An iron(II) pyridyl-benzohydrazonate-based complex decorated with long alkyl chains is reported as a rare spin-crossover compound displaying a wide thermal hysteresis spanning room temperature. On heating, this compound exhibits a spin transition between a LS ground state and an ordered HS-LS phase with symmetry breaking from monoclinic P2/n into orthorhombic P222 space groups. During cooling, the compound first transits into a magnetically distinguishable HS-LS phase with monoclinic P2 symmetry before returning into the LS phase. Interconversion between the two distinct HS-LS phases is the result of subtle structural changes in the alkyl chains and produces a second minor thermal hysteresis that superposes to the large one. This unprecedented result shows that the combination of a conventional cooperative spin transition and ligand-driven magnetic changes can promote magnetic tristability at room temperature.

REF (Hevb1) and SRPP (Hevb3) are two major components of Hevea brasiliensis latex, well known for their allergenic properties. They are obviously taking part in the biosynthesis of natural rubber, but their exact function is still unclear. They could be involved in defense/stress mechanisms after tapping or directly acting on the isoprenoid biosynthetic pathway. The structure of these two proteins is still not described. In this work, it was discovered that REF has amyloid properties, contrary to SRPP. We investigated their structure by CD, TEM, ATR-FTIR and WAXS and neatly showed the presence of β-sheet organized aggregates for REF, whereas SRPP mainly fold as a helical protein. Both proteins are highly hydrophobic but differ in their interaction with lipid monolayers used to mimic the monomembrane surrounding the rubber particles. Ellipsometry experiments showed that REF seems to penetrate deeply into the monolayer and SRPP only binds to the lipid surface. These results could therefore clarify the role of these two paralogous proteins in latex production, either in the coagulation of natural rubber or in stress-related responses. To our knowledge, this is the first report of an amyloid formed from a plant protein. This suggests also the presence of functional amyloid in the plant kingdom.

Lignin is considered as a promising bio-sourced precursor for more sustainable and low-cost carbon fibers (CFs). However, lignin-based CFs generally have a poor graphitic structure, compared to polyacrylonitrile CFs. In this paper, we present an original approach that uses graphene oxide liquid crystal (GOLC) as a templating agent to promote the formation of graphitic structure in the fibers at low carbonization temperature. Both lignin and hybrid lignin/GOLC CFs were carbonized/graphitized up to 2700 °C. Structural analyses by X-ray diffraction, Raman spectroscopy and electrical measurements manifest a significant improvement in graphitic structure and a preferred orientation of graphene planes for lignin/GOLC fibers. These effects are the result of axial propagation of the templated graphitic order nucleated by the large GO flakes. The current approach reveals the possibility of preparing low-cost lignin-based CFs with improved graphitic structure and high electrical conductivity at low temperature for electrochemical or smart textile applications.

Although the double Friedel-Crafts acylation of arenes with ethyl chloroglyoxylate is hindered by the strongly deactivating effect of the first-entering glyoxylic substituent, the double reaction is successful with the reactive arene perylene under long reaction times and with concomitant ester hydrolysis. The reaction is regiospecific, giving the 3,9-regioisomer exclusively. This perylenylenediglyoxylic acid is condensed first with o-bromophenylacetic acid and then with α-branched alkylamines to yield the title compounds. Whilst the corresponding tetraalkyl esters only show monotropic mesophases, these diimides show enantiotropic columnar mesophases that can be maintained at room temperature if racemically branched alkyl chains of moderate size are used. A palladium-induced C-C bond migration during the build-up of the arene system leads to an isomeric side product of reduced symmetry that can be isolated by aggregation-controlled chromatographic separation. The HOMO and LUMO energies of the title compounds are considerably higher than those of established perylenetetracarboxdiimides.

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Graphitic structures, unlike polymers and metals, cannot be directly printed in 3D. We demonstrate here that graphitic structures can be shaped in 3D by using direct-ink writing (DIW) of lignin-graphene oxide solutions that are then dried and carbonized. Lignin is a promising precursor for the elaboration of bio-based carbon materials because of its low cost, natural availability and high carbon content. The rheology of the inks is controlled by the presence of graphene oxide (GO) in order to make the solutions viscoelastic and printable. The GO flakes are found to align during ink extrusion. This behavior is understood by considering the applied extrusion shear stress and the yield stress of the inks. By adjusting the relative fraction of GO and lignin, it is possible to change the density, the graphitic order, and thus the electrical and mechanical properties of the printed materials. In particular, GO promotes not only graphitic order but also porosity. By contrast, high amounts of lignin allow preparing denser but less ordered carbon structures. The possibility to vary density and properties offers an opportunity for the development of graphitic 3D materials with tunable properties.

Dibenzo[a,j]coronene-tetracarboxylic alkyl esters and imides with either a centrosymmetric bis-peri substitution pattern or a polar bis-ortho substitution pattern form hexagonal columnar mesophases, which in the case of the imides persist at room temperature. The bis-peri isomers are obtained via a two-fold oxidative photocyclization; the bis-ortho isomers are accessed via a glyoxylic Perkin reaction of triphenylene and naphthalene building blocks. Steric congestion between the substituents and the adjacent benzo protrusion in the bis-ortho esters and imides leads to bending of the aromatic plane, which thus avoids twisting. These isomers surprisingly show a more pronounced liquid crystalline behaviour than their non-bent bis-peri homologs, accommodating non-planarity with columnar order by slipped stacking. Whereas both types of ester and the bis-peri imide show an optical behaviour typical for perylene chromophores, the strongly bent bis-ortho imide distinguishes itself notably from them by its absorption spectrum. The electron acceptor strength of the isomeric diimides is found to differ, the hexagonal (peri) diimide having a 0.20 eV lower LUMO energy than the pentagonal (ortho) isomer.