A series of new charge transfer (CT) chromophores of \"α-diimine-MII-catecholate\" type (where M is 3d-row transition metals-Cu, Ni, Co) were derived from 4,4\'-di-tert-butyl-2,2\'-bipyridyl and 3,6-di-tert-butyl-o-benzoquinone (3,6-DTBQ) in accordance with three modified synthetic approaches, which provide high yields of products. A square-planar molecular structure is inherent for monomeric [CuII(3,6-Cat)(bipytBu)]∙THF (1) and NiII(3,6-Cat)(bipytBu) (2) chromophores, while dimeric complex [CoII(3,6-Cat)(bipytBu)]2∙toluene (3) units two substantially distorted heteroleptic D-MII-A (where D, M, A are donor, metal and acceptor, respectively) parts through a donation of oxygen atoms from catecholate dianions. Chromophores 1-3 undergo an effective photoinduced intramolecular charge transfer (λ = 500-715 nm, extinction coefficient up to 104 M-1·cm-1) with a concomitant generation of a less polar excited species, the energy of which is a finely sensitive towards solvent polarity, ensuring a pronounced negative solvatochromic effect. Special attention was paid to energetic characteristics for CT and interacting HOMO/LUMO orbitals that were explored by a synergy of UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT study. The current work sheds light on the dependence of CT peculiarities on the nature of metal centers from various groups of the periodic law. Moreover, the \"α-diimine-MII-catecholate\" CT chromophores on the base of \"late\" transition elements with differences in d-level\'s electronic structure were compared for the first time.

OBJECTIVE: Transition-metal coordination complexes are hopeful to make advanced structural materials, since the metal-coordination bonds, unlike typical covalent bonds, can regenerate after rupture, allowing for dynamic, tunable, and reversible mechanical characteristics. Integration of metal-coordinate crosslinking in foam material has rarely been reported.
METHODS: We developed the hydrolyzed rice proteins (HRP) as the building block for amphiphilic transition-metal coordination complexes that could be used to make long-lived foams with high yield stress. Surface properties of the foaming solution were determined using equilibrium and dynamic tensiometers. Structural information of aggregates in the foaming solution was detected by small-angle X-ray scattering (SAXS) and Cryo-Tem. Visualization of liquid flow in the interfacial liquid film was studied by the reflective optical interference technique. Rheological response of liquid foam was characterized by a rheometer with amplitude-sweep and frequency-sweep modes.
RESULTS: In the presence of transition metal ions, HRP formed a mechanically strong rigid film. In the absence of transition metal ions or the addition of alkyl polyglycoside (APG), HRP was desorbed to produce a mobile film with a detergent state. The two interfacial states could be actively switched based on facile changes in bulk solution composition (metal ions or alkyl glycoside or chelating agent), and the switching between the two states led to the formation of extremely stable foam with high yield stress or the collapse of foam with a significant decrease in yield limit. The transition-metal coordination complexes adsorbed on the surface of the liquid film could increase the elastic modulus of liquid foam by more than an order of magnitude without increasing the viscosity of the foaming solution. We further revealed the origin of foam stability/instability and used other well-characterized proteins to prepare transition-metal coordination complexes to make long-lived foams. The cases described in this work illustrate the universal nature of the strategy, which in principle can be extended to many types of protein.

Immobilized metal ion affinity chromatography (IMAC) is useful in purification of histidine-tagged or histidine-rich proteins and peptides from a variety of hosts. However, phenolic compounds including polyphenols interfere with IMAC due to their high affinities for the transition metals immobilized on the column resins, which hampers the purification of proteins from plant-based host systems. In contrast to extensive knowledge of the mechanism of the interactions between phenolic compounds and transition metal ions in solution, an understanding of the interactions on the columns, where transition metal ions are immobilized on the resins, remains elusive. This study systematically investigated the affinity of phenolic compounds for transition metal ions by varying the number and position of phenolic hydroxyl groups (OH groups) and using different transition metals-Fe(II), Cu(II) and Ni(II)-on various IMACs, in which the columns were fabricated by equilibrating the cation-exchange column with transition metal solutions. It was found that the more OH groups the aromatic compounds have, the higher the affinity for transition metal ions; in particular, methyl gallate and pyrogallol were permanently bound to the IMAC column, which reflected coordinate bond formation with the transition metal ions. Importantly, the phenolic compounds showed no obvious affinity for the Ni(II)-IMAC column, in contrast to the Fe(II)- and Cu(II)-IMAC columns, whereas imidazole and histidine-tagged proteins showed evident binding to the Ni(II)-IMAC column. Ni(II)-IMAC should thus be especially effective in isolating histidine-tagged and histidine-rich species from phenolic compound-containing systems. These results indicate that the affinity between phenolic compounds and transition metal ions on the column is consistent with the results in solution. They also provide a comprehensive view for devising strategies to improve IMAC purification of target proteins and peptides from samples containing phenolic compounds.