Search Results (87)

Visible-light photoredox catalysis using biacetyl (BA) as a low-cost photosensitizer enables the efficient formation of triarylethylenes (TAEs) via a Mizoroki–Heck-type coupling. The reaction proceeds efficiently in acetonitrile upon blue LED irradiation under anaerobic conditions. Alternatively, supramolecular viscoelastic gels have also been explored as reaction media, allowing the possibility of working under aerobic atmosphere. Mechanistic investigations by means of transient absorption spectroscopy and quenching experiments support a charge-separated intermediate pathway. Reaction quantum yield measurements further validate the efficiency of BA, demonstrating its potential as an alternative to transition-metal catalysts. Overall, this work presents a sustainable and scalable strategy for TAEs synthesis, integrating photoredox catalysis with soft material engineering. These findings pave the way for broader applications in green chemistry and functional materials. Full article

Seeking a supramolecular chiral system induced by trace chiral molecules instead of traditional complex and expensive chiral ligands to achieve high yield or ee value conversion of the products is of great significance in asymmetric synthesis but still remains a challenge. Herein, two types of double helical supramolecular chiral systems, (M)-Helix and (P)-Helix, with opposite chiral optics were constructed in situ using tyrosine-functionalized pillar[5]arene as inducers. These systems exhibit chiroptical stability and enable remarkable chirality amplification from 7 mol% chiral seeds. When applied to intermolecular olefin cyano-trifluoromethylation, (M)-Helix exhibits remarkable catalytic efficiency (yield up to 89%), whereas (P)-Helix achieves higher enantioselectivity (ee up to 84%). This research will provide new ideas for supramolecular chiral catalysts in organic asymmetric catalysis applications. Full article

Two new Cu(II) (CP1) and Co(II) (CP2) coordination polymers (CPs) with the triazole ligand 5-methyl-1-(pyridin-4-yl-methyl)-1H-1,2,3-triazole-4-carboxylate (L1) have been synthesized and structurally characterized by SCXRD (Single Crystal X-Ray Difraccion), PXRD (Power X-Ray Difracction), FT-IR (Fourier Transform Infrared), TG (Theermo Gravimetric), and electrochemical techniques. Both CPs were obtained at the water/n-butanol interface by reacting nitrate salts of each metal with the NaL1 ligand. SCXRD analysis revealed that CP1 (Coordination Polymer 1) and CP2 (Coordination Polymer 2) crystallize in the monoclinic space groups C2/c (No. 15) and P2₁/n (No. 14), respectively, forming 1D zigzag chain structures, which further lead to a 2D supramolecular network through O-H⋯O and C-H⋯O hydrogen bond interactions, respectively. In CP1, the supramolecular structure is assembled by hydrogen bonds involving water molecules. In contrast, CP2 forms its supramolecular network mainly through hydrogen bonds between adjacent triazole ligand molecules. Hirshfeld surface analysis revealed that the most significant contributions to the crystal packing come from H⋯O/O⋯H, H⋯H, H⋯N/N⋯H, and H⋯C/C⋯H interactions. In addition, FT-IR provided information on the functional groups involved in the coordination, while the decomposition patterns of both CPs were evaluated by TGA. Electrochemical studies conducted in a saline environment showed that CP1 exhibits superior hydrogen evolution reaction (HER) kinetics compared to CP2, as evidenced by a higher exchange current density and a lower Tafel slope. Density functional theory calculations and experimental bandgap measurements provided a deeper understanding of the electronic properties influencing the electrochemical behavior. The results highlight the potential of CP1 as an efficient catalyst for HER under saline conditions. Full article

A series of α-hydroxy-alkylphosphonates and α-hydroxy-alkylphosphine oxides were synthesized by the Pudovik reaction of acetaldehyde and acetone with dialkyl phosphites or diarylphosphine oxides. The additions were performed in three different ways: in liquid phase using triethylamine as the catalyst (1), on the surface of Al₂O₃/KF solid catalyst (2), or by a MW-assisted Na₂CO₃-catalyzed procedure (3). In most of the cases, our methods were more efficient and more robust than those applied in the literature. Two of the α-hydroxy-alkylphosphonates were subjected to single-crystal X-ray analysis, suggesting a dimeric and a chain supramolecular buildup in their respective crystals. Four α-hydroxy-alkylphosphonates and one α-hydroxy-ethylphosphine oxide were reacted with different acid chlorides to afford ten α-acyloxyphosphonates. Diethyl α-hydroxy-ethylphosphonate was transformed to the methanesulfonyloxy derivative that was useful in the Michaelis–Arbuzov reaction with triethyl phosphite and ethyl diphenylphosphinite to afford tetraethyl ethylidenebisphosphonate and diethyl α-(diphenylphosphinoyl)-ethylphosphonate, respectively. The α-hydroxyphosphonates and α-hydroxyphosphine oxides prepared were subjected to bioactivity studies, and the compounds tested exhibited limited cytotoxic effects on U266 cells with modest reductions in viability at a concentration of 100 μM. Full article

