Drying of Hierarchically Organized Porous Silica Monoliths-Comparison of Evaporative and Supercritical Drying.

In this study, we present a detailed comparison between a conventional supercritical drying process and an evaporative drying technique for hierarchically organized porous silica gel monoliths. These gels are based on a model system synthesized by the aqueous sol-gel processing of an ethylene-glycol-modified silane, resulting in a cellular, macroporous, strut-based network comprising anisotropic, periodically arranged mesopores formed by microporous amorphous silica. The effect of the two drying procedures on the pore properties (specific surface area, pore volume, and pore widths) and on the shrinkage of the monolith is evaluated through a comprehensive characterization by using nitrogen physisorption, electron microscopy, and small-angle X-ray scattering. It can clearly be demonstrated that for the hierarchically organized porous solids, the evaporative drying procedure can compete without the need for surface modification with the commonly applied supercritical drying in terms of the material and textural properties, such as specific surface area and pore volume. The thus obtained materials deliver a high specific surface area and exhibit overall comparable or even improved pore characteristics to monoliths prepared by supercritical drying. Additionally, the pore properties can be tailored to some extent by adjusting the drying conditions, such as temperature.

Polyvinylidene Fluoride Aerogels with Tailorable Crystalline Phase Composition.

In this work, polyvinylidene fluoride (PVDF) aerogels with a tailorable phase composition were prepared by following the crystallization-induced gelation principle. A series of PVDF wet gels (5 to 12 wt.%) were prepared from either PVDF−DMF solutions or a mixture of DMF and ethanol as non-solvent. The effects of the non-solvent concentration on the crystalline composition of the PVDF aerogels were thoroughly investigated. It was found that the nucleating role of ethanol can be adjusted to produce low-density PVDF aerogels, whereas the changes in composition by the addition of small amounts of water to the solution promote the stabilization of the valuable ß and γ phases. These phases of the aerogels were monitored by FTIR and Raman spectroscopies. Furthermore, the crystallization process was followed by in-time and in situ ATR−FTIR spectroscopy. The obtained aerogels displayed specific surface areas > 150 m2 g−1, with variable particle morphologies that are dependent on the non-solvent composition, as observed by using SEM and Synchrotron Radiation Computed micro-Tomography (SR-µCT).

Tannin-Based Nanoscale Carbon Spherogels as Electrodes for Electrochemical Applications.

A promising route to monolithic, hollow sphere carbon assemblies based on sustainable precursors with a tailored nanostructure is presented. These carbon assemblies, recently termed carbon spherogels, are generated via a polystyrene sphere template-based sol-gel process of mimosa tannin and biomass-derived 5-(hydroxymethyl)furfural. By completely replacing petroleum-based precursors (especially toxic formaldehyde) highly porous, nanoscale carbon monoliths are obtained, which are investigated as state-of-the-art, sustainable electrode materials for energy storage. This study defines the required synthesis parameters, in particular the highly acidic initial pH and a tannin/water ratio of at least 0.05 or lower, for a successful and homogeneous generation of these biobased carbon spherogels.

Gene regulatory effects of a large chromosomal inversion in highland maize.

Chromosomal inversions play an important role in local adaptation. Inversions can capture multiple locally adaptive functional variants in a linked block by repressing recombination. However, this recombination suppression makes it difficult to identify the genetic mechanisms underlying an inversion's role in adaptation. In this study, we used large-scale transcriptomic data to dissect the functional importance of a 13 Mb inversion locus (Inv4m) found almost exclusively in highland populations of maize (Zea mays ssp. mays). Inv4m was introgressed into highland maize from the wild relative Zea mays ssp. mexicana, also present in the highlands of Mexico, and is thought to be important for the adaptation of these populations to cultivation in highland environments. However, the specific genetic variants and traits that underlie this adaptation are not known. We created two families segregating for the standard and inverted haplotypes of Inv4m in a common genetic background and measured gene expression effects associated with the inversion across 9 tissues in two experimental conditions. With these data, we quantified both the global transcriptomic effects of the highland Inv4m haplotype, and the local cis-regulatory variation present within the locus. We found diverse physiological effects of Inv4m across the 9 tissues, including a strong effect on the expression of genes involved in photosynthesis and chloroplast physiology. Although we could not confidently identify the causal alleles within Inv4m, this research accelerates progress towards understanding this inversion and will guide future research on these important genomic features.

Tannin-Based Hybrid Materials and Their Applications: A Review.

Tannins are eco-friendly, bio-sourced, natural, and highly reactive polyphenols. In the past decades, the understanding of their versatile properties has grown substantially alongside a continuously broadening of the tannins' application scope. In particular, recently, tannins have been increasingly investigated for their interaction with other species in order to obtain tannin-based hybrid systems that feature advanced and/or novel properties. Furthermore, in virtue of the tannins' chemistry and their high reactivity, they either physicochemically or physically interact with a wide variety of different compounds, including metals and ceramics, as well as a number of organic species. Such hybrid or hybrid-like systems allow the preparation of various advanced nanomaterials, featuring improved performances compared to the current ones. Consequently, these diverse-shaped materials have potential use in wastewater treatment or catalysis, as well as in some novel fields such as UV-shielding, functional food packaging, and biomedicine. Since these kinds of tannin-based hybrids represent an emerging field, thus far no comprehensive overview concerning their potential as functional chemical building blocks is available. Hence, this review aims to provide a structured summary of the current state of research regarding tannin-based hybrids, detailed findings on the chemical mechanisms as well as their fields of application.

Rare-Earth Zirconate Ln2Zr2O7 (Ln: La, Nd, Gd, and Dy) Powders, Xerogels, and Aerogels: Preparation, Structure, and Properties.

The physicochemical properties of rare-earth zirconates can be tuned by the rational modification of their structures and phase compositions. In the present work, La3+-, Nd3+-, Gd3+-, and Dy3+-zirconate nanostructured materials were prepared by different synthetic protocols, leading to powders, xerogels, and, for the first time, monolithic aerogels. Powders were synthesized by the co-precipitation method, while xerogels and aerogels were synthesized by the sol-gel technique, followed by ambient and supercritical drying, respectively. Their microstructures, thermogravimetric profiles, textural properties, and crystallographic structures are reported. The co-precipitation method led to dense powders (SBET < 1 m2 g-1), while the sol-gel technique resulted in large surface area xerogels (SBET = 144 m2 g-1) and aerogels (SBET = 168 m2 g-1). In addition, the incorporation of lanthanide ions into the zirconia lattice altered the crystal structures of the powders, xerogels, and aerogels. Single-phase pyrochlores were obtained for La2Zr2O7 and Nd2Zr2O7 powders and xerogels, while defect fluorite structures formed in the case of Gd2Zr2O7 and Dy2Zr2O7. All aerogels contain a mixture of cubic and tetragonal ZrO2 phases. Thus, a direct effect is shown between the drying conditions and the resulting crystalline phases of the nanostructured rare-earth zirconates.