Collembola are ancient arthropods living in soil with extensive exposure to dirt, bacteria, and fungi. To protect from the harsh environmental conditions and to retain a layer of air for breathing when submerged in water, they have evolved a superhydrophobic, liquid-repelling cuticle surface. The nonfouling and self-cleaning properties of springtail cuticle make it an interesting target of biomimetic materials design. Recent research has mainly focused on the intricate microstructures at the cuticle surface. Here we study the role of the cuticle chemistry for the Collembola species Orchesella cincta (Collembola, Entomobryidae). O. cincta uses a relatively simple cuticle structure with prima…

Engineering von Proteinen an Oberflächen: Von komplementärer Charakterisierung zu Materialoberflächen mit maßgeschneiderten Funktionen

IM30 triggers membrane fusion in cyanobacteria and chloroplasts

The thylakoid membrane of chloroplasts and cyanobacteria is a unique internal membrane system harbouring the complexes of the photosynthetic electron transfer chain. Despite their apparent importance, little is known about the biogenesis and maintenance of thylakoid membranes. Although membrane fusion events are essential for the formation of thylakoid membranes, proteins involved in membrane fusion have yet to be identified in photosynthetic cells or organelles. Here we show that IM30, a conserved chloroplast and cyanobacterial protein of approximately 30 kDa binds as an oligomeric ring in a well-defined geometry specifically to membranes containing anionic lipids. Triggered by Mg2+, membr…

Solvothermal Synthesis of Molybdenum–Tungsten Oxides and Their Application for Photoelectrochemical Water Splitting

Molybdenum and tungsten oxides are of interest as semiconductors for the production of clean and sustainable energy. Here we show that synergistic effects arising from a combination of noncrystalli...

Kinetically Controlled Sequential Growth of Surface-Grafted Chiral Supramolecular Copolymers.

We report a facile strategy to grow supramolecular copolymers on Au surfaces by successively exposing a surface-anchored monomer to solutions of oppositely charged peptide comonomers. Charge regulation on the active chain end of the polymer sufficiently slows down the kinetics of the self-assembly process to produce kinetically trapped copolymers at near-neutral pH. We thereby achieve architectural control at three levels: The β-sheet sequences direct the polymerization away from the surface, the height of the supramolecular copolymer brushes is well-controlled by the stepwise nature of the alternating copolymer growth, and 2D spatial resolution is realized by using micropatterned initiatin…

Engineering Proteins at Interfaces: From Complementary Characterization to Material Surfaces with Designed Functions

Abstract Once materials come into contact with a biological fluid containing proteins, proteins are generally—whether desired or not—attracted by the material's surface and adsorb onto it. The aim of this Review is to give an overview of the most commonly used characterization methods employed to gain a better understanding of the adsorption processes on either planar or curved surfaces. We continue to illustrate the benefit of combining different methods to different surface geometries of the material. The thus obtained insight ideally paves the way for engineering functional materials that interact with proteins in a predetermined manner.

Thermal stability and enhanced thermoelectric properties of the tetragonal tungsten bronzes Nb8-xW9+xO47 (0 <x <5)

Thermoelectric materials are believed to play a fundamental role in the energy field over the next years thanks to their ability of directly converting heat into usable electric energy. To increase their integration in the commercial markets, improvements of the efficiencies are needed. At the same time, cheap and non-toxic materials are required along with easily upscalable production cycles. Compounds of the tetragonal tungsten bronze (TTB) series Nb8-xW9+xO47 fulfill all these requirements and are promising materials. Their adaptive structure ensures glass-like values of the thermal conductivity, and the substitution on the cation side allows a controlled manipulation of the electronic p…

Assembly of iron oxide nanosheets at the air-water interface by leucine-histidine peptides

The fabrication of inorganic nanomaterials is important for a wide range of disciplines. While many purely inorganic synthetic routes have enabled a manifold of nanostructures under well-controlled conditions, organisms have the ability to synthesize structures under ambient conditions. For example, magnetotactic bacteria, can synthesize tiny ‘compass needles’ of magnetite (Fe3O4). Here, we demonstrate the bio-inspired synthesis of extended, self-supporting, nanometer-thin sheets of iron oxide at the water–air interface through self-assembly using small histidine-rich peptides.