This study delves into the distinctive selective property exhibited by a non-conjugated cholesterol-based polymer, poly(CEM₁₁-b-EHA₇), in sorting semiconducting single-walled carbon nanotubes (s-SWCNTs) within isooctane. Comprised of 11 repeating units of cholesteryloxycarbonyl-2-hydroxy methacrylate (CEM) and 7 repeating units of 2-ethylhexyl acrylate (EHA), this non-conjugated polymer demonstrates robust supramolecular interactions across the sp² surface structure of carbon nanotubes and graphene. When coupled with the Double Liquid-Phase Extraction (DLPE) technology, the polymer effectively segregates s-SWCNTs into the isooctane phase (nonpolar) while excluding metallic SWCNTs (m-SWCNTs) in the water phase (polar). DLPE proves particularly efficient in partitioning larger-diameter s-SWCNTs (0.85–1.0 nm) compared to those dispersed directly in isooctane by poly(CEM₁₁-b-EHA₇) using direct liquid-phase exfoliation (LPE) techniques for diameters ranging from 0.75 to 0.95 nm. The DLPE method, bolstered by poly(CEM₁₁-b-EHA₇), successfully eliminates impurities from s-SWCNT extraction, including residual metallic catalysts and carbonaceous substances, which constitute up to 20% of raw HiPCO SWCNTs. DLPE emerges as a scalable and straightforward approach for selectively extracting s-SWCNTs in nonpolar, low-boiling-point solvents like alkanes. These dispersions hold promise for fabricating fast-drying s-SWCNT inks, which are ideal for printed and flexible thin-film transistors. Full article

As a key means to solve energy and environmental problems, photocatalytic technology has made remarkable progress in recent years. Organic semiconductor materials offer structural diversity and tunable energy levels and thus attracted great attention. Among them, porphyrin and its derivatives show great potential in photocatalytic reactions and light therapy due to their unique large-π conjugation structure, high apparent quantum efficiency, tailorable functionality, and excellent biocompatibility. Compared to unassembled porphyrin molecules, supramolecular porphyrin assemblies facilitate the solar light absorption and improve the charge transfer and thus exhibit enhanced photocatalytic performance. Herein, the research progress of porphyrin-based supramolecular assemblies, including the construction, the regulation of charge separation and transfer, stability, and application in photocatalysis, was systematically reviewed. The construction strategy of porphyrin supramolecules, the mechanism of charge separation, and the intrinsic relationship of assembling structure-charge transfer-photocatalytic performance received special attention. Surfactants, peptide molecules, polymers, and metal ions were introduced to improve the stability of the porphyrin assemblies. Donor-acceptor structure and co-catalysts were incorporated to inhibit the recombination of the photoinduced charges. These increase the understanding of the porphyrin supramolecules and provide ideas for the design of high-performance porphyrin-based photocatalysts. Full article

The requirement for the development of advanced technologies is the need to create new functional thermostable soluble polysilsesquioxanes. Combining the potential of organosilicon chemistry and the chemistry of heterocyclic compounds is a promising direction for the formation of novel organosilicon polymer systems with new properties and new possibilities for their practical application. Using the classical method of hydrolysis and polycondensation of previously unknown trifunctional (trimethoxysilylpropyl)glutarimide in the presence or absence of an acid or base catalyst, a universal approach to the formation of new thermostable soluble polysilsesquioxanes with glutarimide side-chain groups is proposed, which forms the basis for the synthesis of polysilsesquioxane polymers with different functionality. The weight average molecular weight of silsesquioxanes, determined by gel permeation chromatography, is practically independent of the reaction conditions and is 10–12 kDa; at the same time, the molecular weight distribution remains low and amounts to 1.38–1.47. According to thermogravimetric analysis, the resulting polysiloxanes have high thermal stability up to 335 °C. By the dynamic light scattering method, it was established that in an aqueous solution, silsesquioxane macromolecules are in an associated state, forming supramolecular structures due to the intermolecular interaction of individual macromolecules. The average hydrodynamic diameter of the particles was 46 nm. X-ray diffraction analysis showed the amorphous nature of the polymer. Polymer film coatings based on synthesized silsesquioxanes are characterized by 98% transmission in the visible spectrum and resistance to ultraviolet radiation, which is promising for the creation of functional transparent film coatings. Full article

