Bio-Based Cationic Surfactants from 5-(Hydroxymethyl)furfural for Antimicrobial Applications: The Role of Cationic Substitutes, Alkyl Chains, and Ester Linkages Marina M. Seitkalieva, Anna V. Vavina, Elena N. Strukova, Aida I. Samigullina, Maxim R. Sokolov, et al. Chemsuschem, 2025 A novel series of bio‐based cationic surfactants, synthesized from the platform chemical 5‐(hydroxymethyl)furfural (5‐HMF), fatty acids, and bio‐based amines, has been developed, offering a sustainable alternative to conventional surfactants. These compounds, referred to as surface‐active ionic liquids (SAILs), have critical micelle concentration (CMC) values lower compared to conventional quaternary ammonium cationic surfactants, indicating enhanced surface activity. The surface properties of the SAILs are predominantly influenced by the type of substitution in the cationic head group, with morpholinium‐based surfactants having significantly lower CMC values than diethyl ammonium ones. The length of the alkyl chain also plays a significant role in determining the physicochemical and biological characteristics of these surfactants, which vary depending on the chain length. Surfactants with longer alkyl substituents demonstrate enhanced thermal stability and surface activity. The newly synthesized amphiphiles exhibit antimicrobial activity comparable to known quaternary ammonium cationic agents but with lower cytotoxicity. Importantly, these surfactants show controlled degradation under temperature‐driven hydrolysis and basic conditions while maintaining stability in acidic environments. These findings highlight the potential of developed bio‐based surfactants to deliver high performance with reduced environmental impact, positioning them as potential candidates for antimicrobial applications and industrial uses focusing on sustainability goal.
Electric field-induced amplification of graphene oxide's visible light photocatalytic activity Alsu G. Nugmanova, Maxim R. Sokolov, Alexey E. Alexandrov, Maria A. Kniazeva, Ivan Yu. Eremchev, et al. Journal of Materials Chemistry A, 2024 An electric field accelerates a visible light photocatalysis with dye-sensitized graphene oxide in water. The effect provides the basis for new efficient photocatalytic technologies using contactless electric cells.
Noncovalent Self-Assembly of Single-Layer MoS2 Nanosheets and Zinc Porphyrin into Stable SURMOF Nanohybrids with Multimodal Photocatalytic Properties Maxim R. Sokolov, Konstantin A. Tumbinskiy, Ekaterina A. Varlamova, Alexey A. Averin, Andrey V. Shkolin, et al. ACS Applied Materials and Interfaces, 2023 A noncovalent integration of nanosheets of molybdenum disulfide (MoS 2 ) and the zinc porphyrin complex Zn(II) 5,10,15,20-tetrakis(4-carboxyphenyl)porphine (ZnTCPP) through coordination bonding with metal clusters of zinc acetate (Zn[OAc] 2 ) was applied for synthesis of stable hybrid nanomaterial avoiding surface prefunctionalization. The X-ray powder diffraction in combination with the BET nitrogen adsorption method confirms formation of a ZnTCPP-based surface-attached metal–organic framework (SURMOF) with micropores of 1.63 nm on the MoS 2 nanosheets. Fluorescence spectroscopy confirmed Forster resonance energy transfer (FRET) between MoS 2 and ZnTCPP without contact quenching. Fluorescent trapping with terephthalic acid for hydroxyl radicals and Sensor Green for singlet oxygen was applied for studying the pathways of photodegradation of model organic pollutant 1,5-dihydroxynaphthalene (DHN) in the presence of SURMOF/MoS 2 . Visible light initiates sensitization through the excitation of ZnTCPP generating singlet oxygen, whereas UV-light promotes either aerobic FRET-mediated “Z scheme” or anaerobic “Type II heterojunction” mechanisms. Owing to its multimodal photochemistry, the SURMOF/MoS 2 hybrid showed comparatively high photocatalytic activity in UV-assisted degradation of DHN ( k eff UV = 4.0 × 10 –2 min –1 ) as well as the antibacterial activity confirmed by E. coli survival test under visible light. Noncovalent self-assembly utilizing coordination bonding in SURMOFs as supramolecular adhesive to avoid surface premodification provides a basis for new types of multicomponent nanosystems with switchable functionalities by combining different 2D materials and chromophores in one hybrid structure.
Ion-Mediated Self-Assembly of Graphene Oxide and Functionalized Perylene Diimides into Hybrid Materials with Photocatalytic Properties Maksim Sokolov, Alsu Nugmanova, Andrey Shkolin, Alexandra Zvyagina, Ivan Senchikhin, et al. Journal of Composites Science, 2023 A novel ion-mediated self-assembly method was applied for integration of graphene oxide (GO), propanoic- and glutaric-substituted perylenes (glu-PDI and PA-PDI), and Zn (OAc)2 into new hybrid materials with photocatalytic properties. The structuring of chromophores through coordination bonding on the GO surface is controlled by the chemistry of the PDI linkers. Four-substituted glu-PDI forms consolidated microporous particles, whereas di-substituted PA-PDI binds with GO into a macroporous gel-like structure. The GO/PDI controls without Zn2+ ions form only non-integrated dispersions. Both hybrids can initiate photodestruction of 1,5-dihydroxynaphtalene (DHN) due to the effective charge separation between the PDI components and GO by generating hydroxyl radicals determined by luminescent probing with terephthalic acid. The reduction mechanism of photodegradation was confirmed by MALDI-TOF spectroscopy. The structure of the hybrids controls the rate of photodegradation process. The glu-PDI-based photocatalyst shows a smaller rate of photoreduction of 3.3 × 10−2 min−1 than that with PA-PDA (4 × 10−2 min−1) due to diffusion limitations. Our results suggest that the ion-mediated synthesis is a useful and rational alternative for the conventional synthesis of GO-based functional hybrid materials through aromatic stacking between the graphene oxide and organic chromophores to produce new affordable and efficient photocatalysts.
