Marco M. R. M. Hendrix

Temperature-Triggered Collection and Release of Water from Fogs by a Sponge-Like Cotton Fabric

A sponge-like cotton fabric autonomously collects and releases water from fogs triggered by typical day-and-night temperature variations. The reversible switching between absorbing-superhydrophilic/releasing-superhydrophobic states results from structural changes of a temperature-responsive polymer grafted on the very rough fabric-surface. This material and concept presents a breakthrough into simple and versatile solutions for collection, uni-directional flow, and purification of water captured from the atmosphere.

High-Magnesian Calcite Mesocrystals: A Coordination Chemistry Approach

While biogenic calcites frequently contain appreciable levels of magnesium, the pathways leading to such high concentrations remain unclear. The production of high-magnesian calcites in vitro is highly challenging, because Mg-free aragonite, rather than calcite, is the favored product in the presence of strongly hydrated Mg(2+) ions. While nature may overcome this problem by forming a Mg-rich amorphous precursor, which directly transforms to calcite without dissolution, high Mg(2+)/Ca(2+) ratios are required synthetically to precipitate high-magnesian calcite from solution. Indeed, it is difficult to synthesize amorphous calcium carbonate (ACC) containing high levels of Mg, and the Mg is typically not preserved in the calcite product as the transformation occurs via a dissolution-reprecipitation route. We here present a novel synthetic method, which employs a strategy based on biogenic systems, to generate high-magnesian calcite. Mg-containing ACC is produced in a nonaqueous environment by reacting a mixture of Ca and Mg coordination complexes with CO(2). Control over the Mg incorporation is simply obtained by the ratio of the starting materials. Subsequent crystallization at reduced water activities in an organic solvent/water mixture precludes dissolution and reprecipitation and yields high-magnesian calcite mesocrystals with Mg contents as high as 53 mol %. This is in direct contrast with the polycrystalline materials generally observed when magnesian calcite is formed synthetically. Our findings give insight into the possible mechanisms of formation of biogenic high-magnesian calcites and indicate that precise control over the water activity may be a key element.

Thermal expansion of cubic Si3N4 with the spinel structure

The thermal expansion coefficient of cubic Si3N4 with the spinel structure was determined with high temperature X-ray diffraction. The experimental value agrees well with the lattice parameter predicted by first principles methods, and is significantly larger than the value for β-Si3N4. This difference is discussed in terms of the chemical bonding in these two modifications of Si3N4.

Significance of the Amide Functionality on DOPA-Based Monolayers on Gold

The adhesive proteins secreted by marine mussels contain an unusual amino acid, 3,4-dihydroxyphenylalanine (DOPA), that is responsible for the cohesive and adhesive strength of this natural glue and gives mussels the ability to attach themselves to rocks, metals, and plastics. Here we report a detailed structural and spectroscopic investigation of the interface between N-stearoyldopamine and a single-crystalline Au(111) model surface and an amide-absent molecule, 4-stearylcatechol, also on Au(111), with the aim of understanding the role of the amide functionality in the packing, orientation, and fundamental interaction between the substrate and the monolayer formed from an aqueous environment by the Langmuir-Blodgett technique. The organization of monolayers on gold was observed directly and studied in detail by X-ray photoelectron spectroscopy (XPS), contact angle measurements (CA), surface-enhanced Raman spectroscopy (SERS), infrared reflection-absorption spectroscopy (IRRAS), and atomic force microscopy (AFM). Our study shows that within the monolayer the catecholic oxygen atoms are coordinated to the gold surface, having a more perpendicular orientation with respect to the aromatic ring and the apparently tilted alkyl chains, whereas the amide functionality stabilizes the monolayer that is formed.

Visualizing order in dispersions and solid state morphology with CryoTEM and electron tomography: P3HT:PCBM organic solar cells

Building blocks for organic solar cells are made from P3HT in a P3HT:PCBM solution in toluene and used to tune the morphology of the photoactive layer. The approach presented here decouples the structure and morphology formation, providing precise control over both the structures in solution and the morphology of the photoactive layer. For the characterization of the nanostructures in the organic casting solutions, cryo-TEM was successfully employed, and reveals the P3HT crystals and even the 1.7 nm lamellar stacking, which in combination with cryogenic low dose electron diffraction clearly proves the high crystallinity of P3HT aggregates realized. The photoactive layers made from pre-crystallized solutions show a morphology that is closely related to the structures in solution. A clear trend of decreasing open circuit voltage and increasing short circuit current with increasing order in the casting solutions and the devices was observed, which correlates with the evolution of the morphology from very intermixed with small fibrillar structures to phase-separated with large polymer crystals, as evaluated from representative devices, characterized in 3D with electron tomography.

Sustainable coatings from bio-based, enzymatically synthesized polyesters with enhanced functionalities

Bio-based sorbitol-containing polyester polyols were synthesized via enzymatic polycondensation. The selectivity of the biocatalyst for primary vs. secondary hydroxyl groups allowed for the preparation of close to linear renewable polyester polyols with enhanced hydroxyl functionalities, both as pendant groups and end-groups. In some cases, the sorbitol units were homogeneously distributed in the polyester polyol chains, whereas changes in the comonomers used and experimental conditions led to inhomogeneous and unique distributions of sorbitol, implying that some polyester polyol chains contained none and others contained multiple sorbitol units. Solvent-borne coatings were prepared by cross-linking the functional polyester polyols with polyisocyanate curing agents. An increased functionality of the polyester polyols led to an enhancement of the properties of the resulting cured coatings. Furthermore, when sorbitol units were non-homogeneously distributed, a significant improvement in the chemical resistance and mechanical properties of the cured poly(ester urethane) network was noted. By employing the bio-based diisocyanate EELDI (ethyl ester L-lysine diisocyanate) as a curing agent, almost fully renewable coatings with satisfactory mechanical properties were obtained.

Squaramide-Based Supramolecular Materials for Three-Dimensional Cell Culture of Human Induced Pluripotent Stem Cells and Their Derivatives

Synthetic hydrogel materials can recapitulate the natural cell microenvironment; however, it is equally necessary that the gels maintain cell viability and phenotype while permitting reisolation without stress, especially for use in the stem cell field. Here, we describe a family of synthetically accessible, squaramide-based tripodal supramolecular monomers consisting of a flexible tris(2-aminoethyl)amine (TREN) core that self-assemble into supramolecular polymers and eventually into self-recovering hydrogels. Spectroscopic measurements revealed that monomer aggregation is mainly driven by a combination of hydrogen bonding and hydrophobicity. The self-recovering hydrogels were used to encapsulate NIH 3T3 fibroblasts as well as human-induced pluripotent stem cells (hiPSCs) and their derivatives in 3D. The materials reported here proved cytocompatible for these cell types with maintenance of hiPSCs in their undifferentiated state essential for their subsequent expansion or differentiation into a given cell type and potential for facile release by dilution due to their supramolecular nature.