The spontaneous association of organic ligands and metal ions has given rise to what is known as metallosupramolecular chemistry. This emerging field of chemistry has gathered significant attention due to the numerous supramolecular structures that can be obtained, which have applications in diverse areas, such as materials chemistry, biomedical chemistry, and catalysis, among others. In this context, Schiff base ligands are among the most commonly used ligands for the synthesis of helicates and mesocates. In this study, the Schiff base ligand H₂L was designed, synthesized, and characterized. This ligand is potentially dianionic and tetradentate [N₂O₂], with a long and semiflexible spacer, making it a bicompartmental ligand that promotes the formation of dinuclear helicate compounds. Additionally, the presence of bulky tert-butyl and ethyl groups at specific positions of the skeleton is crucial for enhancing the formation of such structures instead of mesocates. The synthesis was carried out through an imine condensation reaction between two equivalents of 4-(tert-butyl)-2-hydroxybenzaldehyde and one equivalent of 4,4′-methylenebis(2,6-diethylamine) in the presence of p-toluenesulfonic acid monohydrate as a catalyst. The ligand was characterized using standard techniques, and suitable crystals were obtained for study using X-ray diffraction. Full article

Fullerene C₆₀ is by far the most studied of all allotropic modifications of carbon. Chemical modification of the double bond over the years has led to the emergence of a variety of fullerene derivatives. These derivatives have now found numerous applications in medicine, materials and supramolecular chemistry, and as efficient electron acceptors in organic photovoltaic devices. The main method for the functionalization of C₆₀ fullerenes, which makes it possible to obtain its derivatives in a preparative volume, is the Bingel–Hirsch reaction. But this method makes it possible to obtain fullerocyclopropanes containing only carboxyl substituents at the bridging carbon atom. Therefore, in order to obtain new materials, we began to study the interaction with organic carbonates in combination with Grignard reagents in the presence of Ti-containing complex catalysts. We hope that replacing the olefin in the Kulinkovich reaction with a C₆₀ fullerene molecule will lead to new and hard-to-find functionalization products of the latter. Organic carbonates were chosen as the object of study due to the fact that they are used in the industry as solvents for natural and synthetic resins, cellulose ethers, dispersants, blowing agents, emulsifiers, absorbents of hydrogen sulfide and carbon dioxide, starting materials for the industrial synthesis of fibers and plastics, as well as plasticizers, pharmaceuticals and plant protection products. Full article

Circularly polarized luminescence (CPL) materials have been widely used in the fields of bioimaging, optoelectronic devices, and optical communications. The supramolecular interaction, involving harnessing non-covalent interactions between host and guest molecules to control their arrangements and assemblies, represents an advanced approach for facilitating the development of CPL materials and finely constructing and tuning the desired CPL properties. Cyclodextrins (CDs) are cyclic natural polysaccharides, which have also been ubiquitous in various fields such as molecular recognition, drug encapsulation, and catalyst separation. By adjusting the interactions between CDs and guest molecules precisely, composite materials with CPL properties can be facilely generated. This review aims to outline the design strategies and performance of CD-based CPL materials comprehensively and provides a detailed illustration of the interactions between host and guest molecules. Full article

During the preparation of high dilutions, repeated external vibration (shaking) is used. We hypothesized that it was the vibration treatment, and not the negligible content of the initial substance, that underlies the activity of highly diluted preparations. In order to test this, the vibration was separated from the dilution process. After vibrating two tubes together on a vortex mixer (one containing water and the other the initial substance) the electrical conductivity and radio frequency radiation intensity of water differed from the unvibrated control, and the ability to exert a modifying effect on the target solution appeared, as assessed using ELISA and terahertz spectroscopy, appeared. Thus, the properties of the neutral carrier (water) changed after non-contact exposure to the initial substance. We have named this process ‘crossing’ and its products ‘aqueous iterations of the initial substance’. Several aqueous iterations with different physical properties were obtained, some of which have a modifying effect and others cause various chemical (catalytic) and biological (antiviral) effects similar to those of the initial substance. This indicates that during crossing, substances enter into post-vibration supramolecular interactions. At the nanoscale level, aqueous iterations and the initial substance are structurally symmetrical, which allows us to assume that the preservation of the symmetry of substances subjected to vibration treatment is the basis of the post-vibration interaction phenomenon. Full article