Nitrated Fatty Acids Modulate the Physical Properties of Model Membranes and the Structure of Transmembrane Proteins

Nitrated fatty acids (NO2 -FAs) act as anti-inflammatory signal mediators, albeit the molecular mechanisms behind NO2 -FAs' influence on diverse metabolic and signaling pathways in inflamed tissues are essentially elusive. Here, we combine fluorescence measurements with surface-specific sum frequency generation vibrational spectroscopy and coarse-grained computer simulations to demonstrate that NO2 -FAs alter lipid organization by accumulation at the membrane-water interface. As the function of membrane proteins strongly depends on both, protein structure as well as membrane properties, we consecutively follow the structural dynamics of an integral membrane protein in presence of NO2 -FAs. …

The surface chemistry of iron oxide nanocrystals: surface reduction of γ-Fe2O3 to Fe3O4 by redox-active catechol surface ligands

The effect of surface functionalization on the structural and magnetic properties of catechol-functionalized iron oxide magnetic (γ-Fe2O3) nanocrystals was investigated. γ-Fe2O3 nanocrystals (NCs) were synthesized from iron acetyl acetonate in phenyl ether with 1,2-tetradecanediol, oleic acid, and oleylamine. X-ray powder diffraction in combination with Mossbauer spectroscopy revealed the presence of γ-Fe2O3 (maghemite) particles only. Replacement of oleic acid (OA) with catechol-type 3,4-dihydroxyhydrocinnamic acid (DHCA) or polydentate polydopamine acrylate (PDAm) surface ligands leads to a pronounced change of the magnetic behavior of the γ-Fe2O3 nanocrystals and separated them into two …

Membrane Structure of Aquaporin Observed with Combined Experimental and Theoretical Sum Frequency Generation Spectroscopy

High-resolution structural information on membrane proteins is essential for understanding cell biology and for the structure-based design of new medical drugs and drug delivery strategies. X-ray diffraction (XRD) can provide angstrom-level information about the structure of membrane proteins, yet for XRD experiments, proteins are removed from their native membrane environment, chemically stabilized, and crystallized, all of which can compromise the conformation. Here, we describe how a combination of surface-sensitive vibrational spectroscopy and molecular dynamics simulations can account for the native membrane environment. We observe the structure of a glycerol facilitator channel (GlpF)…

Inside Back Cover: Kinetically Controlled Sequential Growth of Surface-Grafted Chiral Supramolecular Copolymers (Angew. Chem. Int. Ed. 25/2016)

The role of intact oleosin for stabilization and function of oleosomes.

Lipid storage in plants is achieved among all plant species by formation of oleosomes, enclosing oil (triacylglycerides) in small subcellular droplets. Seeds are rich in this pre-emulsified oil to provide a sufficient energy reservoir for growing. The triacylglyceride core of the oleosomes is surrounded by a phospholipid monolayer containing densely packed proteins called oleosins. They are anchored in the triacylglycerides core with a hydrophobic domain, while the hydrophilic termini remain on the surface. These specialized proteins are expressed during seed development and maturation. Particularly, they play a major role in the stabilization and function of oleosomes. To better understand…

Peptide-Controlled Assembly of Macroscopic Calcium Oxalate Nanosheets

The fabrication of two-dimensional (2D) biomineral nanosheets is of high interest owing to their promise for applications in electronics, filtration, catalysis, and chemical sensing. Using a facile approach inspired by biomineralization in nature, we fabricate laterally macroscopic calcium oxalate nanosheets using β-folded peptides. The template peptides are composed of repetitive glutamic acid and leucine amino acids, self-organized at the air-water interface. Surface-specific sum frequency generation spectroscopy and molecular dynamics simulations reveal that the formation of oxalate nanosheets relies on the peptide-Ca 2+ ion interaction at the interface, which not only restructures the …

Innenrücktitelbild: Kinetisch kontrolliertes, sequenzielles Wachstum von chiralen supramolekularen Copolymeren auf Oberflächen (Angew. Chem. 25/2016)

Kinetisch kontrolliertes, sequenzielles Wachstum von chiralen supramolekularen Copolymeren auf Oberflächen

Wir berichten uber eine einfache Strategie zur Herstellung supramolekularer Copolymere an Goldoberflachen durch sukzessive Inkubation einer initiatorbeschichteten Oberflache mit Losungen aus gegensatzlich geladenen peptidischen Comonomeren. Ein ladungsreguliertes Wachstum des Polymers verlangsamt die Kinetik der Selbstorganisation in dem Mase, dass kinetisch gehemmte Copolymere im nahezu neutralen pH-Bereich gebildet werden. Auf diese Weise erreichen wir eine Kontrolle der Polymerarchitektur auf drei Ebenen: Die β-faltblattkodierte Peptidsequenz steuert eine Wachstumsrichtung der Polymere senkrecht zur Oberflache, die Hohe der supramolekularen Copolymerbursten wird durch den schrittweisen A…