One-Step Interfacial Integration of Graphene Oxide and Organic Chromophores into Multicomponent Nanohybrids with Photoelectric Properties Alexandra I. Zvyagina, Alexey E. Alexandrov, Alexey A. Averin, Ivan N. Senchikhin, Maxim R. Sokolov, et al. Langmuir, 2022 A one-step protocol for interfacial self-assembly of graphene oxide (GO), glutamine-substituted perylene diimide (PDI-glu), 10,12-pentacosadiynoic acid (PCDA), and zinc acetate into three- and four-component hybrid nanofilms through hydrogen and coordination bonding was developed. The hybrids deposited onto solid supports were studied after polymerization of PCDA by UV-vis absorption, fluorescence, and Raman spectroscopies, scanning electron microscopy (SEM), and atomic force microscopy (AFM). The results of spectroscopic studies suggest that the hybrids assembled through H-bonds can maintain the light-induced Förster energy transfer from the PDI-glu chromophore to the conjugated polymer and then to GO leading to fluorescence quenching. In the hybrids assembled through coordination bonding with zinc clusters, the energy transfer proceeds from PDI-glu to the PDA polymer, whereas the transfer from PDA to GO is quenched completely. Another important characteristic of these ultrathin hybrids is their stability with respect to photobleaching of chromophores due to the acceptor properties of GO. The as-assembled hybrid nanofilms were integrated with conventional photovoltaic planar architectures to study their photoelectric properties. The zinc-containing hybrids integrated with a hole transport layer exhibited photovoltaic properties. The cell with the integrated four-component hybrid comprising both PDI-glu and PDA showed a photocurrent/dark current ratio almost an order higher than that of the three-component hybrid assembled with PDA only. The supramolecular method based on the interfacial self-assembly can be extended to a wide variety of organic chromophores and polymerizable surfactants for integrating them into multicomponent functional GO-based nanohybrids with targeted properties for organic electronics.
A new 2-methylimidazole-assisted liquid-exfoliation method for a rapid scalable fabrication of chemically pure MoS2 nanosheets Maksim R. Sokolov, Konstantin A. Tumbinskiy, Alexandra I. Zvyagina, Ivan N. Senchikhin, Alexey A. Averin, et al. Colloids and Interface Science Communications, 2022 A new liquid exfoliation method of pristine MoS2 in a hot solution of 2-methylimidazole for a rapid fabrication of 1–2 nm-thick MoS2 nanoflakes is developed. The method makes it possible to produce large amounts of stable MoS2 hydrosols with concentrations 0.21–0.53 mg/ml within 2–4 h. Energy-dispersive X-ray spectroscopies and thermogravimetric analysis confirmed chemical purity of MoS2 after the removal of 2-methylimidazole with water. The as-formed MoS2 nanoflakes have a relatively narrow size distribution (50 ± 25 nm) and exhibit a strong aggregation-dependent luminescence at 420–475 nm. The thin films obtained from the MoS2 nanoflakes by spin-coating possess good semiconductor properties showing a non-ohmic linear current-voltage dependence and a surface resistivity up to 7.9 × 10–2 Ω·сm. The reported method may provide an affordable, experimentally simple and ecology-friendly alternative to commonly used techniques for fabricating MoS2 nanosheets with a potentially useful combination of size and properties for further applications in hybrid and composite materials.
Intercalation of Porphyrin-Based SURMOF in Layered Eu(III) Hydroxide: An Approach Toward Symbimetic Hybrid Materials Maksim R. Sokolov, Yulia Yu. Enakieva, Alexey D. Yapryntsev, Andrey A. Shiryaev, Alexandra I. Zvyagina, et al. Advanced Functional Materials, 2020 A strategy for rational design of synergetic hybrid materials exploiting stabilization of intercalated layered matrices via coordination bonding is described. A new hybrid material is assembled through subsequent intercalation of the surface‐anchored metal–organic framework (SURMOF) components, zinc acetate and 5,10,15,20‐tetrakis(4‐carboxyphenyl)‐porphyrin‐zinc(II) (ZnTCPP), into the layered europium(III) hydroxychloride (LEuH). The formation of the SURMOF clusters intercalated in LEuH is confirmed by X‐ray diffraction, FTIR and Raman spectroscopy, and BET nitrogen absorption methods. The catalytic function of the SURMOF/LEuH hybrid and its components in the model reaction of hydrolysis of bis(4‐nitrophenyl) phosphate in the acidic solution is studied by UV–vis and MALDI‐TOF spectroscopy. Both the non‐intercalated matrix and the MOF powder are inactive and unstable in the substrate solution. Unlike its components, the SURMOF/LEuH hybrid exhibits synergetic catalytic activity increasing with the amount of the intercalated compounds because of the mutual stabilization of the components through coordination interactions. The results provide a basis for symbimetic (mimicking the symbiotic behavior in biological systems) hybrid materials, in which stabilization of functional units in the intercalated structure translates into a synergy of useful properties.