The aim of this work was the investigation of novel organocatalysts for the Michael addition of diethyl malonate to β-nitrostyrene. The methodology of the study included NMR titration, reaction monitoring by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS), product characterization by MALDI, IR spectroscopy, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and elemental analysis. As a result, evidence of supramolecular interactions between two pairs of components of the reaction was found. In addition to the supramolecular complexes, an unusual reaction, i.e., the Michael addition of NH-bispidines to β-nitrostyrene, was found, which led to previously unknown oligomers of β-nitrostyrene. A new mechanism for the catalytic action of NH-bispidine was proposed, which involved catalysis not by the initial organocatalyst but rather by its adduct with β-nitrostyrene. Thus, in this reaction, N-benzylbispidine acted as an initiator, and the real catalyst was the betaine formed during the initiation stage. Full article

The peroxidase-like behaviors of gold nanoparticles (AuNPs) have the potential to the development of rapid and sensitive colorimetric assays for specific food ingredients and contaminants. Here, using NaBH₄ as a reducing agent, AuNPs with a supramolecular macrocyclic compound β-cyclodextrin (β-CD) capped were synthesized under alkaline conditions. Monodispersal of β-CD@AuNPs possessed a reduction in diameter size and performed great peroxidase-like activities toward both substrates, H₂O₂ and TMB. In the presence of H₂O₂, the color change of TMB oxidization to oxTMB was well-achieved using β-CD@AuNPs as the catalyst, which was further employed to develop colorimetric assays for ascorbic acid, with a limit of detection as low as 0.2 μM in ddH₂O. With the help of the host-guest interaction between β-CD and adamantane, AuNPs conjugated with nanobodies to exhibit peroxidase-like activities and specific recognition against Salmonella Typhimurium simultaneously. Based on this bifunctional bioprobe, a selective and sensitive one-step colorimetric assay for S. Typhimurium was developed with a linear detection from 8.3 × 10⁴ to 2.6 × 10⁸ CFU/mL and can be provided to spiked lettuce with acceptable recoveries of 97.31% to 103.29%. The results demonstrated that the excellent peroxidase-like behaviors of β-CD@AuNPs can be applied to develop a colorimetric sensing platform in the food industry. Full article

Chiral mono- and bis-(thio)urea supramolecular organocatalysts were studied in the enantioselective vinylogous addition reaction of 2-trimethylsilyloxyfuran (TMSOF) to carbonylic compounds; the corresponding chiral γ-hydroxymethyl-butenolides are obtained in good yields and with high enantiomeric excesses. The catalyst structure, as well as the reaction conditions, strongly influence the efficiency of the reaction. The conformational features of mono(thio)urea catalysts 2 and 3 and bis(thio)urea catalysts 7 and 8 were investigated by DFT calculations along with the structure of their complexes with benzaldehyde. Natural Bond Orbital (NBO) and Non-Covalent Interaction (NCI) calculations provided useful information concerning the activating H-bonding interactions in the complexes. Full article

Bipyridine and related compounds are starting materials or precursors for a variety of valuable substances such as biologically active molecules, ligands for catalysts, photosensitizers, viologens, and supramolecular architectures. Thus, it is important to classify their synthesis methods and understand their characteristics. Representative examples include methods using homo and heterocoupling of pyridine derivatives in the presence of a catalyst. Because bipyridine compounds strongly coordinate with metal centers, a decrease in catalytic activity and yield is often observed in the reaction system. To address this issue, this review provides insights into advances over the last ~30 years in bipyridine synthesis using metal complexes under both homogeneous and heterogeneous conditions. Moreover, strategies for bipyridine synthesis involving sulfur and phosphorous compounds are examined. These alternative pathways offer promising avenues for overcoming the challenges associated with traditional catalysis methods, providing a more comprehensive understanding of the synthesis landscape. Full article